Film and laminate

Abstract

To provide a film which satisfies a desired chromaticity coordinate, has improved visible light transmission and contains a fluorescent dye.SOLUTION: A film contains a polycarbonate resin (A) containing a structural unit (a) derived from a specific dihydroxy compound represented by formula (1), a fluorescent dye (B), and a dye (C) different from the fluorescent dye (B).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a film and a laminate comprising the film. [Background technology]

[0002] Conventionally, films containing fluorescent dyes have been used for marking and the like. In addition to exhibiting a desired color, such films containing fluorescent dyes are required to have improved physical properties such as weather resistance or light resistance. For example, Patent Document 1 discloses a fluorescent retroreflective sheeting having excellent fluorescent appearance and weather resistance durability of the fluorescent color. Patent Document 2 discloses a resin molded product obtained by molding a polycarbonate resin composition that exhibits good color development, has excellent light resistance and transparency, and is also excellent in mechanical strength. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2001-296413 A [Patent Document 2] JP 2017-039947 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, the above-mentioned conventional techniques have not yet achieved a film that satisfies the desired chromaticity coordinates and has an improved visible light transmittance, and further development of films is desired.

[0005] An object of one aspect of the present invention is to provide a film or the like containing a fluorescent dye that satisfies desired chromaticity coordinates and has improved visible light transmittance. [Means for solving the problem]

[0006] As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by a film made of a resin composition containing a polycarbonate resin containing a specific structural unit, a fluorescent dye, and a dye different from the fluorescent dye, and have achieved the present invention.

[0007] [1] A polycarbonate resin (A) containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1), A fluorescent dye (B); A film made of a resin composition containing the fluorescent dye (B) and a dye (C) different from the fluorescent dye (B). [ka] [2] The film according to [1], wherein the content of the dye (C) is 0.1 to 5.0 parts by mass per 100 parts by mass of the polycarbonate resin (A). [3] The film according to [1] or [2], wherein the dye (C) comprises at least one dye selected from the group consisting of anthraquinone dyes, quinoline dyes, azo dyes and methine dyes. [4] The film according to any one of [1] to [3], wherein the dye (C) is a yellow dye. [5] The film according to any one of [1] to [4], wherein the dye (C) is CI Solvent Yellow 163. [6] The film according to any one of [1] to [5], wherein the fluorescent dye (B) includes at least one dye selected from the group consisting of thioxanthene-based dyes, thioindigoid-based dyes, anthraquinone-based dyes, benzoxazole coumarin-based dyes, perylene-based dyes, perylene imide-based dyes, benzopyran-based dyes, anthracene-based dyes, and isoquinoline-based dyes. [7] The film according to any one of [1] to [6], wherein the content of the fluorescent dye (B) is 0.1 to 4.0 parts by mass per 100 parts by mass of the polycarbonate resin (A).[8] The film according to any one of [1] to [7], wherein the polycarbonate resin (A) further contains a structural unit (b) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, and ether-containing dihydroxy compounds. [9] The film according to any one of [1] to [8], whose chromaticity coordinates (x, y) in the XYZ color system are within the range enclosed by the straight lines sequentially connecting each of the four points: (0.583, 0.416), (0.535, 0.400), (0.642, 0.305), and (0.692, 0.309).

[10] A laminate comprising the film according to any one of [1] to [9] and a retroreflective sheet.

[11] The laminate described in

[10] , wherein the retroreflective sheet has a two or more layer structure including at least a substrate and a retroreflective element layer, and the retroreflective element layer is provided with spherical lenses or prisms. Effect of the Invention

[0008] According to one aspect of the present invention, it is possible to provide a film containing a fluorescent dye, which satisfies desired chromaticity coordinates and has improved visible light transmittance. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a diagram illustrating a layer structure of an example of a laminate according to an embodiment of the present invention. [Diagram 2] FIG. 1 is a diagram showing the chromaticity of laminates of Examples and Comparative Examples before an exposure test. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, one embodiment of the present invention will be described in detail. In this specification, the symbol "to" means a range including both ends of the symbol.

[0011] 〔film〕 A film according to one embodiment of the present invention is made of a resin composition containing a polycarbonate resin (A), a fluorescent dye (B), and a dye (C) different from the fluorescent dye (B).

[0012] [Resin composition] [Polycarbonate resin (A)] The polycarbonate resin (A) contains a structural unit (a) derived from a dihydroxy compound represented by the following formula (1).

[0013] [ka]

[0014] In this specification, the term "structural unit" refers to a partial structure constituting a resin, and a specific partial structure contained in the repeating structural unit of the resin. For example, it is a partial structure sandwiched between adjacent linking groups in a resin, or a partial structure sandwiched between a polymerizable reactive group present at the terminal portion of a polymer and a linking group adjacent to the polymerizable reactive group. More specifically, in the case of polycarbonate resin (A), a carbonyl group is a linking group, and it is a partial structure sandwiched between adjacent carbonyl groups.

[0015] <Structural unit (a)> The dihydroxy compound represented by formula (1) includes isosorbide, isomannide and isoidet. These are stereoisomers of each other. The dihydroxy compound may be one of these stereoisomers or more. Among them, isosorbide obtained by dehydration condensation of sorbitol produced from various starches, which are abundant and easily available as a plant-derived resource, is most preferred from the viewpoints of availability and ease of production, moldability, and properties of the obtained molded product (for example, heat resistance, impact resistance, surface hardness and carbon neutrality).

[0016] <Structural unit (b)> The polycarbonate resin (A) may further contain other structural units within the range in which the effects of the present invention can be obtained. For example, the polycarbonate resin (A) may further contain a structural unit (b) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, and ether-containing dihydroxy compounds.

[0017] The dihydroxy compounds from which the structural unit (b) is derived all have flexible molecular structures. It is preferable that the polycarbonate resin (A) is a copolymer polycarbonate resin containing the structural unit (a) and the structural unit (b) from the viewpoint of improving the chemical resistance of the polycarbonate resin (A). From this viewpoint, the dihydroxy compound from which the structural unit (b) is derived is more preferably an aliphatic hydrocarbon dihydroxy compound and an alicyclic hydrocarbon dihydroxy compound, and even more preferably an alicyclic hydrocarbon dihydroxy compound.

[0018] Examples of the aliphatic hydrocarbon dihydroxy compound include linear aliphatic dihydroxy compounds and branched aliphatic dihydroxy compounds. Examples of linear aliphatic dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol. Examples of branched aliphatic dihydroxy compounds include 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol.

[0019] Examples of alicyclic hydrocarbon dihydroxy compounds include dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons, and dihydroxy compounds which are secondary or tertiary alcohols of alicyclic hydrocarbons. Examples of dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons include dihydroxy compounds derived from terpene compounds. Examples of the terpene compounds include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol and limonene. Examples of the dihydroxy compound which is a secondary or tertiary alcohol of an alicyclic hydrocarbon include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0020] Examples of the ether-containing dihydroxy compound include oxyalkylene glycols, such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.

[0021] The dihydroxy compound from which the structural unit (b) is derived is preferably 1,4-cyclohexanedimethanol or tricyclodecane dimethanol, and more preferably 1,4-cyclohexanedimethanol. For example, when the dihydroxy compound from which the structural unit (b) is derived is 1,4-cyclohexanedimethanol, the good polymerization reactivity of 1,4-cyclohexanedimethanol makes it easier to obtain a high molecular weight polycarbonate resin (A). In addition, when the dihydroxy compound from which the structural unit (b) is derived is 1,4-cyclohexanedimethanol, a polycarbonate resin (A) having extremely excellent mechanical properties such as impact resistance can be obtained, and the warpage suppression effect in the laminate described below is more fully exhibited.

[0022] In addition, both the dihydroxy compound represented by formula (1) and the dihydroxy compound from which the structural unit (b) is derived may contain a stabilizer in order to further improve the quality of the resin composition. Examples of the stabilizer include reducing agents, antioxidants, oxygen scavengers, light stabilizers, antacids, pH stabilizers, and heat stabilizers. In particular, the dihydroxy compound represented by formula (1) has a property of being easily altered under acidic conditions. Therefore, it is preferable to use a basic stabilizer in the production process of the polycarbonate resin (A) in order to suppress the alteration of the dihydroxy compound in the production process.

[0023] <Other structural units> Examples of other structural units that may be included in the polycarbonate resin (A) include structural units derived from dihydroxy compounds containing aromatic groups such as bisphenol compounds, structural units derived from dicarboxylic acid compounds, and structural units derived from diester compounds.Polycarbonate resins partially incorporating structural units derived from diester compounds are also called polyestercarbonate resins.The polycarbonate resin (A) may include such polyestercarbonate resins.

[0024] For example, it is preferable that the polycarbonate resin (A) further contains a structural unit derived from a dihydroxy compound containing an aromatic group or a structural unit derived from a dicarboxylic acid compound from the viewpoint of enhancing the heat resistance of the polycarbonate resin (A). From such a viewpoint, the amount of these structural units in the polycarbonate resin (A) is preferably 10% by mass or less, more preferably 5% by mass or less.

[0025] <Ratio of structural units (a) and (b)> The ratio of the structural unit (a) and the structural unit (b) in the polycarbonate resin (A) is preferably within a range of 40 / 60 to 90 / 10 from the viewpoint of sufficiently enhancing the physical properties of the resin composition. The ratio referred to here is the molar ratio of the structural unit (a) to the structural unit (b) (structural unit (a) / structural unit (b)). The molar ratio being within the above range is suitable from the viewpoint of realizing a resin composition having sufficient heat resistance, mechanical properties, and moldability in practical use, and further having sufficient moist heat resistance and chemical resistance. Furthermore, it is also preferable from the viewpoint of suppressing fading of the resin composition over time. From this viewpoint, the molar ratio is more preferably 42 / 58 or more, and even more preferably 45 / 55 or more. From the same viewpoint, the molar ratio is more preferably 85 / 15 or less, and even more preferably 80 / 20 or less.

[0026] <Weight average molecular weight (Mw)> The weight average molecular weight of the polycarbonate resin (A) is preferably 20,000 or more, more preferably 25,000 or more, and even more preferably 30,000 or more, from the viewpoint of improving impact resistance, chemical resistance, and moist heat resistance. The weight average molecular weight of the polycarbonate resin (A) is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 60,000 or less, from the viewpoint of exhibiting good fluidity during production of the resin composition and film.

[0027] The weight average molecular weight of the polycarbonate resin (A) is a value calculated as a standard polystyrene equivalent, measured by gel permeation chromatography (GPC) under the following GPC measurement conditions. The weight average molecular weight of the polycarbonate resin (A) can be adjusted, for example, by the amount of polymerization catalyst used during the production of the polycarbonate resin (A). (GPC measurement conditions) Equipment used: Tosoh Corporation HLC-8320GPC system Column: 2 TGKgel SuperHZM-H (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Column temperature: 40℃ Detector: Refractive index (RI)

[0028] <Glass transition temperature (Tg)> The glass transition temperature (hereinafter also referred to as "Tg") of the polycarbonate resin (A) is preferably 90°C or higher, more preferably 92°C or higher, and even more preferably 95°C or higher, from the viewpoint of sufficiently increasing the heat resistance of the resin composition. Moreover, the glass transition temperature of the polycarbonate resin (A) is preferably 150°C or lower, more preferably 145°C or lower, and even more preferably 140°C or lower, from the viewpoint of ease of molding and processing of the resin composition.

[0029] The glass transition temperature of the polycarbonate resin (A) is a value calculated from the FOX formula using the values ​​described in Polymer Handbook (J. Brandrup, Interscience, 1989). The Tg of the polycarbonate resin (A) can be adjusted, for example, by changing the type of dihydroxy compound or the ratio of structural units derived therefrom.

[0030] <Manufacturing method> The polycarbonate resin (A) can be synthesized by polycondensing the above-mentioned dihydroxy compound and carbonic acid diester through an ester exchange reaction. Along with the polycondensation, the monohydroxy compound and the like that are by-produced in the ester exchange reaction are removed from the system. The polycarbonate resin (A) may be a commercially available product.

[0031] The carbonic acid diester used as a raw material in the synthesis of the polycarbonate resin (A) may be one or more kinds. Examples of the carbonic acid diester include diphenyl carbonate (DPC), substituted diphenyl carbonate such as ditolyl carbonate, and alkyl carbonate such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate. Among these carbonic acid diesters, diphenyl carbonate or substituted diphenyl carbonate is preferred, and diphenyl carbonate is more preferred.

[0032] [Fluorescent dye (B)] The fluorescent dye (B) can be appropriately selected from known fluorescent dyes depending on the application of the resin composition. For example, when the above-mentioned resin composition is used for the skin material on the retroreflective sheet in the retroreflective member, the fluorescent dye (B) can be appropriately selected from known fluorescent dyes in consideration of the chromaticity coordinates (x, y) required for the retroreflective member. The fluorescent dye (B) may be one or more kinds. The retroreflective member is a member having a retroreflective sheet and a skin material having a desired color that is arranged on top of the retroreflective sheet, and corresponds to the laminate described below.

[0033] The fluorescent dye (B) preferably contains at least one dye selected from the group consisting of thioxanthene dyes, thioindigoid dyes, anthraquinone dyes, benzoxazole coumarin dyes, perylene dyes, perylene imide dyes, benzopyran dyes, anthracene dyes, and isoquinoline dyes, because these dyes have excellent transparency and hue.

[0034] The thioxanthene dye means a dye containing a compound having a thioxanthene skeleton in the molecule. The thioindigoid dye means a dye containing a compound having a thioindigo skeleton in the molecule. The anthraquinone dye means a dye containing a compound having an anthraquinone skeleton in the molecule. The benzoxazole coumarin dye means a dye containing a compound having a 3-(benzoxazol-2-yl)coumarin skeleton in the molecule. The perylene dye means a dye containing a compound having a perylene skeleton in the molecule. However, those corresponding to the perylene imide dyes described below are excluded. The perylene imide dye means a dye containing a compound having a perylene tetracarboxydiimide skeleton in the molecule. The benzopyran dye means a dye containing a compound having a benzopyran skeleton in the molecule. However, those corresponding to the benzoxazole coumarin dyes described above are excluded. The anthracene dye means a dye containing a compound having an anthracene skeleton in the molecule. The isoquinoline dye means a dye containing a compound having an isoquinoline skeleton in the molecule.

[0035] When the resin composition is used as a skin material in a retroreflective member, the fluorescent dye (B) preferably contains either or both of a yellow fluorescent dye and a red fluorescent dye from the viewpoint of realizing a suitable chromaticity coordinate (x, y) for such an application. In another embodiment, the fluorescent dye (B) preferably contains either or both of a yellow fluorescent dye and a red fluorescent dye from the viewpoint described above, and does not contain any other fluorescent dye. The yellow fluorescent dye means a fluorescent dye whose hue is yellow in the color index name. The red fluorescent dye means a fluorescent dye whose hue is red in the color index name.

[0036] Commercially available products can be used as the fluorescent dye (B). Commercially available examples of the fluorescent dye (B) include CI Solvent Yellow 98 (DYMIC MBR D-70, manufactured by Dainichi Seika Chemicals Mfg. Co., Ltd.) for thioxanthene dyes, CI Solvent Orange 63 (DYMIC MBR D-74, manufactured by Dainichi Seika Chemicals Mfg. Co., Ltd.) for anthraquinone dyes, and CI Solvent Orange 83 (DYMIC MBR D-74, manufactured by Dainichi Seika Chemicals Mfg. Co., Ltd.) for perylene dyes. Examples of suitable dyes include BASF's Lumogen F Orange 240 and Lumogen F Red 305 peryleneimide dyes, CI Solvent Red 197 (Dainichi Seika Color & Chemicals Mfg. Co., Ltd.'s DYMIC MBR D-75), CI Solvent Red 196 (Dainichi Seika Color & Chemicals Mfg. Co., Ltd.'s DYMIC MBR D-77), and CI Solvent Yellow 104 (Dainichi Seika Color & Chemicals Mfg. Co., Ltd.'s DYMIC MBR D-71).

[0037] The content of the fluorescent dye (B) in the resin composition of one embodiment of the present invention is preferably 0.1 parts by mass or more, more preferably 0.15 parts by mass or more, and even more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin (A), from the viewpoint of enhancing color development and visibility in the resin composition. The content of the fluorescent dye (B) in the resin composition is preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, more preferably 3.5 parts by mass or less, even more preferably 3.0 parts by mass or less, and particularly preferably 2.0 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A), from the viewpoint of suppressing fading of the resin composition and enhancing weather resistance.

[0038] [Dye (C)] The dye (C) is a dye different from the fluorescent dye (B). For example, when the film according to one embodiment of the present invention is used as a skin material on a retroreflective sheet in a retroreflective member, the dye (C) can be appropriately selected from known dyes in consideration of the chromaticity coordinates (x, y) required for the retroreflective member. The dye (C) may be one or more kinds.

[0039] The dye (C) preferably contains at least one dye selected from the group consisting of anthraquinone dyes, quinoline dyes, azo dyes and methine dyes, because these dyes have excellent transparency and hue.

[0040] Examples of anthraquinone dyes that can be used as the dye (C) include CISolvent Includes Yellow 163.

[0041] Commercially available examples of CISolvent Yellow 163 include "DYMIC MBR D-05 Yellow" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. and "Oracet (registered trademark) Yellow GHS" manufactured by BASF.

[0042] Examples of anthraquinone dyes include CI Disperse Red 22, CI Disperse Red 57, CI Disperse Red 60, CI Solvent Red 4, CI Solvent Red 9, CI Solvent Red 11, CI Solvent Red 15, CI Solvent Red 52, CI Solvent Red 111, CI Solvent Red 168, and CI Solvent Red 207.

[0043] Quinoline dyes refer to dyes containing compounds with a quinoline skeleton in the molecule. Examples of quinoline dyes include dyes commercially available under the color indexes CI Solvent Yellow 33, CI Solvent Yellow 98, CI Solvent Yellow 157, CI Disperse Yellow 54, and CI Disperse Yellow 160.

[0044] Azo dyes refer to dyes containing compounds with an azo skeleton in the molecule. Examples of azo dyes include dyes that are commercially available under the color indexes Solvent Yellow 14, Solvent Yellow 16, Solvent Yellow 21, Solvent Yellow 61, Solvent Yellow 81, Solvent Red 23, Solvent Red 24, Solvent Red 27, Solvent Red 8, Solvent Red 83, Solvent Red 84, Solvent Red 121, Solvent Red 132, Solvent Violet 21, Solvent Black 21, Solvent Black 23, Solvent Black 27, Solvent Black 28, Solvent Black 31, Solvent Orange 37, Solvent Orange 40, and Solvent Orange 45.

[0045] Methine dyes refer to dyes containing compounds with a methine skeleton in the molecule. Examples of methine dyes include dyes commercially available under the color indexes CI Solvent Orange 80 and CI Solvent Yellow 93.

[0046] When the film according to one embodiment of the present invention is used as a skin material in a retroreflective member, the dye (C) is preferably a yellow dye, more preferably CI Solvent Yellow 163, from the viewpoint of realizing suitable chromaticity coordinates (x, y) for such an application. The yellow dye means a dye whose hue is yellow according to the Color Index name.

[0047] The content of the dye (C) in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of the polycarbonate resin (A) from the viewpoint of suppressing the change in the hue of the resin composition under an exposure environment and from the viewpoint of improving weather resistance. Also, the content of the dye (C) in the resin composition is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 2.0 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A) from the viewpoint of the vividness of the fluorescent color due to the fluorescent dye (B).

[0048] The total content of the fluorescent dye (B) and the dye (C) in the resin composition is preferably 1.5 parts by mass or more, more preferably 2.0 parts by mass or more, based on 100 parts by mass of the polycarbonate resin (A), from the viewpoint of easily coloring the resin composition to the color of the desired chromaticity coordinates (x, y). Also, the total content of the fluorescent dye (B) and the dye (C) in the resin composition is preferably 10.0 parts by mass or less, more preferably 7.0 parts by mass or less, and even more preferably 5.0 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (A), from the viewpoint of maintaining the transparency of the resin composition in the film.

[0049] The resin composition may contain other components in addition to the polycarbonate resin (A), the fluorescent dye (B), and the dye (C), such as a pigment (C'), a light stabilizer (D), an ultraviolet absorber (E), an antioxidant (F), or an additive (G).

[0050] [Pigment (C')] The resin composition may further contain a pigment (C') from the viewpoint of easily coloring the resin composition to a color of a desired chromaticity coordinate (x, y). A known compound can be used as the pigment (C'). The pigment (C') may be one or more kinds.

[0051] The pigment (C') is preferably selected from a white pigment, a yellow pigment, a red pigment, and an orange pigment, and from the viewpoint of visible light transmittance, it is preferable to use a white pigment.

[0052] An example of a commercially available white pigment is "DYMIC MBR 002 White" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.

[0053] The content of the pigment (C') in the resin composition is preferably 0.2 parts by mass or more, more preferably 0.4 parts by mass or more, based on 100 parts by mass of the polycarbonate resin (A) from the viewpoint of weather resistance, while being 1.0 part by mass or less, more preferably 0.8 part by mass or less, from the viewpoint of visible light transmittance.

[0054] [Light stabilizer (D)] The resin composition may further contain a light stabilizer (D) from the viewpoint of improving the light stability of the resin composition. The light stabilizer (D) may be a compound known as a light stabilizer. The light stabilizer (D) may be one or more kinds.

[0055] From the viewpoint of suppressing bleeding, the molecular weight of the light stabilizer (D) is preferably 500 or more, more preferably 700 or more, and even more preferably 1000 or more. From the viewpoint of dispersibility of the light stabilizer (D), the molecular weight of the light stabilizer (D) is preferably 4000 or less, more preferably 3800 or less, and even more preferably 3500 or less.

[0056] The light stabilizer (D) is preferably a hindered amine light stabilizer from the viewpoint of maintaining the transparency of the resin composition and suppressing deterioration of the resin. The hindered amine light stabilizer is a compound in which each of the two carbon atoms adjacent to the nitrogen atom in the piperidine ring has a plurality of substituents that exhibit steric hindrance. Examples of the substituents that exhibit steric hindrance include a methyl group. Examples of the hindered amine light stabilizer include a compound having a 2,2,6,6-tetramethyl-4-piperidyl group and a compound having a 1,2,2,6,6-pentamethyl-4-piperidyl group.

[0057] Examples of commercially available hindered amine light stabilizers or compositions containing the same include Chimassorb (registered trademark) 119FL, 2020FDL, 944FD, 944LD, Tinuvin (registered trademark) 622LD, 123S, 144, 765, 770, 770DF, 770FL, 111FD, 123, 292 manufactured by BASF, Sanol (registered trademark) LS-770, LS-765, LS-292, LS-2626, LS-744, LS-440 manufactured by Sankyo Co., Ltd., and Adeka STAB (registered trademark) LA-52, LA-57, LA-62, LA-63P, LA-68, LA-81, LA-82 and LA-87 (all trade names) manufactured by ADEKA Corporation.

[0058] The content of the light stabilizer (D) in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.15 parts by mass or more, and even more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin (A), from the viewpoint of improving the weather resistance of the resin composition. Also, the content of the light stabilizer (D) in the resin composition is preferably 3.0 parts by mass or less, more preferably 1.5 parts by mass or less, and even more preferably 1.0 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A), from the viewpoint of suppressing the production cost of the resin composition.

[0059] [Ultraviolet absorber (E)] From the viewpoint of improving weather resistance, the resin composition preferably further contains an ultraviolet absorber (E). The ultraviolet absorber may be one or more kinds. From the viewpoint of suppressing staining of a mold during molding of the resin composition, the molecular weight of the ultraviolet absorber is preferably 300 or more, more preferably 400 or more. The molecular weight of the ultraviolet absorber is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1000 or less, more preferably 800 or less.

[0060] Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers. Commercially available examples of benzotriazole-based ultraviolet absorbers include Tinuvin 234 manufactured by BASF and Adeka STAB LA-31 manufactured by ADEKA (both trade names). Commercially available examples of triazine-based ultraviolet absorbers include Tinuvin 1577, 1600 manufactured by BASF and Adeka STAB LA-F70 manufactured by ADEKA (both trade names).

[0061] The content of the ultraviolet absorber in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin (A), from the viewpoint of improving the weather resistance of the resin composition. Also, the content of the ultraviolet absorber in the resin composition is preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A), from the viewpoint of suppressing the production cost of the resin composition.

[0062] [Antioxidants (F)] The resin composition preferably further contains an antioxidant from the viewpoint of suppressing coloration accompanying molding of the resin composition, for example, thermal coloration when molding the resin composition into pellets or a film. The antioxidant can be appropriately selected from compounds known as antioxidants, and may be one or more kinds.

[0063] Preferred examples of the antioxidant include phenolic antioxidants, and examples of the phenolic antioxidant include hindered phenolic compounds. Hindered phenolic compounds have a bulky group at the ortho position of the hydroxyl group of the phenolic compound. As a result, the properties of the phenolic hydroxyl group are not expressed or are suppressed from being expressed.

[0064] Commercially available examples of antioxidants or compositions containing the same include Irganox® 1010, 1076, 1098, 245, and 3114 manufactured by BASF, and Adeka STAB AO-20, AO-50, AO-60, AO-80, and AO-330 (all of which are trade names) manufactured by ADEKA.

[0065] The content of the antioxidant in the resin composition is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.03 parts by mass or more, per 100 parts by mass of the polycarbonate resin (A), from the viewpoint of coloring due to molding of the resin composition. Also, the content of the antioxidant in the resin composition is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, and even more preferably 1.0 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A), from the viewpoint of suppressing the production cost of the resin composition.

[0066] [Additive (G)] Examples of the additive (G) include heat stabilizers, fillers such as fillers, neutralizing agents, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity imparting agents, crosslinking agents, crosslinking assistants, metal deactivators, molecular weight regulators, antibacterial agents, antifungal materials, fluorescent brightening agents, and light diffusing agents such as organic diffusing agents or inorganic diffusing agents.

[0067] The resin composition may further contain other resins other than the polycarbonate resin (A) within the range in which the effects of the present invention can be obtained. Examples of the other resins include synthetic resins, elastomers, and biodegradable resins. Examples of the synthetic resins include aromatic polyesters, aliphatic polyesters, polyamides, polystyrenes, polyolefins, amorphous polyolefins, acrylonitrile-butadiene-styrene copolymers (ABS resins), and acrylonitrile-styrene copolymers (AS resins). Examples of the elastomers include acrylic rubbers and butadiene rubbers. Examples of the biodegradable resins include polylactic acid and polybutylene succinate. The other resins may be kneaded with the polycarbonate resin (A). That is, the resin composition may be a polymer alloy.

[0068] [Method of producing resin composition] The resin composition can be produced by a method of mechanically melt-kneading the materials of the resin composition described above. Examples of melt-kneading machines used for the melt-kneading include a single-screw extruder, a twin-screw extruder, a Brabender, a Banbury mixer, a kneader blender, and a roll mill. When kneading, each material of the resin composition may be kneaded at once, or after kneading an arbitrary part of the components, the remaining components may be added and kneaded. The latter is preferable from the viewpoint of suppressing color unevenness of the resin composition, particularly color unevenness in a film when a film is formed from the resin composition. In addition, a method of obtaining a resin composition by continuously feeding each material of the resin composition into a twin-screw extruder equipped with a vacuum vent and melt-kneading the materials is preferable from the viewpoint of productivity and quality uniformity.

[0069] The kneading temperature in the melt kneading is usually 150° C. or higher, preferably 180° C. or higher, and more preferably 200° C. or higher. The kneading temperature is usually 280° C. or lower, preferably 260° C. or lower, and more preferably 250° C. or lower. The kneading temperature in this range is preferable from the viewpoint of suppressing thermal deterioration of the polycarbonate resin (A) during kneading and from the viewpoint of suppressing coloration or deterioration of the mechanical properties of the resin composition.

[0070] Suitable examples of the shape of the resin composition include a lump shape, a powder shape and a pellet shape. The shape of the resin composition is preferably a pellet shape because the resin composition is easy to handle.

[0071] A film according to one embodiment of the present invention, which is made of a resin composition containing polycarbonate resin (A), fluorescent dye (B), and dye (C), has a complementary color due to dye (C), thereby satisfying the desired chromaticity coordinates and improving the visible light transmittance.

[0072] [Film thickness] From the viewpoint of excellent handleability, the thickness of the film is preferably from 10 to 500 μm, and more preferably from 30 to 200 μm.

[0073] [Film Color] When the film is used as the skin material, the chromaticity coordinates (x, y) in the XYZ color system required for the retroreflective member are, for example, the following ranges of chromaticity coordinates for yellow-green, yellow, and orange disclosed in ASTM D4956. It is preferable that the film satisfies any of the ranges of chromaticity coordinates (x, y) as required.

[0074] The range of chromaticity coordinates for fluorescent yellow-green is the range enclosed by the straight lines connecting the four points (0.387, 0.610), (0.369, 0.546), (0.428, 0.496), and (0.460, 0.540), in order.

[0075] The range of chromaticity coordinates for fluorescent yellow is the range enclosed by the straight lines connecting, in order, the four points (0.479, 0.520), (0.446, 0.483), (0.512, 0.421), and (0.557, 0.442).

[0076] The range of chromaticity coordinates for orange (Fluorescent Orange) is the range enclosed by the straight lines connecting, in order, the four points (0.583, 0.416), (0.535, 0.400), (0.595, 0.351), and (0.645, 0.355).

[0077] From the viewpoint of enhancing the visibility of the retroreflective member, the chromaticity coordinates (x, y) of the film in the XYZ color system are preferably within the range surrounded by the straight lines sequentially connecting the four points (0.583, 0.416), (0.535, 0.400), (0.642, 0.305), and (0.692, 0.309). When the chromaticity coordinates of the film are within the above range, the retroreflective member having the film exhibits a fluorescent orange color, and is suitable for retroreflective members that require high visibility, such as construction signs.

[0078] From the above viewpoint, it is more preferable that the chromaticity coordinates (x, y) of the film in the XYZ color system be within the range surrounded by straight lines sequentially connecting the four points (0.583, 0.416), (0.535, 0.400), (0.614, 0.330), and (0.662, 0.338), and it is even more preferable that the chromaticity coordinates be within the range surrounded by straight lines sequentially connecting the four points (0.609, 0.390), (0.558, 0.380), (0.614, 0.330), and (0.662, 0.338).

[0079] The Y value ("visual reflectance" or "stimulus value") of the film in the XYZ color system is preferably 10 or more, more preferably 15 or more, from the viewpoint of realizing good reflective performance when used in a retroreflective member. Moreover, the Y value is preferably 40 or less, from the viewpoint of realizing good visibility when used in a retroreflective member.

[0080] The chromaticity coordinates and Y value of the film can be appropriately determined from the measured values ​​of the film's spectral reflectance spectrum. The chromaticity coordinates of the film can be adjusted by the types of fluorescent dye (B) and dye (C). The Y value of the film can be increased by increasing the content of a bright dye, such as yellow.

[0081] [Film Haze] The haze of the film is preferably 5% or more, more preferably 8% or more, from the viewpoint of realizing a good appearance when used as a retroreflective member, and is preferably 40% or less, more preferably 30% or less, from the viewpoint of realizing good visibility when used as a retroreflective member.

[0082] The haze of the film can be determined according to JIS K7136: 2000. The haze of the film can be adjusted by changing the content of the dye or the ratio of the yellow dye to the red dye.

[0083] [Film visible light transmittance] The visible light transmittance of the film is preferably 20% or more, more preferably 25% or more, from the viewpoint of realizing a good appearance when used as a retroreflective member. The visible light transmittance of the film is preferably 31% or less, more preferably 30% or less, from the viewpoint of realizing a good appearance when used as a retroreflective member. The lower limit of the visible light wavelength range is 360 to 400 nm, and the upper limit is 760 to 830 nm.

[0084] The visible light transmittance of the film can be determined by measuring the transmittance of the film at 380 to 780 nm and calculating the visible light transmittance and visible light reflectance according to the calculation method of JIS R3106:2019.

[0085] [Film manufacturing method] The film can be produced by molding the resin composition by a known molding method. Examples of the molding method include melt extrusion and calendaring, and examples of the melt extrusion method include melt casting, T-die and inflation methods. The molding method of the film from the resin composition is preferably the T-die method because it is economically advantageous.

[0086] [Laminate] A laminate according to one embodiment of the present invention is a laminate having the above-mentioned film and a retroreflective sheet. The laminate is, for example, the above-mentioned retroreflective member in which a film is arranged as a surface material of the retroreflective sheet. The retroreflective sheet may include retroreflective elements composed of a minute repeating structure that provides retroreflection. Examples of a retroreflective element layer including retroreflective elements include spherical lenses and prisms. It is preferable that the retroreflective element layer includes spherical lenses or prisms from the viewpoint of enhancing the retroreflectivity of the retroreflective element layer. The retroreflective element layer may have a binder layer for holding the spherical lenses or prisms or for adhering to the surface material. Examples of the binder layer include a layer of a thermoplastic resin.

[0087] The retroreflective sheet may be composed of only the retroreflective elements, or may further include other structures. For example, when a film can be formed into a laminate by forming prisms on its surface, the side on which the prisms are not formed becomes the front side of the prism-type retroreflective sheet, and the side on which the prisms are formed becomes the retroreflective elements.

[0088] There are various types of retroreflective sheeting, and the retroreflective sheeting may be of any type. Examples of retroreflective sheeting include encapsulated lens type retroreflective sheeting, encapsulated type retroreflective sheeting, and prism type retroreflective sheeting.

[0089] It is preferable that the retroreflective sheet has a two-layer structure including at least a substrate and a retroreflective element layer from the viewpoints of improving strength, dimensional stability, waterproofness, and chemical resistance. The form of the substrate is not limited, and may be a sheet or various forms such as a plate. Examples of materials constituting the substrate include resin, fiber, cloth, and thin metal sheets such as stainless steel and aluminum. The material may be one or more types.

[0090] The laminate may further have other configurations other than those described above within the scope in which the effects of the present invention can be obtained. Examples of other configurations include an adhesive layer and a release material layer. The adhesive layer may be a layer that is interposed between the substrate and the retroreflective element layer to bond them together, or may be a layer that is interposed between the film and the retroreflective element layer to bond them together. The release material layer is a layer for protecting the adhesive surface of the adhesive layer, and may be composed of a sheet that can be adhered to and peeled off from the adhesive layer, such as a release sheet or a resin film. The adhesive that constitutes the adhesive layer and the release material that constitutes the release agent layer can be appropriately selected from known ones.

[0091] [Specific aspects] Fig. 1 is a diagram showing a schematic layer structure of an example of a laminate according to an embodiment of the present invention. The laminate shown in Fig. 1 shows an example of a prism-type retroreflective sheet. As shown in Fig. 1, the laminate 10 is formed by stacking a film 11, a retroreflective element layer 12, and a substrate 13 in this order.

[0092] The film 11 is a film according to one embodiment of the present invention described above. The film 11 is a film manufactured by the T-die method using a pellet-shaped resin composition obtained by melt-kneading polycarbonate resin (A), fluorescent dye (B), dye (C) and any additives. The film 11 has chromaticity coordinates (x, y) within a range surrounded by straight lines sequentially connecting four points (0.583, 0.416), (0.535, 0.400), (0.642, 0.305) and (0.692, 0.309) in the XYZ color system described above, and exhibits fluorescent orange.

[0093] The retroreflective element layer 12 is composed of prisms formed into a cone-like or corrugated shape by heat pressing on one side of the film 11, and a space formed between the prisms and the base material 13 by partial adhesion between the two. The partial adhesion between the prisms and the base material 13 is achieved, for example, by heating a grid-like portion on the surface of the base material 13 and heat fusing the prisms of the retroreflective element layer 12 and the grid-like heat-melted portions of the base material 13 together.

[0094] The substrate 13 is a plate-shaped resin member. For example, from the viewpoint of achieving both weight reduction and strength, the substrate 13 has a plurality of grid-like sections formed by intersecting a plurality of concave stripes extending in the vertical and horizontal directions on the side of the retroreflective element layer 12. The concave stripes are adhesive parts for bonding to the prisms. EXAMPLES

[0095] An embodiment of the present invention will now be described.

[0096] [Preparation of resin material] The abbreviations and manufacturers of the compounds used in the following Production Examples and Examples are as follows.

[0097] [Polycarbonate resin] (Abbreviations, etc.) A-1: Isosorbide polycarbonate resin (Mitsubishi Chemical Corporation DURABIO D5380R (ISB / CHDM=50 / 50 (molar ratio)) A-2: Bisphenol-based polycarbonate resin (Mitsubishi Engineering Plastics Corporation, Iupilon S-3000F) [Dihydroxy compounds] (Abbreviation) ISB: Isosorbide CHDM: 1,4-Cyclohexanedimethanol

[0098] The weight average molecular weight Mw of A-1 was 55,000. The weight average molecular weight of A-1 was measured by gel permeation chromatography (GPC) under the following GPC measurement conditions. The weight average molecular weight Mw of A-1 is a value calculated in terms of standard polystyrene in the following measurement. (GPC measurement conditions) Equipment used: Tosoh Corporation HLC-8320GPC system Column: 2 TGKgel SuperHZM-H (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Column temperature: 40℃ Detector: Refractive index (RI)

[0099] The glass transition temperature Tg of A-1 was 100° C. The glass transition temperature was calculated from the FOX formula using the values ​​given in the Polymer Handbook (J. Brandrup, Interscience, 1989).

[0100] Production examples of resin compositions will be described below. The abbreviations and manufacturers in the production examples are as follows. (Abbreviations, etc.) Fluorescent dye B-1: DYMIC MBR D-77 Red, manufactured by Dainichiseika Color & Chemicals Co., Ltd. Fluorescent dye B-2: DYMIC MBR D-71 Yellow, manufactured by Dainichiseika Color & Chemicals Co., Ltd. Dye C-1: Manufactured by Dainichiseika Chemical Co., Ltd., DYMIC MBR D-05 Yellow Pigment C'-1: DYMIC MBR 002 White, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. Light stabilizer D-1: hindered amine light stabilizer, manufactured by BASF, Chimassorb(R) 2020FDL UV absorber E-1: Benzotriazole UV absorber, manufactured by ADEKA, Adeka STAB LA-31RG Antioxidant F-1: Hindered phenol antioxidant, manufactured by BASF, Irganox 1076

[0101] Example 1 The following components in the amounts shown below were mixed using a Henschel mixer to obtain a resin composition 1. A-1 100 copies E-1 1.875 copies D-1 0.3 parts F-1 0.1 part B-1 0.12 parts B-2 0.2 parts C-1 0.5 part C'-1 0.6 part

[0102] Resin composition 1 was fed to a degassing twin-screw kneading extruder (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) heated to 240°C and kneaded to obtain pellets 1 of resin composition 1. Pellets 1 were fed into a 30 mmφ (diameter) non-vent screw extruder (L / D=26) equipped with a 150 mm wide T-die, and film-formed by the screw extruder under conditions of a cylinder temperature of 200°C to 240°C, a T-die temperature of 240°C, and a cooling roll temperature of 80°C. The resulting resin film was wound up on a paper tube by a winding machine. In this way, a fluorescently colored transparent resin film 1 having a thickness of 60 μm was obtained.

[0103] Example 2 Resin film 2 was obtained in the same manner as in the production of resin film 1, except that the amount of dye C-1 was changed to 1 part.

[0104] Comparative Example 1 A resin film c1 was obtained in the same manner as in the production of resin film 1, except that dye C-1 was not used.

[0105] Comparative Example 2 A resin film c2 was obtained in the same manner as in the production of resin film 1, except that the polycarbonate resin was changed to A-2.

[0106] Comparative Example 3 A resin film c3 was obtained in the same manner as in the production of resin film 2, except that the polycarbonate resin was changed to A-2.

[0107] Table 1 shows the material compositions of resin films 1 to 2 and c1 to c3.

[0108] [Table 1]

[0109] [evaluation] (1) Transparency For each of the resin films 1 to 2 and c1 to c3, the total light transmittance (TT, %) was measured in accordance with JIS K7361-1:1997.

[0110] Moreover, the haze (HAZE, %) of each of the resin films 1 to 2 and c1 to c3 was measured in accordance with JIS K7136:2000.

[0111] (2)Visible light transmittance For each of the resin films 1-2 and c1-c3, the visible light transmittance was measured using a UV-Vis-NIR spectrophotometer V-630 (manufactured by JASCO Corporation) to measure the transmittance of the film at 380 to 780 nm, and calculated in accordance with the calculation method for visible light transmittance and visible light reflectance described in JIS R3106:2019.

[0112] (3) Hue Laminates 1-2 and c1 were prepared by overlaying resin films 1-2 and c1-c3, respectively, on a commercially available prism-type retroreflective sheet (white) (Nikkalite (registered trademark) CRG, manufactured by Nippon Carbide Industries Co., Ltd.). Then, for each of laminates 1-2 and c1-c3, the spectral reflectance spectrum was measured from the resin film side under the conditions of 0° illumination, 45° circumferential light reception, standard light source light D65, and 10° visual field for reflection measurement, and tristimulus values ​​X, Y, and Z in the XYZ color system were obtained, from which chromaticity coordinates (x, y) were calculated.

[0113] The transparency of the resin films 1 to 2 and c1 and the hues of the laminates 1 to 2 and c1 to c3 are shown in Table 2. The chromaticity coordinates of the laminates 1 to 2 and c1 to c3 are shown in FIG.

[0114] [Table 2]

[0115] The "Color Box" in Fig. 2 shows a range formed by sequentially connecting the four points (0.583, 0.416), (0.535, 0.400), (0.642, 0.305), and (0.692, 0.309) with straight lines. This range shows a range of chromaticity coordinates in the XYZ color system that is suitable from the viewpoint of enhancing the visibility of the retroreflective member described above.

[0116] The chromaticity coordinates of the laminates of Examples 1 and 2 were located within the color box in Fig. 2. In addition, the visible light transmittance of the film of Example 1 was improved compared to that of the film of Comparative Example 2, and the visible light transmittance of the film of Example 2 was improved compared to that of the film of Comparative Example 3. [Industrial Applicability]

[0117] The film according to one embodiment of the present invention satisfies the desired chromaticity coordinates and has an improved visible light transmittance, and is therefore suitable for use in molded products such as electric parts, electronic parts, office automation equipment, toys, stationery, automobile interior parts, automobile exterior parts, and other useful molded products in other fields. [Explanation of symbols]

[0118] 10 Laminate 11 Film 12 Retroreflective element layer 13 Base material

Claims

1. A polycarbonate resin (A) containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1), A fluorescent dye (B); A film made of a resin composition containing the fluorescent dye (B) and a dye (C) different from the fluorescent dye (B). 【Chemistry 1】

2. The film according to claim 1, wherein the content of the dye (C) is 0.1 to 5.0 parts by mass per 100 parts by mass of the polycarbonate resin (A).

3. The film according to claim 1 , wherein the dye (C) comprises at least one dye selected from the group consisting of anthraquinone dyes, quinoline dyes, azo dyes, and methine dyes.

4. The film of claim 1 , wherein the dye (C) is a yellow dye.

5. 2. The film of claim 1, wherein the dye (C) is C.I. Solvent Yellow 163.

6. 2. The film according to claim 1, wherein the fluorescent dye (B) comprises at least one selected from the group consisting of thioxanthene-based dyes, thioindigoid-based dyes, anthraquinone-based dyes, benzoxazole coumarin-based dyes, perylene-based dyes, perylene imide-based dyes, benzopyran-based dyes, anthracene-based dyes, and isoquinoline-based dyes.

7. The film according to claim 1, wherein the content of the fluorescent dye (B) is 0.1 to 4.0 parts by mass per 100 parts by mass of the polycarbonate resin (A).

8. 2. The film according to claim 1, wherein the polycarbonate resin (A) further contains a structural unit (b) derived from one or more dihydroxy compounds selected from the group consisting of an aliphatic hydrocarbon dihydroxy compound, an alicyclic hydrocarbon dihydroxy compound, and an ether-containing dihydroxy compound.

9. 2. The film according to claim 1, wherein the chromaticity coordinates (x, y) in the XYZ color system are within a range enclosed by lines sequentially connecting four points: (0.583, 0.416), (0.535, 0.400), (0.642, 0.305), and (0.692, 0.309).

10. A laminate comprising the film according to any one of claims 1 to 9 and a retroreflective sheet.

11. The laminate according to claim 10 , wherein the retroreflective sheet has a two or more layer structure including at least a substrate and a retroreflective element layer, and the retroreflective element layer includes spherical lenses or prisms.

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