Films, multilayer bodies, and heat-bent molded bodies
A polycarbonate resin film with a specific yellow dye and UV absorber combination addresses the challenge of blue LED glare and UV protection, ensuring effective light transmission and glare suppression.
Patent Information
- Application Number
- JP2024174829
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-10-04
- Publication Date
- 2026-04-16
AI Technical Summary
Existing polycarbonate resin films used in sunglasses struggle to effectively suppress glare from blue LEDs while maintaining sufficient transmission of light at 485 nm and providing UV protection.
A film comprising polycarbonate resin, a yellow dye with a specific absorption coefficient, and an ultraviolet absorber is developed, with the yellow dye having a predetermined absorption coefficient and content, and the ultraviolet absorber being incorporated to achieve the desired light transmittance and glare suppression.
The film effectively cuts UV rays, suppresses blue LED glare, and transmits light above 485 nm, enhancing visibility and UV protection.
Smart Images

Figure 2026065841000001_ABST
Abstract
Description
[Technical Field]
[0001] This invention relates to films, multilayers, and heat-bendable molded articles. In particular, it relates to films having polycarbonate resin as a main component. [Background technology]
[0002] Polycarbonate resin is produced by the condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene. It possesses excellent impact strength, numerical stability, heat resistance, and transparency, and is applied to a wide range of fields, including exterior materials for electrical and electronic products, automotive parts, building materials, and optical components.
[0003] On the other hand, optical lenses used in sunglasses and similar products require a transmittance sufficient to prevent glare from external light sources without affecting the field of view. Furthermore, they need to protect the eyes from harmful light rays of specific wavelengths, such as ultraviolet light. Therefore, various technologies have been developed to use polycarbonate resin, which possesses excellent optical properties in addition to mechanical properties, for optical lenses used in outdoor activities such as sunglasses (Patent Documents 1, 2, etc.). [Prior art documents] [Patent Documents]
[0004] [Patent Document 1] Japanese Patent Publication No. 2019-202542 [Patent Document 2] International Publication No. 2019 / 066493 [Overview of the project] [Problems that the invention aims to solve]
[0005] Previously, the idea of incorporating UV absorbers into polycarbonate resin films used for sunglass lenses has been considered. However, in recent years, the glare from blue LEDs (Light Emitting Diodes) has become a problem, and there is a demand for polycarbonate resin films that can suppress the glare of blue LEDs. On the other hand, even if a polycarbonate resin film can suppress the glare of blue LEDs, its usefulness as sunglasses will be reduced if it cannot transmit light with a wavelength of around 485 nm. The present invention aims to solve these problems by providing a film that can cut ultraviolet rays, suppress the glare of blue LEDs, and transmit light of 485 nm or higher, as well as a multilayer and a heat-bending molded article. [Means for solving the problem]
[0006] Based on the above problems, the inventors conducted research and found that the above problems can be solved by blending a predetermined amount of a yellow dye having a predetermined absorption coefficient with a UV absorber into a polycarbonate resin. Specifically, the above problem was solved by the following means. [1] A film comprising polycarbonate resin, a yellow dye, and an ultraviolet absorber, The aforementioned yellow dye has an absorption coefficient (I) at a wavelength of 520 nm. 520 ) is 1.0 × 10 -7 It is less than or equal to / ppm·μm. Amount to 100 parts by mass of the polycarbonate resin: The content of the aforementioned yellow dye is 100 to 4000 ppm by mass. The content of the aforementioned ultraviolet absorber is 0.01 to 1 part by mass. The average light transmittance of the aforementioned film at wavelengths of 350 to 460 nm is 5.0% or less. The light transmittance of the aforementioned film at a wavelength of 485 nm is 20.0% or more. film. [2] The film according to [1], wherein the thickness of the film is 200 to 600 μm. [3] The yellow dye is defined as the ratio of the absorption coefficient at a wavelength of 520 nm to the absorption coefficient at a wavelength of 460 nm. 520 / I460 is 3.0×10 -3 or less, the film according to [1] or [2]. [4] The yellow dye contains at least one compound represented by the formula (YP), the film according to any one of [1] to [3]. Formula (YP)
Chemical formula
Chemical formula
[0007] The present invention makes it possible to provide a film that can cut ultraviolet rays, suppress the glare of blue LEDs, and transmit light of 485 nm or higher, as well as a multilayer and a heat-bendable molded product. [Brief explanation of the drawing]
[0008] [Figure 1] This is a schematic diagram illustrating an example of the layer structure of a multilayer body, a heat-bent molded body, or sunglasses, according to this embodiment. [Modes for carrying out the invention]
[0009] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). Note that the following embodiment is illustrative for explaining the present invention, and the present invention is not limited to this embodiment. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits. "A~B" means that it is greater than or equal to A and less than or equal to B. Furthermore, the upper and lower limits of the numerical values in this specification are given as examples of this embodiment, regardless of the combination of upper and lower limits.
[0010] In this specification, a preferred combination of embodiments is a more preferred embodiment. In this specification, all physical properties and characteristic values shall be those at 23°C unless otherwise specified. In this specification, "film" refers to a molded article that is thin in thickness relative to its length and width, and is generally flat. Furthermore, in this specification, "film" includes sheets and may be single-layer or multi-layer. If the measurement methods, etc., described in the standards shown in this specification differ from year to year, unless otherwise specified, the standards as of January 1, 2024 shall apply. If the measurement methods, etc., described in the standards shown in this specification have been discontinued as of January 1, 2024, the standards in effect at the time of discontinuation shall apply. Figure 1 may not accurately reflect reality due to its scale and other factors.
[0011] The film of this embodiment is a film comprising a polycarbonate resin, a yellow dye, and an ultraviolet absorber, wherein the yellow dye has an absorption coefficient (I) at a wavelength of 520 nm. 520 ) is 1.0 × 10 -7 The film is characterized by having a particle size of 1 / ppm·μm or less, a content of the yellow dye per 100 parts by mass of the polycarbonate resin of 100 to 4000 ppm by mass, a content of the ultraviolet absorber of 0.01 to 1 part by mass, an average light transmittance of the film at a wavelength of 350 to 460 nm of 5.0% or less, and a light transmittance of the film at a wavelength of 485 nm of 20.0% or more. This configuration makes it possible to provide a film that can cut ultraviolet rays, suppress the glare of blue LEDs, and transmit light of 485nm or higher. UV protection is achieved by incorporating UV absorbers into the polycarbonate resin. Furthermore, it was hypothesized that the glare of blue LEDs originates from light with a peak wavelength of 460nm, and that the glare of blue LEDs could be reduced if light around 460nm could be cut. On the other hand, if light rays around 485nm were also cut in addition to the 460nm wavelength, the visibility of objects would decrease, rendering the sunglasses unsuitable. Under these circumstances, the inventors conducted an investigation and found that the absorption coefficient at a wavelength of 520 nm (I 520 ) is 1.0 × 10 -7 By using a predetermined amount of yellow dye with a particle size of 1 / ppm·μm or less, we found that it is possible to cut down on the glare of blue LEDs while still allowing sufficient transmission of 485nm light.
[0012] The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is merely one example of an embodiment of the present invention and is not limited to these.
[0013] <Polycarbonate resin> The film of this embodiment contains polycarbonate resin. By using polycarbonate resin, a film with excellent transparency can be obtained. The polycarbonate resin used in this embodiment is not particularly limited as long as it contains a carbonate ester bond-containing -[OR-OC(=O)]- unit in the molecular main chain (where R is a hydrocarbon group, specifically an aliphatic group, an aromatic group, or a group containing both an aliphatic and an aromatic group, and furthermore, a linear or branched structure). In this embodiment, an aromatic polycarbonate resin is preferred, and a polycarbonate resin having a bisphenol skeleton is more preferred. In the polycarbonate resin having a bisphenol skeleton, it is preferable that 90 mol% or more (preferably 95 mol% or more, more preferably 97 mol% or more) of the total constituent units are constituent units having a bisphenol skeleton. The bisphenol is preferably at least one selected from bisphenol A, bisphenol AP, bisphenol Z, and bisphenol TMC, and is more preferably bisphenol A.
[0014] Furthermore, the viscosity-average molecular weight (Mv) of the polycarbonate resin is preferably 10,000 or more, more preferably 12,000 or more, even more preferably 15,000 or more, and even more preferably 18,000 or more. Setting it above the lower limit tends to further improve the durability of the substrate. The upper limit of the viscosity-average molecular weight (Mv) of the polycarbonate resin is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. Setting it below the upper limit tends to further improve the moldability of the substrate. The viscosity-average molecular weight (Mv) is calculated using methylene chloride as the solvent, determining the intrinsic viscosity [η] (unit: dL / g) at 25°C using an Ubbelohde viscometer, and then using Schnell's viscosity formula, i.e., η = 1.23 × 10⁻⁶ -4 ×Mv 0.83 It means a value calculated from ,. When using two or more types of polycarbonate resin, the viscosity-average molecular weight of the mixture shall be used.
[0015] In this embodiment, the polycarbonate resin may be bio-polycarbonate resin or recycled polycarbonate resin.
[0016] The method for producing polycarbonate resin is not particularly limited, and any method can be used. Examples include interfacial polymerization, molten transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers.
[0017] Further details regarding the polycarbonate resin can be found in paragraphs 0011-0020 of Japanese Patent Application Publication No. 2012-144604 and paragraphs 0014-0035 of Japanese Patent Application Publication No. 2019-002023, without departing from the spirit of this embodiment, and these contents are incorporated herein.
[0018] The polycarbonate resin content in the film of this embodiment is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 97% by mass or more, even more preferably 98% by mass or more, and may also be 99% by mass or more. Furthermore, the polycarbonate resin content in the film of this embodiment is preferably such that, in 100% by mass of the film, all components other than the yellow dye and ultraviolet absorber are polycarbonate resin. When the film of this embodiment contains two or more types of polycarbonate resin, it is preferable that the total amount falls within the above range.
[0019] <yellow dye> The film of this embodiment has an absorption coefficient (I) at a wavelength of 520 nm. 520 )(The following is simply, "I 520 (Sometimes referred to as "") but 1.0 × 10 -7A yellow dye with a particle size of 1 / ppm·μm or less is included in a ratio of 100 to 4000 ppm by mass per 100 parts by mass of polycarbonate resin. By including the specified yellow dye in the above ratio, a film can be obtained that effectively cuts glare from blue LEDs while transmitting light rays with a wavelength of approximately 485 nm. Yellow dye refers to a dye that appears yellow to the human eye.
[0020] The yellow dye I 520 90.0 × 10 -9 It is preferable that the concentration is less than or equal to / ppm·μm, and is 50.0 × 10 -9 It is more preferable that the concentration is less than or equal to / ppm·μm, and 10.0 × 10 -9 It is even more preferable that the concentration be less than or equal to / ppm·μm, and 7.0 × 10 -9 It is even more preferable that the concentration be less than or equal to / ppm·μm. 520 By setting it below the aforementioned upper limit, the visibility of the object tends to improve further. 520 The lower limit is preferably 0, but 1.0 × 10 -10 Even at levels of / ppm·μm or higher, the required performance is fully met. The film of this embodiment may contain only one of the above-mentioned predetermined yellow dyes, or it may contain two or more. If it contains two or more, 520 This is the I of each yellow dye. 520 The weighted average value is calculated by multiplying the mass fraction of each yellow dye by the value obtained by multiplying by the mass fraction of each yellow dye. The absorption coefficient I at a wavelength of 460 nm will be described later. 460 The same applies to this matter.
[0021] The yellow dye used in this embodiment has an absorption coefficient (I) at a wavelength of 520 nm. 520 ) and the absorption coefficient at a wavelength of 460 nm (I 460 The ratio of I 520 / I 460 However, for example, 50.0 × 10 -3 The following is true: 35.0 × 10 -3 Preferably, it is 30.0 × 10 -3 It is more preferable that the following conditions apply: 10.0 × 10 -3 It is even more preferable that the following conditions apply: 7.0 × 10-3 It is even more preferable that the following conditions apply: 3.0 × 10 -3 It is even more preferable that the following conditions apply, and furthermore, 2.5 × 10 -3 Below, 2.0 × 10 -3 Below, 1.5 × 10 -3 The following is preferable: The above yellow dye (especially I 520 / I 460 3.0 × 10 -3 By using the following yellow dyes, the yellow tint of the resulting film can be suppressed. In other words, even with a reduced amount of yellow dye, the glare originating from the blue LED can be effectively suppressed. 520 / I 460 The lower limit is, for example, 1.0 × 10⁻⁶. -3 That's all.
[0022] The method for measuring the absorption coefficient of the yellow dye can be the general method used to measure the absorption coefficient of dyes. Specifically, it can be measured using the method described in the examples.
[0023] Examples of yellow dyes include dyes whose color index (CI) is classified as solvent yellow. The yellow dyes used in this embodiment include solvent yellow 33, 201, 93, 104, 167, etc., and preferably include at least one of solvent yellow 33 or 201 (compounds represented by formula (YP)). Formula (YP) [ka] Furthermore, the molecular weight of the yellow dye used in this embodiment is preferably 200 to 800.
[0024] The yellow dye content in the film of this embodiment is 100 ppm by mass or more, preferably 200 ppm by mass or more, more preferably 300 ppm by mass or more, even more preferably 500 ppm by mass or more, even more preferably 700 ppm by mass or more, and even more preferably 900 ppm by mass or more, per 100 parts by mass of polycarbonate resin. Setting the yellow dye content above the lower limit tends to further improve the effect of cutting ultraviolet rays and high-energy visible light. Furthermore, the yellow dye content in the film of this embodiment is 4000 ppm by mass or less, preferably 3500 ppm by mass or less, more preferably 2500 ppm by mass or less, even more preferably 1500 ppm by mass or less, even more preferably 1300 ppm by mass or less, and even more preferably 1100 ppm by mass or less, per 100 parts by mass of polycarbonate resin. Setting the yellow dye content below the upper limit can more effectively suppress the yellowing of the film. Furthermore, in this embodiment, as described above, I 520 / I 460 3.0 × 10 -3 By using the following yellow dyes, glare from blue LEDs can be effectively suppressed even with a reduced amount of yellow dye. The film of this embodiment may contain only one type of yellow dye, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.
[0025] The film of this embodiment is I 520 is 1.0 × 10 -7 The present invention may contain yellow dye in a concentration greater than / ppm·μm, but it is preferable that it is substantially free of such dye. I 520 is 1.0 × 10 -7 "Substantially free of yellow dye exceeding / ppm·μm" means that in the film of this embodiment, I 520 is 1.0 × 10 -7 The amount of yellow dye greater than / ppm·μm is I 520 is 1.0 × 10-7 This means that the content of the yellow dye is less than 1.5% by mass, preferably less than 1% by mass, more preferably less than 0.7% by mass, even more preferably less than 0.5% by mass, even more preferably less than 0.3% by mass, and even more preferably less than 0.1% by mass.
[0026] <UV absorber> The film of this embodiment contains an ultraviolet absorber. By including an ultraviolet absorber, a film is obtained that effectively suppresses ultraviolet light transmission and has excellent weather resistance. The ultraviolet absorber is preferably one having a maximum absorption wavelength of 280 nm to 380 nm, and more preferably one having a maximum absorption wavelength of only 280 nm to 380 nm. However, if the ultraviolet absorber also falls under the category of the yellow dye, it shall be referred to as the yellow dye. Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, benzoate-based UV absorbers, hindered amine-based UV absorbers, and triazine-based UV absorbers, with the inclusion of a triazine-based UV absorber being preferable.
[0027] Benzotriazole-based UV absorbers include 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-[5-chloro(2H)-benzotriazole-2-yl]-4-methyl-6-(t-butyl)phenol, 2,4-di-tert-butyl-6-(5-chlorobenzotriazole-2-yl)phenol, (2-[5-chloro(2H)-benzotriazole-2-yl]-4,6-di(tert-pentyl)phenol), and 3-[3-tert-butyl-5-(5 [-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]octylpropionate, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-[(2H)-benzotriazol-2-yl]-4,6-bis-(1-methyl-1-phenylethyl)phenol, 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-t-octylphenol], etc. are preferred.
[0028] The triazine-based ultraviolet absorber used in this embodiment preferably contains a compound represented by formula (UV-1), more preferably contains a compound represented by formula (UV-2), and even more preferably contains a compound represented by formula (UV-3). [ka] (In formula (UV-1), R 1 R is a group consisting of a hydrocarbon group having 1 to 10 carbon atoms, or a combination of a hydrocarbon group having 1 to 10 carbon atoms and -O- and / or -C(=O)-, 2 ~R 4Each of these groups is independently a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a group consisting of a hydrocarbon group having 1 to 10 carbon atoms and -O- and / or -C(=O)-, where n2 is an integer from 0 to 3, and n3 and n4 are independently integers from 0 to 4.
[0029] R 1 The group is a hydrocarbon group having 1 to 10 carbon atoms, or a combination of a hydrocarbon group having 1 to 10 carbon atoms and -O- and / or -C(=O)-, preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a combination of an aliphatic hydrocarbon group having 1 to 10 carbon atoms and -O- and / or -C(=O)-, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, even more preferably a linear aliphatic hydrocarbon group having 3 to 10 carbon atoms, and even more preferably a linear alkyl group having 3 to 10 carbon atoms. R 1 The number of carbon atoms in the hydrocarbon group (preferably an aliphatic hydrocarbon group, more preferably an alkyl group) is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, even more preferably 5 or more, and also preferably 9 or less, more preferably 8 or less, and even more preferably 7 or less.
[0030] R 2 ~R 4 Each of these is independently a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a group consisting of a hydrocarbon group having 1 to 10 carbon atoms and -O- and / or -C(=O)-, R 2 ~R 4 At least one of them is a hydroxyl group, R 2 ~R 4 Preferably, at least one of the other members is a hydrocarbon group having 1 to 10 carbon atoms, or a group consisting of a hydrocarbon group having 1 to 10 carbon atoms and -O- and / or -C(=O)-. R 2 ~R 4The hydrocarbon group having 1 to 10 carbon atoms may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably a linear aliphatic hydrocarbon group (preferably a linear alkyl group) or a phenyl group. R 2 ~R 4 The number of carbon atoms in the hydrocarbon group having 1 to 10 carbon atoms is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, even more preferably 5 or more, and also preferably 9 or less, more preferably 8 or less, and even more preferably 7 or less.
[0031] n2 is an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and even more preferably 1. n3 and n4 are each an independent integer between 0 and 4, preferably an integer of 1 or greater, more preferably an integer of 2 or greater, even more preferably an integer of 3 or greater, and preferably an integer of 4 or less.
[0032] [ka] (In formula (UV-2), R 11 , R 31 , and R 41 Each of these is independently an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and R 2 , R 32 , and, R 42 Each of these groups is independently a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a combination of a hydrocarbon group having 1 to 10 carbon atoms and -O- and / or -C(=O)-, and n2, n3-1, and n4-1 are independently integers from 0 to 3.
[0033] R 11 , R 31 , and R 41Each is independently an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and the number of carbon atoms of the aliphatic hydrocarbon group is preferably 4 or more, more preferably 5 or more, and preferably 9 or less, more preferably 8 or less, and even more preferably 7 or less. Further, the aliphatic hydrocarbon group is preferably a linear aliphatic hydrocarbon group, and more preferably a linear alkyl group. The aliphatic hydrocarbon group is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkyl group, and preferably a propyl group, a butyl group, a pentyl group, or a hexyl group, and more preferably a butyl group, a pentyl group, or a hexyl group.
[0034] R 2 、R 32 、and R<� 42 are each independently a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or a group composed of a combination of a hydrocarbon group having 1 to 10 carbon atoms, -O- and / or -C(=O)-. R 2 The preferred range of is the same as that of R 2 in formula (UV-1). R 32 、and R 42 The preferred ranges of are each independently preferably a hydroxyl group and an alkyl group having 1 to 3 carbon atoms, and more preferably a hydroxyl group and a methyl group. n2 is an integer of 0 to 3, preferably 1 or 2, and more preferably 1. n3-1 and n4-1 are each independently an integer of 0 to 3, preferably 1 or 2, and more preferably 2.
[0035]
Chemical formula
[0036] R 11 , R 31 , and R 41 Each of these is independently an aliphatic hydrocarbon group having 3 to 10 carbon atoms, wherein the number of carbon atoms in the aliphatic hydrocarbon group is preferably 4 or more, more preferably 5 or more, preferably 9 or less, more preferably 8 or less, and even more preferably 7 or less. Furthermore, the aliphatic hydrocarbon group is preferably a linear aliphatic hydrocarbon group, and more preferably a linear alkyl group. The aliphatic hydrocarbon group is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkyl group, even more preferably a propyl group, a butyl group, a pentyl group, or a hexyl group, and even more preferably a butyl group, a pentyl group, or a hexyl group.
[0037] Examples of triazine-based UV absorbers used in this embodiment are given below. It goes without saying that the UV absorbers used in this embodiment are not limited to these. [ka]
[0038] The molecular weight of the ultraviolet absorber used in this embodiment is preferably 400 or more, more preferably 500 or more, even more preferably 550 or more, even more preferably 610 or more, and even more preferably 650 or more. By setting the molecular weight of the ultraviolet absorber to be above the lower limit, the ultraviolet absorber becomes less volatile, and roll soiling can be suppressed more effectively. Furthermore, the molecular weight of the ultraviolet absorber used in this embodiment is preferably 1000 or less, more preferably 900 or less, and even more preferably 800 or less. By setting the molecular weight of the ultraviolet absorber to be below the upper limit, the compatibility with the polycarbonate resin tends to improve further.
[0039] The amount of ultraviolet absorber in the film of this embodiment is 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass or more, and also 1 part by mass or less, preferably 0.8 parts by mass or less, more preferably 0.5 parts by mass or less, even more preferably 0.3 parts by mass or less, and even more preferably 0.2 parts by mass or less, per 100 parts by mass of polycarbonate resin. By setting the amount of ultraviolet absorber above the lower limit, the weather resistance of the resulting molded product tends to improve further. Furthermore, by setting the amount of ultraviolet absorber below the upper limit, the weather resistance of the resulting molded product tends to improve further without reducing hue, mechanical properties, or heat resistance. The film of this embodiment may contain only one type of ultraviolet absorber, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.
[0040] <Other ingredients> The film of this embodiment may or may not contain other components other than those mentioned above. Other examples of components include antioxidants, mold release agents, heat stabilizers, flame retardants, flame retardant additives, colorants other than yellow dyes, antistatic agents, fluorescent whitening agents, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, sliding improvers, hue improvers, and acid trapping agents. Furthermore, the film of this embodiment may contain additives described in paragraphs 0047 to 0103 of International Publication No. 2021 / 241471, without departing from the spirit of the present invention, and this is incorporated herein. If other components are included, their total content is preferably 0.001 to 3% by mass of the film, more preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and may be less than 0.01% by mass. The other ingredients may consist of only one type or two or more types. If two or more other ingredients are included, it is preferable that the total amount falls within the above range.
[0041] <Film thickness> The film of this embodiment preferably has a thickness of 200 to 600 μm. By setting the film thickness to be above the lower limit, the average light transmittance of the film at wavelengths of 350 to 460 nm tends to be reduced. By setting the film thickness to be below the upper limit, the heat bending processability tends to be improved. In particular, when the film of this embodiment is laminated with lenses such as eyeglasses, its thickness is preferably half or less the thickness of the lens. The thickness of the film is more preferably 250 μm or more, even more preferably 300 μm or more, even more preferably 350 μm or more, and most preferably 550 μm or less.
[0042] <Light transmittance of the film and b * value> The film of this embodiment has an average light transmittance of 5.0% or less at wavelengths of 350 to 460 nm, and a light transmittance of 20.0% or more at a wavelength of 485 nm. The aforementioned light transmittance is mainly achieved by incorporating a yellow dye. The average light transmittance of the film of this embodiment at wavelengths of 350 to 460 nm is 5.0% or less, preferably 3.0% or less, more preferably 2.0% or less, and the lower limit is substantially greater than 0%.
[0043] The light transmittance of the film of this embodiment at a wavelength of 485 nm is 20.0% or more, preferably 30.0% or more, more preferably 40.0% or more, even more preferably 50.0% or more, even more preferably 60.0% or more, and even more preferably 70.0% or more. The upper limit is 100%, but even if it is 99.0% or less, or even 95.0% or less, the required performance can be met.
[0044] Furthermore, the light transmittance of the film of this embodiment at a wavelength of 460 nm is preferably 5.0% or less, more preferably 4.0% or less, even more preferably 3.0% or less, even more preferably 2.0% or less, and especially even more preferably 1.8% or less. There is no lower limit for the light transmittance of the film of this embodiment at a wavelength of 460 nm, but it is practical to be greater than 0%. A film that satisfies the above-mentioned light transmittance can be achieved, for example, by compounding a predetermined amount of a specific yellow dye into a polycarbonate resin.
[0045] The film of this embodiment is b * A low value is preferable. Specifically, the b of the film. * The value is preferably 112 or less, more preferably 110 or less, even more preferably 105 or less, even more preferably 101 or less, even more preferably 90 or less, and even more preferably 85 or less. Film b of this embodiment * The lower limit of the value may be 0, but 1 or greater is practical, and 3 or greater is sufficient to meet the required performance. * The values represent the amount of yellow dye used and the type of yellow dye (especially I 520 / I 460 This is achieved by adjusting the value.
[0046] Light transmittance of the film, b * A general method can be used to measure the value. Specifically, it can be measured using the method described in the examples.
[0047] <Film manufacturing method> As a method for manufacturing the film of this embodiment, known manufacturing methods can be employed. For example, a polycarbonate resin, a yellow dye, and an ultraviolet absorber, along with other components as needed, may be melt-kneaded together and then extruded into a film. Furthermore, it is preferable that the film be manufactured by roll-to-roll.
[0048] <Wound body> The film of this embodiment can be in the form of a winding body wound around a core material.
[0049] <Multilayer body> The multilayer body of this embodiment comprises the film of this embodiment and a polarizing film. An example of a multilayer structure in this embodiment is a polarizing sheet. In this embodiment, the first embodiment of the multilayer is a sheet in which the film of this embodiment, a polarizing film, and a polarizing film substrate are laminated in that order. In other words, the film of this embodiment is preferably used as at least one of the polarizing film substrates of a polarizing sheet. The polarizing film substrate is usually bonded to the polarizing film via an adhesive. In this embodiment, one of the polarizing film substrates of the polarizing sheet is the film of this embodiment. The other polarizing film substrate of the polarizing sheet can be a known polarizing film substrate of a polarizing sheet, or it may be the film of this embodiment. The polarizing film can be a known one, and an example is one in which iodine or a dichroic organic dye is adsorbed or impregnated onto a polyvinyl alcohol (PVA) film. The adhesive used to bond the film and / or polarizing film substrate to the polarizing film in this embodiment can be a known adhesive, such as an acrylic adhesive, a urethane adhesive, an epoxy adhesive, a silicone adhesive, or a polyvinyl alcohol adhesive. Among these, a urethane adhesive is preferred. The thickness of the adhesive is typically 1 μm or more, and typically 30 μm or less. Furthermore, the polarizing sheet of this embodiment may have a masking film or the like provided on the outside of the film and / or polarizing film substrate of this embodiment.
[0050] In this embodiment, the second embodiment of the multilayer is a sheet in which the film of this embodiment, a polarizing film substrate, a polarizing film, and a polarizing film substrate are laminated in that order. That is, in addition to the polarizing film substrate, the film of this embodiment can be laminated and used. The polarizing film substrate, polarizing film, adhesive, etc. in the second embodiment are the same as in the first embodiment of the multilayer, and the preferred ranges are also the same.
[0051] Furthermore, in this embodiment, the multilayer body of this embodiment is preferably used in a heat-bent molded body that has undergone heat bending. When the multilayer body of this embodiment is used as a polarizing sheet, the film of this embodiment may be provided on either side of the polarizing film, or on both sides. Furthermore, the film of this embodiment may be a polarizing film substrate, or it may be a film provided separately from the polarizing film substrate. The first embodiment is arranged such that, after heat bending, the film of this embodiment is positioned on the concave side of the polarizing film, for example, on the side of the polarizing film substrate 3 in Figure 1. The second embodiment is one in which the film of this embodiment is positioned on the convex side of the polarizing film after heat bending, for example, on the side of the polarizing film substrate 4 in Figure 1. A third embodiment is such that the film of this embodiment is located on both sides of the polarizing film, for example, both polarizing film substrates 3 and 4 in Figure 1 are the film of this embodiment. In Figure 1, the polarizing sheet is shown as lens 1, the polarizing film 2, and the polarizing film substrates 3 and 4 are bent; however, it goes without saying that this embodiment also includes cases where the polarizing film is not bent.
[0052] In this embodiment, the polarizing sheet is preferably used as a polarizing sheet for liquid crystal display devices, a polarizing lens (sunglass lens, ski goggle lens, prescription eyeglass lens, camera viewfinder lens), a cover for various instruments, automobile glass, train glass, polarizing sheets for in-vehicle display panels and electronic device housings, an in-vehicle rearview mirror, a silver mirror for helmets, etc.
[0053] The multilayer body of this embodiment may have a hard coat layer. The hard coat layer is preferably obtained by applying a hard coat material that can be cured by heat or by active energy rays, and then curing it. Examples of materials (paints) that are cured using active energy rays include resin compositions consisting of one or more monofunctional or polyfunctional (preferably 2 to 10-functional) (meth)acrylate monomers or oligomers, and preferably resin compositions containing monofunctional or polyfunctional (preferably 2 to 10-functional) urethane (meth)acrylate oligomers. These resin compositions preferably contain a photopolymerization initiator as a curing catalyst. Furthermore, thermosetting materials (paints) include polyorganosiloxane-based and cross-linked acrylic-based materials. Some of these resin compositions are commercially available as hard coat agents for acrylic resin or polycarbonate resin films or sheets, and should be selected appropriately considering their suitability for the painting line. For the hard coat layer, reference can be given to paragraphs 0045 to 0055 of Japanese Patent Publication No. 2013-020130, paragraphs 0073 to 0076 of Japanese Patent Publication No. 2018-103518, and paragraphs 0062 to 0082 of Japanese Patent Publication No. 2017-213771, and these contents are incorporated herein by reference.
[0054] In addition to the above components, the hard coat layer may also contain light stabilizers, heat stabilizers, flame retardants, flame retardant additives, antistatic agents, fluorescent whitening agents, anti-fogging agents, flow modifiers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact modifiers, sliding modifiers, color modifiers, acid trapping agents, etc. One of these components may be used, or two or more may be used in combination.
[0055] The multilayer body of this embodiment may further have an infrared-cutting layer.
[0056] The multilayer material of this embodiment is preferably used as a polarizing sheet for liquid crystal display devices, a polarizing lens (sunglass lens, ski goggle lens, prescription eyeglass lens, camera viewfinder lens), a cover for various instruments, automobile glass, train glass, polarizing sheets for in-vehicle display panels and electronic device housings, an in-vehicle rearview mirror, a silver mirror for helmets, etc. [Examples]
[0057] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or other reasons, measurements can be taken using other instruments with equivalent performance.
[0058] 1. Raw materials The following ingredients were used. <Polycarbonate resin (A)> A1: Bisphenol A type polycarbonate sheet resin: Manufactured by Mitsubishi Gas Chemical Company, Inc., S-3000
[0059] <Yellow dye (B)> B1: Plast yellow 8005 (CI: Solvent yellow 33), manufactured by Arimoto Chemical Industry Co., Ltd. [ka] B2: Plast yellow 8070 (CI: Solvent yellow 201), manufactured by Arimoto Chemical Industry Co., Ltd. [ka] B3: Plast yellow 8000 (CI: Solvent yellow 93), manufactured by Arimoto Chemical Industry Co., Ltd. [ka] B4: KP Plast yellow F (CI: Solvent yellow 104), manufactured by Kiwa Chemical Industry Co., Ltd. B5: KP Plast yellow MK (CI: Solvent yellow 167), manufactured by Kiwa Chemical Industry Co., Ltd. [ka] B6: KP Plast yellow HK (CI: Solvent yellow 163), manufactured by Kiwa Chemical Industry Co., Ltd. [ka]
[0060] <UV absorber (C)> C1:LA-F70, Triazine-based UV absorber, manufactured by ADEKA Corporation C2:LA-31, benzotriazole-based UV absorber, manufactured by ADEKA Corporation.
[0061] <Measurement of the absorption coefficient of yellow dye> The absorption coefficient of the yellow dye at wavelengths of 520 nm and 460 nm (I 520 , I 460 The following method was used to measure the results. Using a spectrophotometer, the absorbance at wavelengths of 520 nm and 460 nm was measured for polycarbonate resin films containing 50 ppm by mass of each yellow dye and with a thickness of 500 μm, under conditions of a scan speed of 300 nm / min and a sampling interval of 1 nm. Similarly, the absorbance at wavelengths of 520 nm and 460 nm was measured for a film of the same thickness as the above film but without the yellow dye. The difference in absorbance at each wavelength between the film containing the yellow dye and the film without the yellow dye was defined as the absorbance of each yellow dye in a 500 μm thick film. The absorption coefficient at each wavelength (unit: / ppm·μm) was calculated by dividing this by the dye concentration (50 ppm by mass) and the film thickness (500 μm). A U-4100 spectrophotometer (manufactured by Hitachi High-Tech Corporation) was used for the measurements. The absorption coefficient of the yellow dye at a wavelength of 520 nm (I 520 Regarding ), in Table 1 or Table 2, Unit: 10 -9 The values are shown in ppm / μm. The ratio of the absorption coefficient of a yellow dye at a wavelength of 520 nm to the absorption coefficient at a wavelength of 460 nm (I 520 / I 460 The figures are shown in Table 1 or Table 2.
[0062] 2. Examples 1-5, Comparative Examples 1-5 <Film Manufacturing> Polycarbonate resin film was manufactured using the following method. Each component listed in Table 1 or 2 was weighed to the amount indicated in Table 1 or 2 (Tables 1 and 2 show amounts in parts by mass). After mixing in a tumbler for 15 minutes, a T-die melt extruder consisting of a vented twin-screw segment extruder with a barrel diameter of 25 mm and a screw L / D = 30 (Toyo Seiki Co., Ltd., "2D30W2") was used to extrude the mixture into a molten state at a discharge rate of 8 kg / h and a screw rotation speed of 100 rpm. The mixture was then cooled and solidified using only the first roll of a film / sheet take-up device (Toyo Seiki Co., Ltd., "FT3W20") to produce a polycarbonate resin film. The cylinder / die head temperature was 280°C and the roll temperature was 130°C. The roll speed of the first roll was adjusted so that the final film thickness obtained would be 500 μm.
[0063] <Average light transmittance for wavelengths of 350-460nm> The average light transmittance of the obtained polycarbonate resin film was measured at wavelengths of 350 to 460 nm. Specifically, a spectrophotometer was used to measure the light transmittance (in %) of the film at wavelengths of 350 to 460 nm under conditions of a scan speed of 300 nm / min and a sampling interval of 1 nm. The average value was calculated from the light transmittance values for each 1 nm wavelength. A U-4100 spectrophotometer (manufactured by Hitachi High-Tech Corporation) was used for the measurements. The following categories were used for evaluation. A: 5.0% or less B: More than 5.0%
[0064] <Light transmittance at a wavelength of 460nm> The light transmittance of the obtained polycarbonate resin film at a wavelength of 460 nm was measured. The light transmittance was measured in the same manner as the average light transmittance for wavelengths of 350 to 460 nm described above. The unit is expressed in %.
[0065] <Light transmittance at a wavelength of 485nm> The light transmittance of the obtained polycarbonate resin film was measured at a wavelength of 485 nm. The light transmittance was measured in the same manner as the average light transmittance for wavelengths of 350 to 460 nm described above. The following categories were used for evaluation. A: 20.0% or more B: Less than 20.0%
[0066] <Dazzling Light Rating> The glare from a lit blue LED viewed through a film from a distance of 5 meters was evaluated as follows. The evaluation was conducted by five experts, and the decision was made by majority vote. The blue LED used was an ultra-high brightness bulb-type LED (manufactured by Elekit Co., Ltd.). A: I don't feel any glare. B: I can feel the glare.
[0067] * value> Regarding the obtained polycarbonate resin film, b * The values were measured using a spectrophotometer under the following conditions, in accordance with JIS Z 8781-4. Measurement method: Transmission Specular reflection processing: SCI Light source: D65 Field of view: 2° The spectrophotometer used was the "SD-7000" manufactured by Nippon Denshoku Industries Co., Ltd.
[0068] [Table 1]
[0069] [Table 2]
[0070] I in Tables 1 and 2 above 520 This is the extinction coefficient of the yellow dye at a wavelength of 520 nm, and its unit is 10. -9 The density is / ppm·μm. For example, the absorption coefficient of the yellow dye used in Example 1 at a wavelength of 520 nm is 4.3 × 10⁻¹⁰. -9 It becomes / ppm·μm. The I of the yellow dye 520 / I 460 [10 -3 Regarding ], for example, in Example 1, I 520 / I 460 is 1.0 × 10 -3 This is the result.
[0071] As is clear from the above results, the film of this embodiment was able to cut out light in the ultraviolet region, reduce the glare of blue LEDs, and transmit light with a wavelength of 485 nm (Examples 1-5). In contrast, when the yellow dye and UV absorber were not included (Comparative Example 1), the glare of the blue LED could not be reduced. Furthermore, light in the ultraviolet region was also transmitted. Also, the yellow dye I 520 is 1.0 × 10 -7 When the concentration exceeded / ppm·μm (Comparative Example 2), the glare of the blue LED was reduced, but light with a wavelength of 485nm could not be transmitted. Furthermore, when the yellow dye content was below the lower limit of the present invention (Comparative Example 3), the glare of the blue LED could not be reduced. In addition, light in the ultraviolet region was also transmitted. On the other hand, when the content of the yellow dye exceeded the upper limit of the present invention (Comparative Example 4), light with a wavelength of 485 nm could not be transmitted. Furthermore, when no UV absorber was included (Comparative Example 5), it was not possible to block light in the ultraviolet region.
[0072] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications are possible without departing from the intent and scope of the invention. [Explanation of symbols]
[0073] 1 lens 2 Polarizing film 3. Polarizing film substrate 4 Polarizing film substrate
Claims
1. A film containing polycarbonate resin, a yellow dye, and an ultraviolet absorber, The aforementioned yellow dye has an absorption coefficient (I) at a wavelength of 520 nm. 520 ) is 1.0 × 10 -7 / ppm·μm or less, Amount to 100 parts by mass of the polycarbonate resin: The content of the aforementioned yellow dye is 100 to 4000 ppm by mass. The amount of the ultraviolet absorber is 0.01 to 1 part by mass. The average light transmittance of the aforementioned film at wavelengths of 350 to 460 nm is 5.0% or less. The light transmittance of the aforementioned film at a wavelength of 485 nm is 20.0% or more. film.
2. The film according to claim 1, wherein the thickness of the film is 200 to 600 μm.
3. The yellow dye is defined as the ratio of the absorption coefficient at a wavelength of 520 nm to the absorption coefficient at a wavelength of 460 nm. 520 / I 460 3.0 x 10 -3 The film according to claim 1 or 2, which is as follows:
4. The film according to claim 1 or 2, wherein the yellow dye comprises at least one compound represented by formula (YP). Formula (YP) 【Chemistry 1】
5. The film according to claim 1 or 2, wherein the ultraviolet absorber comprises a compound represented by formula (UV-1). 【Chemistry 2】 (In formula (UV-1), R 1 This refers to a hydrocarbon group having 1 to 10 carbon atoms, or A group consisting of a hydrocarbon group having 1 to 10 carbon atoms and a combination of -O- and / or -C(=O)-, R 2 ~R 4 Each of these independently consists of a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or A group consisting of a hydrocarbon group having 1 to 10 carbon atoms and a combination of -O- and / or -C(=O)-, n2 is an integer between 0 and 3. n3 and n4 are each independent integers between 0 and 4.
6. The film according to claim 1 or 2, wherein the light transmittance at a wavelength of 460 nm is 3.0% or less.
7. The thickness of the aforementioned film is 200 to 600 μm. The yellow dye has a ratio I 520 520 / I 460 460 of the absorption coefficient at a wavelength of 520 nm to the absorption coefficient at a wavelength of 460 nm of 3.0×10 -3 -3 or less. The yellow dye comprises at least one compound represented by formula (YP), The aforementioned ultraviolet absorber includes a compound represented by formula (UV-1), The film according to claim 1, wherein the light transmittance at a wavelength of 460 nm is 3.0% or less. Formula (YP) 【Transformation 3】 【Chemistry 4】 (In formula (UV-1), R 1 This refers to a hydrocarbon group having 1 to 10 carbon atoms, or A group consisting of a hydrocarbon group having 1 to 10 carbon atoms and a combination of -O- and / or -C(=O)-, R 2 ~R 4 Each of these independently consists of a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms, or A group consisting of a hydrocarbon group having 1 to 10 carbon atoms and a combination of -O- and / or -C(=O)-, n2 is an integer between 0 and 3. n3 and n4 are each independent integers between 0 and 4.
8. A multilayer having the film and polarizing film according to claim 1, 2, or 7.
9. A multilayer heat-bendable molded article according to claim 8.
Citation Information
Patent Citations
Optical sheet and optical component
JP2019202542A
Polycarbonate resin composition and optical molded product comprising same
WO2019066493A1