JP2015147915A - Film, laminated film, and retroreflective sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film capable of giving a retroreflective sheet which has fluorescence, excellent weather resistance, and excellent visibility.SOLUTION: The film of the present embodiment contains a polycarbonate resin (A), a fluorescent dye (B), and a white pigment (C). The content of the fluorescent dye (B) is 0.10 pts.mass or more and 3.00 pts.mass or less based on 100 pts.mass of the polycarbonate resin (A), and the content of the white pigment (C) is 0.03 pts.mass or more and 3.00 pts.mass or less based on 100 pts.mass of the polycarbonate resin (A).

Description

  The present invention relates to a film having a fluorescent color, a laminated film, or a retroreflective sheet.

  A retroreflective sheet that reflects incident light toward a light source is conventionally known. The retroreflective sheet is used in various fields by utilizing the retroreflective property and excellent visibility in a dark place.

  For example, a sign such as a road sign or a construction sign using a retroreflective sheet reflects light from a light source of a headlight of a vehicle traveling in a dark place such as at night toward the light source, that is, the direction of the traveling vehicle. be able to. Therefore, the sign using the retroreflective sheet provides excellent visibility to the driver of the vehicle and can transmit clear information.

  As a retroreflective sheet used for the above-mentioned applications, from the viewpoint of excellent retroreflective performance, an enclosed lens type retroreflective sheet and a prism type retroreflective sheet using a prism (for example, a triangular pyramid cube corner retroreflective sheet) are also available. It's being used.

  By using a colored film as a skin material of a retroreflective sheet used as a sign for such road signs and construction signs, it is possible to impart excellent properties such as weather resistance and visibility to the retroreflective sheet. .

  Further, in order to further improve the visibility in road signs and the like, it is required to provide not only retroreflective performance but also fluorescence to the signs. As a retroreflective sheet having fluorescence, Patent Document 1 discloses a retroreflective sheet in which a colored layer containing a fluorescent dye is provided with a screen layer for imparting weather resistance.

Japanese Patent Laid-Open No. 4-292940

  However, the retroreflective sheet is required to further improve the visibility.

  The subject of this embodiment is providing the film which can obtain the retroreflection sheet which has fluorescence, is excellent in a weather resistance, and is excellent in visibility.

(1) including a polycarbonate resin (A), a fluorescent dye (B) and a white pigment (C),
The content of the fluorescent dye (B) is 0.10 parts by mass or more and 3.00 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A).
Content of the said white pigment (C) is 0.03 mass part or more and 3.00 mass part or less with respect to 100 mass parts of said polycarbonate resins (A).

  (2) The film according to (1), wherein the content of the polycarbonate resin (A) in the film is 85% by mass or more.

  (3) The fluorescent dye (B) is at least one selected from the group consisting of thioxanthene dyes, thioindigoid dyes, anthraquinone dyes, benzoxazole coumarin dyes, perylene dyes, peryleneimide dyes, and benzopyran dyes. The film according to (1) or (2), which is a seed.

  (4) The film according to any one of (1) to (3), wherein the white pigment (C) contains titanium oxide.

  (5) A laminated film comprising the film according to any one of (1) to (4) and an acrylic resin layer disposed on at least one surface of the film.

  (6) The laminated film according to (5), wherein the haze is 0.10% or more and 25% or less.

(7) The chromaticity coordinates (x, y) in the XYZ color system under the following measurement conditions are (0.387, 0.610), (0.369, 0.546), (0.428, 0). .496) and (0.460, 0.540), the laminated film according to (5) or (6) within a range surrounded by four points;
Measurement conditions: The laminated film and a standard white plate are overlapped, and the acrylic resin layer side of the laminated film is measured with 0 ° illumination for reflection measurement, 45 ° circumferential light reception, standard light D65, and 2 ° visual field. When the standard white plate was measured with 0 ° illumination for reflection measurement, 45 ° circumferential light reception, standard light C, and 2 ° field of view, XYZ in the XYZ color system was X = 93.96, Y = 95.90, Z = 113.05.

  (8) A retroreflective sheet comprising a reflective element layer and a skin layer disposed on the reflective element layer, wherein the laminated film according to any one of (1) to (7) is used as the skin layer Retroreflective sheet.

  (9) The retroreflective sheet according to (8), wherein the acrylic resin layer is an outer layer of the laminated film.

  (10) Chromaticity coordinates in the XYZ color system (x, x, when measured from the acrylic resin layer side under the conditions of standard light D65 and 2 ° field of view by 0 ° illumination and 45 ° circumferential light reception for reflection measurement y) is a range surrounded by four points (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540) The retroreflective sheet as described in (9) in the inside.

  (11) The retroreflective sheet according to (10), wherein the Y value in the XYZ color system of the retroreflective sheet measured under the above conditions is 45 or more.

  (12) The retroreflective sheet according to any one of (8) to (11), wherein the reflective element layer is a bead-shaped lens or a prism-shaped lens.

  According to one embodiment of the present embodiment, it is possible to provide a film that can obtain a retroreflective sheet having fluorescence, excellent weather resistance, and excellent visibility.

  According to one embodiment of the present embodiment, it is possible to provide a laminated film capable of obtaining a retroreflective sheet having fluorescence, excellent weather resistance, and excellent visibility.

  According to one embodiment of the present embodiment, it is possible to provide a retroreflective sheet that is excellent in weather resistance, visibility, and retroreflective performance.

(0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540) and first in chromaticity coordinates (x, y) It is a figure which shows the area | region enclosed by connecting each coordinate of (0.387, 0.610) of this by a straight line in order. It is a figure which shows the chromaticity coordinate (x, y) of the laminated | multilayer film in an Example. It is a figure which shows the chromaticity coordinate (x, y) of the retroreflection sheet | seat in an Example.

<Polycarbonate resin (A)>
The film of this embodiment uses a polycarbonate resin as a base material from the viewpoint of the weather resistance of the film and the maintenance of fluorescence.

  The polycarbonate resin (A) is not particularly limited, and examples thereof include aromatic polycarbonate resins having an aromatic ring. As the polycarbonate resin (A), a polycarbonate resin having no aromatic ring may be used, but it is preferable to use an aromatic polycarbonate from the viewpoint of availability. Polycarbonate resin (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

The polycarbonate resin (A) preferably has fluidity that can be formed as a film depending on conditions such as temperature. The fluidity can be determined by using, for example, a melt volume flow rate (MVR) measured under conditions of 300 ° C. and 1.2 kgf based on ISO 1133. MVR of the polycarbonate resin (A) ^is preferably 5~70cm 3 / ^10min, more preferably 7~60cm 3 / ^10min, still more preferably 9~50cm 3 / 10min.

  The production method of the polycarbonate resin is not particularly limited, and any production method can be selected and produced. As a manufacturing method, the method of superposing | polymerizing using a dihydroxy compound and a carbonate precursor is mentioned, for example. More specifically, examples of the production method include an interfacial polycondensation method in which a polycarbonate resin is produced by reacting a dihydroxy compound and a carbonate precursor at the interface between an organic phase and an aqueous phase. Moreover, for example, a melt polycondensation method in which a polycarbonate resin is produced by subjecting a dihydroxy compound and a carbonate precursor to a transesterification reaction in a molten state in the presence of a catalyst.

  Although it does not restrict | limit especially as a dihydroxy compound, For example, an aliphatic dihydroxy compound or an aromatic dihydroxy compound etc. are mentioned. Examples of the aromatic dihydroxy compound include an aromatic compound having two phenolic hydroxyl groups. Specific examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, and 2,2-bis (4-hydroxy-3,5-dimethyl). Phenyl) propane and the like.

  Although it does not restrict | limit especially as a carbonate precursor, A carbonyl halide, carbonyl ester, or a haloformate etc. are mentioned. Specific examples of the carbonate precursor include phosgene, diphenyl carbonate, or divalent phenol haloformate.

  The content of the polycarbonate resin (A) in the film is preferably 85% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and 99% by mass or more. It is particularly preferred.

  In addition to polycarbonate resin (A), fluorescent dye (B), and white pigment (C), the film can be stabilizer, lubricant, processing aid, matting agent, light diffusing agent, plasticizer, impact resistance Various compounding agents such as an auxiliary agent, a foaming agent, a filler, a colorant, an antibacterial agent, a fungicide, a mold release agent, an antistatic agent, a light stabilizer, an ultraviolet absorber, and an antioxidant can be included.

  The total amount of the compounding agent is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 8 parts by mass, and 0.1 to 6 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is more preferable that

  As a kind of ultraviolet absorber, a benzotriazole type ultraviolet absorber or a triazine type ultraviolet absorber is mentioned, for example.

  Examples of commercially available benzotriazole-based ultraviolet absorbers include “TINUVIN 234” manufactured by BASF, “ADEKA STAB LA-31” manufactured by ADEKA (all are trade names), and the like.

  Examples of commercially available triazine ultraviolet absorbers include “TINUVIN 1577” manufactured by BASF, “LA-F70” and “LA-46” manufactured by ADEKA (both are trade names).

  An ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the ultraviolet absorber is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and 0.3 More preferably, it is -6 mass parts. When content of a ultraviolet absorber is 0.1 mass part or more, favorable weather resistance can be provided to the film obtained. Moreover, when content of a ultraviolet absorber is 10 mass parts or less, manufacturing cost can be suppressed, maintaining sufficient weather resistance.

  As the antioxidant, for example, a known compound can be used. Although it does not restrict | limit especially as an antioxidant, For example, a phenolic antioxidant or a phosphite type antioxidant is mentioned preferably.

  Examples of the phenolic antioxidant include hindered phenolic compounds in which a bulky group is present at the ortho position of the hydroxyl group of the phenolic compound and the properties of the phenolic hydroxyl group are concealed.

  As commercially available products of antioxidants or compositions containing antioxidants, for example, “IRGANOX1010”, “IRGANOX1076”, “IRGANOX1098”, “IRGANOX245”, “IRGANOX3114” (all trade names) manufactured by BASF, Examples include “ADK STAB AO-20”, “AO-50”, “AO-60”, “AO-80”, “AO-330”, “2112” (all trade names) manufactured by ADEKA.

  An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the antioxidant is preferably 0.01 to 2 parts by mass, more preferably 0.02 to 1.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). More preferably, it is 0.03 to 1 part by mass. When the content of the antioxidant is 0.01 parts by mass or more, when the polycarbonate resin composition containing the polycarbonate resin (A), the fluorescent dye (B) and the white pigment (C) is molded into a pellet or film It is possible to suppress the coloration (thermal coloring) caused by the heat. Moreover, when content of an antioxidant is 2 mass parts or less, manufacturing cost can be suppressed, maintaining sufficient heat-resistant coloring property.

<Fluorescent dye (B)>
The film of this embodiment contains a fluorescent dye (B).

  The fluorescent dye (B) is not particularly limited, and for example, a known fluorescent dye can be used. The fluorescent dye (B) is preferably selected and used in consideration of the chromaticity coordinates (x, y) required as a retroreflective sheet.

  Regarding the chromaticity coordinates (x, y) required for the retroreflective sheet, for example, in ASTM D4956, the color of the yellow-green (Fluorescent Yellow-Green) retroreflective sheet is (0.387, 0.610), ( 0.369, 0.546), (0.428, 0.496), and (0.460, 0.540) within the range surrounded by four points, and the color of the retroreflective sheet of yellow (Fluorescent Yellow) Is within a range surrounded by four points (0.479, 0.520), (0.446, 0.483), (0.512, 0.421), and (0.557, 0.442). Yes, the color of the orange (Fluorescent Orange) retroreflective sheet is (0.583, 0.416), (0.535, 0.400), (0.595,0 .351) and (0.645, 0.355). The retroreflective sheet preferably satisfies any chromaticity coordinate (x, y) range as necessary.

  Here, as illustrated in FIG. 1, the range surrounded by the four points exemplified is (0.387, 0.610), (0.369, 0.546) in chromaticity coordinates (x, y), It means a region surrounded by connecting the coordinates of (0.428, 0.496) and (0.460, 0.540) and the first (0.387, 0.610) in order with a straight line.

  The type of fluorescent dye is at least one selected from the group consisting of thioxanthene dyes, thioindigoid dyes, anthraquinone dyes, benzoxazole coumarin dyes, perylene dyes, peryleneimide dyes, and benzopyran dyes. preferable.

  Specific examples of commercially available fluorescent dyes include C.I., which is a thioxanthene dye. I. "DIMIC MBR-D70" manufactured by Dainichi Seika Kogyo Co., Ltd., consisting of Solvent Yellow 98, C.I. I. “DIMIC MBR D-74” manufactured by Dainichi Seika Kogyo Co., Ltd. consisting of Solvent Orange 63, C.I. I. “DIMIC MBR 120830 Orange” manufactured by Dainichi Seika Kogyo Co., Ltd. consisting of Solvent Orange 55, “Lumogen F Yellow 083” manufactured by BASF, which is also a perylene dye, “Lumogen F Yellow 170” manufactured by BASF, which is a perylene imide dye. “Lumogen F Orange 240”, “Lumogen F Red 305”, C.I. I. Examples include “MBR D-75” manufactured by Dainichi Seika Kogyo Co., Ltd., which consists of Solvent Red197.

  Content of fluorescent dye (B) is 0.10 mass part or more and 3.00 mass part or less with respect to 100 mass parts of polycarbonate resin (A). By setting the content of the fluorescent dye (B) to 0.10 parts by mass or more and 3.00 parts by mass or less, the film can be easily accommodated in the range of desired chromaticity coordinates (x, y). . The content of the fluorescent dye (B) is more preferably 0.20 parts by mass or more and 2.50 parts by mass or less, and further preferably 0.30 parts by mass or more and 2.00 parts by mass or less.

<White pigment (C)>
The film of this embodiment contains a white pigment (C).

  The white pigment (C) is not particularly limited, and can be appropriately selected and used.

  Examples of the white pigment (C) include titanium oxide and zinc oxide. The white pigment (C) is preferably titanium oxide from the viewpoint of availability.

The average particle diameter (volume average: D ₅₀ ) of titanium oxide is preferably 500 nm or less. By using titanium oxide having an average particle diameter of 500 nm or less, it becomes easy to suppress a decrease in transparency of the obtained film, and it becomes easy to improve the luminance of the obtained retroreflective sheet. The average particle size of titanium oxide is more preferably 300 nm or less, and further preferably 100 nm or less.

  Specific examples of commercially available titanium oxide include “DIMIC MBR 030 White” and “DIMIC MBR 002 White” manufactured by Dainichi Seika Kogyo Co., Ltd., which are white pigments containing titanium oxide as a main component.

  Content of a white pigment (C) is 0.03 mass part or more and 3.00 mass part or less with respect to 100 mass parts of polycarbonate resin (A). By making content of a white pigment (C) 0.03 mass part or more, it becomes possible to improve the brightness | luminance of the retroreflective sheet obtained more effectively. By setting the content of the white pigment (C) to 3.00 parts by mass or less, the haze of the film can be more effectively suppressed. As a result, the visibility of the retroreflective sheet obtained can be kept good.

<Other colorants>
The film of this embodiment can contain other colorants as necessary in addition to the fluorescent dye (B) and the white pigment (C).

  The colorant is not particularly limited, and a dye or a pigment can be arbitrarily selected and used. A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the colorant, it is preferable to use a dye from the viewpoint of the transparency of the obtained laminated film and the visibility of the retroreflective sheet.

<Acrylic resin (D)>
The laminated film of this embodiment has the film of this embodiment and an acrylic resin layer (also referred to as an acrylic resin film) disposed on at least one surface of the film. The acrylic resin film contains an acrylic resin (D).

  Although it does not restrict | limit especially as an acrylic resin (D), For example, you may use the thermoplastic polymer (D-1) which has an alkyl methacrylate unit as a main component, and the rubber containing polymer mentioned later is mentioned. (D-2) may be used. Moreover, as an acrylic resin (D), you may use them individually or in combination.

  The content of the thermoplastic polymer (D-1) and the rubber-containing polymer (D-2) in the acrylic resin (D) is 0 to 100% by mass of the thermoplastic polymer (D-1) and contains rubber. It is preferable to make a polymer (D-2) into 100 to 0 mass%. Further, the content of the thermoplastic polymer (D-1) in the acrylic resin (D) is 20 to 80% by mass, and the content of the rubber-containing polymer (D-2) in the acrylic resin (D) is 80. It is more preferable to set it as -20 mass%. Further, it is more preferable that the content of the thermoplastic polymer (D-1) is 40 to 60% by mass and the content of the rubber-containing polymer (D-2) is 60 to 40% by mass.

  The content of the acrylic resin (D) in the acrylic resin film is preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 99% by mass. The above is particularly preferable.

  In the present specification, “(meth) acryl” means “acryl” or “methacryl”.

  In addition, acrylic resin films can be used as needed, stabilizers, lubricants, processing aids, matting agents, light diffusing agents, plasticizers, impact aids, foaming agents, fillers, colorants, antibacterial agents, antibacterial agents. Various compounding agents such as fungicides, mold release agents, antistatic agents, light stabilizers, ultraviolet absorbers and antioxidants can be included.

  The total amount of the compounding agent is, for example, 0.1 to 10 parts by mass, preferably 0.2 to 8 parts by mass, and 0.3 to 6 parts by mass with respect to 100 parts by mass of the acrylic resin (D). It is more preferable that

  As a kind of ultraviolet absorber, the thing similar to what was described in the term of polycarbonate resin (A) can be used. An ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the ultraviolet absorber is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass with respect to 100 parts by mass of the acrylic resin (D), and 0.3 More preferably, it is -6 mass parts. When content of a ultraviolet absorber is 0.1 mass part or more, a weather resistance can be effectively provided to the acrylic resin film obtained. Therefore, the polycarbonate resin (A) and the fluorescent dye (B) in the laminated film of the present embodiment can be effectively protected. Moreover, when content of a ultraviolet absorber is 10 mass parts or less, manufacturing cost can be suppressed, maintaining sufficient weather resistance.

  Although it does not restrict | limit especially as a light stabilizer, For example, a well-known compound can be used and a hindered amine type radical scavenger is used preferably.

  A hindered amine-based radical scavenger is a compound having a piperidine ring having a substituent having a plurality of steric hindrances on two adjacent carbon atoms of a nitrogen atom. Examples of the substituent exhibiting such steric hindrance include a methyl group. Preferred examples of the compound having such a substituent include a compound having a 2,2,6,6-tetramethyl-4-piperidyl group and a 1,2,2,6,6-pentamethyl-4-piperidyl group. And the like. As a commercial item of the composition containing a hindered amine radical scavenger or a hindered amine radical scavenger, for example, trade names manufactured by BASF: Chimassorb 119FL, 2020FDL, 944FD, 944LD, Tinuvin 622LD, 123S, 144, 765, 770 770DF, 770FL, 111FD, 123, 292, trade names manufactured by Sankyo Co., Ltd .: Sanol LS-770, LS-765, LS-292, LS-2626, LS-744, LS-440, products manufactured by ADEKA Name: ADK STAB LA-52, LA-57, LA-62, LA-63P, LA-68, LA-81, LA-82, LA-87 and the like. A light stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the light stabilizer is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 4 parts by mass with respect to 100 parts by mass of the acrylic resin (D), and 0.05 More preferably, it is -3 mass parts. When the content of the light stabilizer is 0.01 parts by mass or more, good weather resistance can be imparted to the acrylic resin film. Moreover, when content of a light stabilizer is 5 mass parts or less, manufacturing cost can be suppressed, maintaining sufficient weather resistance.

  As the antioxidant, those similar to those described in the section of the polycarbonate resin (A) can be used.

  An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the antioxidant is preferably 0.01 to 2 parts by mass, more preferably 0.02 to 1.5 parts by mass with respect to 100 parts by mass of the acrylic resin (D). More preferably, it is 0.03 to 1 part by mass. When the content of the antioxidant is 0.01 parts by mass or more, it is possible to effectively suppress thermal coloring that occurs when the acrylic resin composition containing the acrylic resin (D) is formed into pellets and films. it can. Moreover, when content of an antioxidant is 2 mass parts or less, manufacturing cost can be suppressed, maintaining sufficient heat-resistant coloring property effectively.

<Thermoplastic polymer (D-1)>
As a thermoplastic polymer (D-1) which has an alkyl methacrylate unit as a main component, from a heat resistant viewpoint of an acrylic resin film, alkyl methacrylate 50-50 mass%, alkyl acrylate 0-50 mass%, and A monomer containing 0 to 49% by mass of another monomer having a double bond copolymerizable with these (alkyl methacrylate, alkyl acrylate) (hereinafter referred to as a monomer having a double bond). Polymers obtained by polymerizing the components are preferred.

  Examples of the alkyl methacrylate include those having a linear alkyl group and a branched chain.

  Specific examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate and n-butyl methacrylate. These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the alkyl acrylate include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. Of these, n-butyl acrylate is preferred. These can be used individually by 1 type or in combination of 2 types.

  Examples of the monomer having a double bond include acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, and (meth) acrylic acid; aromatic vinyl monomers such as styrene and alkyl-substituted styrene. And vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. These can be used individually by 1 type or in combination of 2 or more types.

  The content of alkyl methacrylate is preferably 50 to 100% by mass, more preferably 85 to 99.9% by mass, and still more preferably 92 to 99.9% by mass, from the viewpoint of heat resistance of the acrylic resin film.

  The content of alkyl acrylate is preferably 0 to 40% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.1 to 8% by mass, from the viewpoint of heat resistance of the acrylic resin film.

  The content of the monomer having a double bond in the monomer component is preferably 0 to 49% by mass, more preferably 0 to 35% by mass, from the viewpoint of heat resistance of the acrylic resin film.

  The monomer component can contain a chain transfer agent.

  Examples of the chain transfer agent include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol and carbon tetrachloride. These can be used individually by 1 type or in combination of 2 or more types. Examples of the chain transfer agent include n-octyl mercaptan.

  As the thermoplastic polymer (D-1), a polymer having a reduced viscosity (0.1 g of polymer dissolved in 100 ml of chloroform and measured at 25 ° C.) of 0.1 L / g or less is preferable.

  Examples of the polymerization method of the thermoplastic polymer (D-1) include a suspension polymerization method, an emulsion polymerization method, and a bulk polymerization method.

<Rubber-containing polymer (D-2)>
The acrylic resin (D) may contain a rubber-containing polymer (D-2) as necessary.

  The rubber-containing polymer (D-2) is a rubber polymer (D2a) obtained by polymerizing a monomer component (D-2-a) containing an alkyl acrylate and a polyfunctional monomer as essential components. A rubber-containing polymer obtained by polymerizing a monomer component (D-2-b) containing an alkyl methacrylate as an essential component in the presence thereof.

  As alkyl acrylate, the thing similar to what was described by the thermoplastic polymer (D-1) can be used, for example.

  Examples of the polyfunctional monomer include a crosslinkable monomer having two or more copolymerizable double bonds in one molecule. Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, and di (meth). Alkylene glycol di (meth) acrylates such as propylene glycol acrylate; polyvinylbenzenes such as divinylbenzene and trivinylbenzene; cyanurate monomers such as triallyl cyanurate and triallyl isocyanurate; α, such as allyl methacrylate β-unsaturated carboxylic acid; allyl, methallyl or crotyl ester of dicarboxylic acid. These can be used individually by 1 type or in combination of 2 or more types.

  In the monomer component (D-2-a), examples of the monomer other than the alkyl acrylate and the polyfunctional monomer include, for example, alkyl methacrylate, or these (alkyl acrylate, polyfunctional monomer). ) And other monomers having a double bond copolymerizable therewith.

  As the other monomers having an alkyl methacrylate and a copolymerizable double bond, for example, the same monomers as those described for the thermoplastic polymer (D-1) can be used.

  The monomer component (D-2-a) can contain a chain transfer agent. As a chain transfer agent, the thing similar to what was described by the thermoplastic polymer (D-1) can be used, for example.

  The glass transition temperature (hereinafter referred to as Tg) of the rubber polymer (D2a) is preferably less than 25 ° C., more preferably 10 ° C. or less, more preferably from the viewpoint of the flexibility of the rubber-containing polymer (D-2). 0 ° C. or lower.

  In the present invention, Tg refers to a value calculated from the FOX equation using values described in a polymer handbook [Polymer HandBook (J. Brandrup, Interscience, 1989)].

  The rubber-containing polymer (D-2) is a rubber-containing polymer obtained by polymerizing a monomer component (D-2-b) containing an alkyl methacrylate as a main component in the presence of the rubber polymer (D2a). A polymer is preferred.

  In addition to the alkyl methacrylate, the monomer component (D-2-b) is described as another monomer having a double bond copolymerizable therewith (for example, a thermoplastic polymer (D-1)). Things). Moreover, the monomer component (D-2-b) can contain a chain transfer agent. As a chain transfer agent, the thing similar to what was described by the thermoplastic polymer (D-1) can be used, for example.

<Method for producing rubber-containing polymer (D-2)>
Examples of the method for producing the rubber-containing polymer (D-2) include a sequential multistage emulsion polymerization method. Moreover, as a manufacturing method of a rubber containing polymer (D-2), a monomer component (D-2-b) is sequentially multistage emulsified as needed, for example in presence of rubber-like polymer (D2a). An emulsion suspension polymerization method in which, after polymerization, further monomer components are further polymerized, it is converted into a suspension polymerization system.

  Examples of the method for producing the rubber-containing polymer (D-2) by the sequential multistage emulsion polymerization method include, for example, a monomer component (D-2-a), water and an interface for obtaining the rubber-like polymer (D2a). An emulsion prepared by mixing an activator is supplied to the reactor for polymerization, and then the monomer component (D-2-b) is sequentially supplied to the reactor for polymerization.

  The acrylic resin film obtained by using the rubber-containing polymer (D-2) obtained by the above method is preferable in that it has a characteristic that the number of fish eyes in the film is small.

  Examples of the surfactant used when producing the rubber-containing polymer (D-2) by the sequential multi-stage emulsion polymerization method include anionic, cationic and nonionic surfactants. These can be used individually by 1 type or in combination of 2 or more types.

  As a method of preparing an emulsion by mixing the monomer component (D-2-a), water and a surfactant, for example, after charging the monomer component (D-2-a) in water, A method of charging a surfactant; a method of charging a monomer component (D-2-a) after charging the surfactant into water; and a surfactant in the monomer component (D-2-a) There is a method of adding water after charging.

  The latex of the obtained rubber-containing polymer (D-2) can be treated using a filtration device provided with a filter medium, if necessary. In this filtration treatment, removal of the scale generated during the polymerization from the latex of the rubber-containing polymer (D-2) is used for removing impurities mixed in from the polymerization raw material or during the polymerization.

  The rubber-containing polymer (D-2) can be obtained as a powder by recovering from the latex containing the rubber-containing polymer (D-2).

  Examples of a method for recovering the rubber-containing polymer (D-2) from the latex containing the rubber-containing polymer (D-2) include a salting out coagulation method by acid precipitation, a spray drying method, and a freeze drying method. .

  When the rubber-containing polymer (D-2) is recovered by a coagulation method by salting out using a metal salt, the residual metal content in the finally obtained rubber-containing polymer (D-2) is determined. It is preferable to make it 800 ppm or less, and it is so preferable that content of a residual metal is small.

  As a polymerization initiator used when superposing | polymerizing the monomer component in a rubber containing polymer (D-2), it does not restrict | limit in particular, For example, a well-known thing can be used. Examples of the method for adding the polymerization initiator include a method of adding to one of the aqueous phase and the monomer phase, or a method of adding to both.

  Examples of the polymerization initiator include peroxides, azo initiators, and peroxides that are redox initiators in which an azo initiator is combined with an oxidizing agent / reducing agent.

  The polymerization temperature for obtaining the latex containing the rubber-containing polymer (D-2) varies depending on the type and amount of the polymerization initiator used, and examples thereof include 40 to 120 ° C.

<Film>
The film of this embodiment can be obtained by molding a polycarbonate resin composition containing at least a polycarbonate resin (A), a fluorescent dye (B), and a white pigment (C).

  The laminated film of this embodiment has the film of this embodiment and an acrylic resin layer disposed on at least one surface of the film.

  The retroreflective sheet of the present embodiment includes a reflective element layer and a skin layer disposed on the reflective element layer, and the laminated film of the present embodiment is used as the skin layer. In this form, it is preferable that the polycarbonate resin film faces the reflective element layer and the acrylic resin film becomes the outer layer.

  The retroreflective sheet using the laminated film of the present embodiment as the skin layer is excellent in visibility because of excellent brightness, and has little change in appearance even when exposed to a long-term weather resistance test or outdoors, It has good weather resistance.

  In the laminated film of this embodiment, the chromaticity coordinates (x, y) in the XYZ color system when measured under the following measurement conditions are any of the chromaticity coordinates (x, y) in ASTM D4956 described above. It is preferable to satisfy these conditions.

  Measurement conditions: The laminated film and a standard white plate are overlapped, and the acrylic resin layer side of the laminated film is measured with 0 ° illumination for reflection measurement, 45 ° circumferential light reception, standard light D65, and 2 ° visual field. The standard white plate used here has XYZ in the XYZ color system of X = 93. When measured with 0 ° illumination for reflection measurement, 45 ° circumferential light reception, standard light C, and 2 ° field of view. 96, Y = 95.90, Z = 113.05.

  The laminated film has chromaticity coordinates (x, y) of (0.387, 0.610), (0.369, 0.546), (0.428, 0. 496) and (0.460, 0.540) are more preferable.

  The acrylic resin layer may be disposed only on one side of the film of the present embodiment (also referred to as a polycarbonate resin film), or may be disposed on both sides.

  The thickness of the laminated film is preferably 30 to 500 μm. When the thickness of the laminated film is 30 μm or more, handling of the laminated film becomes easy. Moreover, if the thickness of a laminated film is 500 micrometers or less, manufacturing cost can be suppressed. The thickness of the laminated film is more preferably 60 to 450 μm, and further preferably 70 to 400 μm.

  The thickness of the film of this embodiment is preferably 20 to 450 μm. If the thickness of the film of this embodiment is 20 μm or more, sufficient toughness can be effectively imparted to the laminated film. If the thickness of the film of this embodiment is 450 micrometers or less, manufacturing cost can be suppressed. As for the thickness of the film of this embodiment, it is more preferable that it is 40-400 micrometers, and it is further more preferable that it is 50-350 micrometers.

  The polycarbonate resin film may be composed of a single layer or a plurality of layers.

  The thickness of the acrylic resin layer is preferably 10 to 200 μm. If the thickness of the acrylic resin layer is 10 μm or more, the polycarbonate resin film and the fluorescent dye can be more effectively protected. If the thickness of the acrylic resin layer is 200 μm or less, the manufacturing cost can be suppressed. The thickness of the acrylic resin layer is more preferably 15 to 150 μm, and further preferably 20 to 100 μm.

  The acrylic resin layer may be composed of a single layer or a plurality of layers.

  The haze of the laminated film is preferably 0.10% or more and 25% or less. If the haze of the laminated film is from 0.10% to 25%, the visibility and retroreflective performance of the retroreflective sheet using the laminated film can be effectively ensured. The haze of the laminated film is more preferably 0.10% or more and 22% or less, and further preferably 0.10% or more and 19% or less.

<Method for producing laminated film>
It does not restrict | limit especially as a method of manufacturing the laminated | multilayer film of this embodiment, For example, well-known various methods can be used. As a method for producing a laminated film, for example, a method of forming a laminated structure composed of a polycarbonate resin composition and an acrylic resin composition by a coextrusion molding method via a feed block die or a multi-manifold die, or a polycarbonate resin composition And an acrylic resin composition, each of which is formed into a film using a melt extrusion method using a T-die, and the two kinds of films are laminated by a thermal laminating method. Moreover, the extrusion lamination method etc. etc. which make a polycarbonate resin composition into a film form and arrange | position on an polycarbonate resin film by a melt extrusion method after that are also mentioned. In this case, the polycarbonate resin composition and the acrylic resin composition may be exchanged. Alternatively, after the polycarbonate resin composition and the acrylic resin composition are each formed into a film shape, an adhesive layer and / or an adhesive layer may be provided and bonded together.

  In particular, from the viewpoint of economy and process simplification, it is preferable to form a laminated structure of a polycarbonate resin composition and an acrylic resin composition by a coextrusion molding method. Specifically, for example, a coextrusion molding method through a feed block die or a multi-manifold die as described above is particularly preferable.

  In addition, when melt extrusion is performed, the resin composition constituting each layer in a molten state is extruded while filtering with a screen mesh of 200 mesh or more in order to remove nuclei and foreign matters that cause poor appearance. Is preferred.

<Retroreflective sheet>
The types of retroreflective sheets include, for example, an encapsulated lens type retroreflective sheet, a capsule type retroreflective sheet in which glass beads subjected to aluminum vapor deposition are embedded in a substrate, and a prism using a resin sheet subjected to prism processing as a reflector. There is a type retroreflective sheet. The retroreflective sheet of this embodiment is not particularly limited, and may be any type.

  The retroreflective sheet having the laminated film of the present embodiment has chromaticity in the XYZ color system when measured under the conditions of standard light D65 and 2 ° field of view by 0 ° illumination of reflection measurement and 45 ° circumferential light reception. It is preferable that the coordinates (x, y) satisfy any one of the chromaticity coordinates (x, y) in ASTM D4956 described above. The retroreflective sheet of this embodiment preferably exhibits a yellowish green color, that is, the chromaticity coordinates (x, y) are (0.387, 0.610), (0.369, 0.546), (0. 428, 0.496) and (0.460, 0.540).

  The Y value of the retroreflective sheet exhibiting a yellowish green color according to this embodiment is preferably 45 or more under the measurement conditions. By setting the Y value to 45 or more, it is possible to further improve the visibility of the retroreflective sheet exhibiting a fluorescent color.

  Examples of the configuration of the retroreflective sheet include a configuration in which an acrylic resin layer, a polycarbonate resin film (film of the present embodiment), a reflective element layer, and a binder layer are formed in this order from the light incident direction. . Moreover, an acrylic resin layer is arrange | positioned on the surface for protection of a retroreflection sheet, and designability provision.

  On the back surface of the binder layer, a support layer can be disposed for the purpose of improving the strength of the retroreflective sheet, improving the dimensional stability, and preventing moisture and / or chemicals from entering. . Examples of the material constituting the support layer include resins, fibers, cloth, metal sheets such as stainless steel and aluminum. These may be used individually by 1 type and may be used in combination of 2 or more type.

  An adhesive layer and a release material layer for protecting the adhesive layer are provided on the back surface of the binder layer or the support layer in order to attach the retroreflective sheet to a metal plate, a wooden plate, a glass plate, a plastic plate, or the like. Is possible. The materials for the adhesive and the release material are not particularly limited and can be appropriately selected.

  For example, a capsule-type retroreflective sheet is manufactured as follows.

  First, the upper hemisphere portion of the glass beads is once embedded in the temporary support layer, and a metal film is deposited on one surface across the gap between the lower hemisphere portion of the beads and the beads, and then a support film made of a thermoplastic polymer in close contact therewith. Is formed by coating. Next, the surface is further covered with a film made of a heat-resistant resin, the temporary support layer on the opposite side is peeled off, and the laminated film of this embodiment is overlaid on the exposed upper hemisphere portion of the glass beads. Next, with a mold having a convex mesh pattern for creating a desired independent small compartment vacant space, it is heated and pressed from the film side made of heat-resistant resin, etc. Adhere closely. And the connection wall as the said pattern is formed, an independent subcompartment empty space is formed, and a capsule type retroreflection sheet is manufactured.

  Also, the above-mentioned prism processing may be performed directly on the polycarbonate resin film side of the laminated film, and the non-prism processed side may be used as the surface side, the prism processed side as the retroreflective element, and the laminated film may be used as it is as a prism type retroreflective sheet. it can. At this time, it is preferable to perform prism processing on the polycarbonate resin layer side, but prism processing may be performed on the acrylic resin layer side as necessary.

  As a method of processing a laminated film into a prism-type retroreflective sheet, for example, a laminated film having a microstructure is first produced by hot pressing, and the obtained laminated film and a binder layer or a binder layer and a support layer are integrated. There is a method of forming a hermetically sealed structure by passing the formed sheet between a mold roll having a mesh-like protrusion and a rubber roll.

(Example)
Hereinafter, the present invention will be described based on examples. In the following, “part” represents “part by mass”, and “%” represents “mass%”. The abbreviations used in the following description are as follows.

MMA: methyl methacrylate n-BA: n-butyl acrylate St: styrene 1,3-BD: 1,3-butylene glycol dimethacrylate AMA: allyl methacrylate CHP: cumene hydroperoxide t-BH: t-butyl hydroperoxide n -OM: n-octyl mercaptan EDTA: disodium ethylenediaminetetraacetate SFS: sodium formaldehyde sulfoxylate (Longalite)
RS610NA: Sodium polyoxyethylene alkyl ether phosphate (manufactured by Toho Chemical Co., Ltd., trade name: Phosphanol RS610NA)
Various evaluations on the laminated film and the retroreflective sheet were performed by the following methods.

(1) Optical properties of laminated film (total light transmittance and haze)
About the laminated film immediately after manufacture, the acrylic resin layer side was turned to the light source, and the total light transmittance and haze of the laminated film were measured.

  The haze was measured using NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7136.

(2) Initial chromaticity coordinates (x, y) of laminated film
XYZ in the XYZ color system when measured with 0 ° illumination for reflection measurement, 45 ° circumferential light reception, standard light C, and 2 ° visual field, respectively, X = 93.96, Y = 95.90, Z = A standard white plate showing 113.05 was prepared. The laminated film was placed on this standard white plate, and the chromaticity coordinates were measured on the acrylic resin layer side under conditions of standard light D65 and 2 ° visual field by 0 ° illumination of reflection measurement and 45 ° circumferential light reception. The obtained chromaticity coordinates (x, y) are (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540) was confirmed to be within the range surrounded by four points.

  The chromaticity coordinates (x, y) were measured using SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.

(3) Initial chromaticity coordinates (x, y) and Y value of retroreflective sheet A laminated film was bonded onto a commercially available prism-type retroreflective sheet (White) manufactured by 3M to prepare a retroreflective sheet. This retroreflective sheet is bonded to a stainless steel plate, and the chromaticity coordinates and Y value are measured on the acrylic resin layer side with 0 ° illumination for reflection measurement and 45 ° circumferential light reception under the conditions of standard light D65 and 2 ° visual field did. The obtained chromaticity coordinates (x, y) are (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540) was confirmed to be within the range surrounded by four points.

  The chromaticity coordinates (x, y) were measured using SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.

[Production Example 1]
<Adjustment of polycarbonate resin composition>
Fluorescent dye (B), white pigment (C) and antioxidant are added to 100 parts of polycarbonate resin (A) in the amounts shown in Table 1, and mixed using a Henschel mixer to obtain a polycarbonate resin composition. It was. As the fluorescent dye (B), a thioxanthene dye C.I. I. “DIMIC MBR-D70 (trade name)” manufactured by Dainichi Seika Kogyo Co., Ltd., consisting only of a single component of Solvent Yellow 98, was used. The white pigment (C) contains titanium oxide (particle diameter: about 20 nm, CI Pigment White 12) at 45% by mass (90% by mass when only the pigment component is 100% by mass). “DIMIC MBR-002 White (trade name)” manufactured by Kagaku Kogyo Co., Ltd. was used. Antioxidants include “Irganox 1076 (trade name)”, a hindered phenol-based antioxidant manufactured by BASF, and “Adekastab 2112 (trade name)”, a phosphite-based antioxidant, manufactured by ADEKA. Using.

  The polycarbonate resin composition was supplied to a degassing twin-screw kneading extruder (trade name: TEM-35B, manufactured by Toshiba Machine Co., Ltd.) heated to 290 ° C. and kneaded to obtain a pellet-like product of the polycarbonate resin composition. Obtained.

  As the polycarbonate resin (A), S-3000 (manufactured by Mitsubishi Engineering Plastics Co., Ltd., MVR = 14 cm 3/10 min (300 ° C., 1.2 kgf)) was used.

[Production Example 2]
<Adjustment of acrylic resin composition>
An ultraviolet absorber and an antioxidant were added to 100 parts of the acrylic resin (D) in the amounts shown in Table 1, and mixed using a Henschel mixer to obtain an acrylic resin composition. As the UV absorber, “TINUVIN 234 (trade name)” which is a benzotriazole UV absorber manufactured by BASF Corporation and “ADK STAB LA31” which is a benzotriazole UV absorber manufactured by ADEKA Corporation were used. As the antioxidant, “Irganox 1076 (trade name)” which is a hindered phenol antioxidant manufactured by BASF Corporation was used.

  The acrylic resin composition was supplied to a degassing twin-screw kneading extruder (Toshiba Machine Co., Ltd., trade name: TEM-35B) heated to 240 ° C., and kneaded to obtain a pellet-like product of the acrylic resin composition. Obtained.

  As the acrylic resin (D), Dianal BR-75 (manufactured by Mitsubishi Rayon Co., Ltd., reduced viscosity 0.060 l / g, JIS K 7191 load deflection temperature at 1.8 MPa, 89 ° C.) was used.

[Example 1]
The polycarbonate resin composition pellets and the acrylic resin composition pellets obtained in Production Example 1 and Production Example 2 were dried overnight at 80 ° C. in a dehumidifying dryer.

The dried pellets of the carbonate resin composition of Production Example 1 were supplied to a 40 mmφ single-screw extruder having a cylinder temperature of 270 to 320 ° C., and the dried pellets of the acrylic resin composition of Production Example 2 were subjected to a cylinder temperature of 230 to 260. Supplied to a 30 mmφ single-screw extruder at 30 ° C., individually melt-plasticized, supplied to a multi-manifold die heated to 260 ° C., and the polycarbonate resin side is in contact with a 140 ° C. first cooling roll and a 90 ° C. second cooling roll Thus, the film was conveyed to obtain a laminated film having a two-layer structure of a polycarbonate resin layer and an acrylic resin layer. As for the thickness of this laminated film, the polycarbonate resin layer was 150 μm, the acrylic resin layer was 50 μm, and the total thickness was 200 μm.
The haze of the obtained laminated film was 6.4% and was a film excellent in transparency. The chromaticity coordinates (x, y) are (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540). It was within the range surrounded by 4 points.

  Moreover, the polycarbonate resin film side of the obtained laminated film was bonded to the retroreflective sheet, and the chromaticity coordinates (x, y) measured from the acrylic resin layer side were (0.387, 0.610), (0. 369, 0.546), (0.428, 0.496) and (0.460, 0.540), and the Y value was 47.

  The results are shown in Table 1.

[Example 2]
A laminated film and a retroreflective sheet were produced and evaluated in the same manner as in Example 1 except that the white pigment (C) was added in the amount shown in Table 1.

  The haze of the obtained laminated film was 9.9% and was a transparent laminated film. The chromaticity coordinates (x, y) are (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540). It was within the range surrounded by 4 points.

  Moreover, the polycarbonate resin film side of the obtained laminated film was bonded to the retroreflective sheet, and the chromaticity coordinates (x, y) measured from the acrylic resin layer side were (0.387, 0.610), (0. 369, 0.546), (0.428, 0.496) and (0.460, 0.540), and the Y value was 51.

  The results are shown in Table 1.

[Example 3]
A laminated film and a retroreflective sheet were produced and evaluated in the same manner as in Example 1 except that the white pigment (C) was added in the amount shown in Table 1.

  The haze of the obtained laminated film was 15.5%, and was a transparent laminated film. The chromaticity coordinates (x, y) are (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540). It was within the range surrounded by 4 points.

  Moreover, the polycarbonate resin film side of the obtained laminated film was bonded to the retroreflective sheet, and the chromaticity coordinates (x, y) measured from the acrylic resin layer side were (0.387, 0.610), (0. 369, 0.546), (0.428, 0.496) and (0.460, 0.540), and the Y value was 55.

  The results are shown in Table 1.

[Example 4]
A laminated film and a retroreflective sheet were produced and evaluated in the same manner as in Example 1 except that the white pigment (C) was added in the amount shown in Table 1.

  The haze of the obtained laminated film was 26.2%, and the film was inferior in transparency. The chromaticity coordinates (x, y) are (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540). It was within the range surrounded by 4 points.

  Moreover, the polycarbonate resin film side of the obtained laminated film was bonded to the retroreflective sheet, and the chromaticity coordinates (x, y) measured from the acrylic resin layer side were (0.387, 0.610), (0. 369, 0.546), (0.428, 0.496) and (0.460, 0.540), and the Y value was 62.

  The results are shown in Table 1.

[Example 5]
A laminated film and a retroreflective sheet were produced and evaluated in the same manner as in Example 1 except that the white pigment (C) was added in the amount shown in Table 1.

  The haze of the obtained laminated film was 38.3%, and the film was inferior in transparency. The chromaticity coordinates (x, y) are (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540). It was within the range surrounded by 4 points.

  Moreover, the polycarbonate resin film side of the obtained laminated film was bonded to the retroreflective sheet, and the chromaticity coordinates (x, y) measured from the acrylic resin layer side were (0.387, 0.610), (0. 369, 0.546), (0.428, 0.496) and (0.460, 0.540), and the Y value was 67.

  The results are shown in Table 1.

[Comparative example]
A laminated film and a retroreflective sheet were produced and evaluated in the same manner as in Example 1 except that the white pigment (C) was not added.

  The haze of the obtained laminated film was 3.3% and was a film excellent in transparency. The chromaticity coordinates (x, y) are (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540). It was within the range surrounded by 4 points.

  Moreover, the polycarbonate resin film side of the obtained laminated film was bonded to the retroreflective sheet, and the chromaticity coordinates (x, y) measured from the acrylic resin layer side were (0.387, 0.610), (0. 369, 0.546), (0.428, 0.496) and (0.460, 0.540), and the Y value is 41, resulting in inferior luminance. It was.

  The results are shown in Table 1.

  As described above, according to this embodiment, it is possible to provide a laminated film that can obtain a retroreflective sheet having fluorescence, excellent weather resistance, and excellent visibility. Moreover, according to this embodiment, the retroreflection sheet excellent in weather resistance, visibility, and retroreflection performance can be provided.

Claims (12)

Including polycarbonate resin (A), fluorescent dye (B) and white pigment (C),
The content of the fluorescent dye (B) is 0.10 parts by mass or more and 3.00 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A).
Content of the said white pigment (C) is 0.03 mass part or more and 3.00 mass part or less with respect to 100 mass parts of said polycarbonate resins (A).   The film according to claim 1, wherein the content of the polycarbonate resin (A) in the film is 85% by mass or more.   The fluorescent dye (B) is at least one selected from the group consisting of thioxanthene dyes, thioindigoid dyes, anthraquinone dyes, benzoxazole coumarin dyes, perylene dyes, peryleneimide dyes, and benzopyran dyes. The film according to claim 1 or 2.   The film according to any one of claims 1 to 3, wherein the white pigment (C) contains titanium oxide.   A laminated film comprising the film according to claim 1 and an acrylic resin layer disposed on at least one surface of the film.   The laminated film according to claim 5, wherein the haze is 0.10% or more and 25% or less. The chromaticity coordinates (x, y) in the XYZ color system under the following measurement conditions are (0.387, 0.610), (0.369, 0.546), (0.428, 0.496). And (0.460, 0.540), a laminated film according to claim 5 or 6 within a range surrounded by four points;
Measurement conditions: The laminated film and a standard white plate are overlapped, and the acrylic resin layer side of the laminated film is measured with 0 ° illumination for reflection measurement, 45 ° circumferential light reception, standard light D65, and 2 ° visual field. When the standard white plate was measured with 0 ° illumination for reflection measurement, 45 ° circumferential light reception, standard light C, and 2 ° field of view, XYZ in the XYZ color system was X = 93.96, Y = 95.90, Z = 113.05.   A retroreflective sheet comprising a reflective element layer and a skin layer disposed on the reflective element layer, wherein the laminated film according to claim 1 is used as the skin layer.   The retroreflection sheet according to claim 8, wherein the acrylic resin layer is an outer layer of the laminated film.   The chromaticity coordinates (x, y) in the XYZ color system when measured from the acrylic resin layer side under the conditions of standard light D65 and 2 ° field of view by 0 ° illumination of reflection measurement and 45 ° circumferential light reception , (0.387, 0.610), (0.369, 0.546), (0.428, 0.496) and (0.460, 0.540). The retroreflective sheet according to claim 9.   The retroreflective sheet according to claim 10, wherein the Y value in the XYZ color system of the retroreflective sheet measured under the above conditions is 45 or more.   The retroreflective sheet according to claim 8, wherein the reflective element layer is a bead-shaped lens or a prism-shaped lens.