JP6583006B2 - Colored acrylic resin film - Google Patents

Description

  The present invention relates to a transparent and colored acrylic resin film that protects the surface of a retroreflective sheet or the like used for signboards, road signs, and the like, and relates to an acrylic resin film that can impart designability to a substrate.

Retroreflective sheets that reflect incident light toward the direction of the light source are used in various fields by utilizing the retroreflective property and excellent visibility at night. For example, road signs and construction signs using retroreflective sheets reflect light from the headlight of a traveling vehicle toward the light source direction, i.e. the direction of the traveling vehicle, at night. It has excellent characteristics of providing excellent visibility to a driver of a vehicle and enabling clear information transmission.
Retroreflective sheets used as such road signs, construction signs, etc. are colored to improve visibility, and further, characters and patterns are directly screen printed on the colored retroreflective sheets. It is formed by.

There are white, yellow, red, yellow-red, green, and blue as the types of colors of the colored retroreflective sheeting. For each color, the color range and the lower limit of the luminance rate (β) are defined in the standard. . For example, in the case of the JIS standard, the color of the green retroreflective sheet according to JIS Z9117, and the color and the light receiving geometric condition a (45 ° illumination, vertical light reception) stipulated in JIS Z8722 The chromaticity coordinates (x, y) in the XYZ color system when measured in (0.1, 0.492), (0.191, 0.441), (0.157, 0.379) And (0.116, 0.387), and the lower limit of the luminance rate (β) is determined to be 0.04. Here, the luminance rate (β) is a value indicating the ratio of the sample luminance to the value of 1.00 as the value of the complete diffuse reflection surface.
Further, in ASTM D4956, the color of the green retroreflective sheet is such that the chromaticity coordinates (x, y) in the XYZ color system are (0.026, 0.399), (0.166, 0.364), It is within the range of (0.286, 0.446) and (0.207, 0.771), and the lower limit value of the Y value is set to 3.0.

As a method of obtaining the colored retroreflective sheet as described above, it is obtained by kneading a colorant in any of the steps up to the production of the film in addition to the method of coloring the surface layer of the retroreflective sheet by printing. A method of laminating the colored film as a protective layer on the substrate of the retroreflective sheet is conceivable. Among these methods, the latter is preferable in consideration of the reflection performance and manufacturing cost of the retroreflective sheet.
As a cover film for a retroreflective sheet, XYZ when measured under the condition of standard light D65 under the illumination and light reception geometric condition a (45 ° illumination, vertical light reception) specified in JIS Z8722 in Patent Document 1. A colored acrylic resin film for a retroreflective sheeting skin in which chromaticity coordinates (x, y) and Y value in a color system are controlled is disclosed.

JP 2005-126517 A

  An object of the present invention is to provide a colored acrylic resin film that, when used as a retroreflective sheet, satisfies the standard as a retroreflective sheet, and can easily distinguish the color.

  The present inventors have found that the colored acrylic resin film disclosed in Patent Document 1 has good visibility but has poor visibility and contrast when the retroreflective sheet to be laminated is white. In the case of producing a green colored acrylic resin film, the present inventors also colored with a colorant and, if necessary, a complementary colorant so that the total light transmittance, haze, and Y value fall within a certain range. It has been found that when used as a retroreflective sheet, the visibility becomes high, and particularly when a white retroreflective sheet is overlaid, a highly visible colored acrylic resin film can be obtained, and the present invention has been achieved. did.

That is, the present invention provides the following inventions.
[1] A colored acrylic resin film that satisfies the following conditions (1) to (3) when the thickness is 50 to 100 μm;
(1) The total light transmittance is 22 to 35% when measured by the method specified in ISO 13468-1.
(2) The haze is 2.0 to 4.0% when measured by the method specified in ISO 14782-1.
(3) The colored acrylic resin film is superposed on a mouse-colored oil-colored paper whose Munsell symbol is N5.5, and the colored acrylic resin film side is illuminated and received in geometric conditions a (45 °) as defined in JIS Z8722. The chromaticity coordinates (x, y) in the XYZ color system when measured under the conditions of the standard light D65 by illumination and vertical light reception are (0.016, 0.381), (0.185, 0 .340), (0.317,0.436), and (0.224,0.806), with a Y value of 3-5.
[2] The colored acrylic resin film according to the above [1], containing at least one selected from the group consisting of phthalocyanine colorants, condensed polycyclic colorants, and inorganic colorants.
[3] The colored acrylic resin film according to the above [1] or [2], wherein the acrylic resin component comprises a rubber-containing polymer.
[4] A skin material for the retroreflective sheet, including the colored acrylic resin film according to [1].
[5] A retroreflective material obtained by laminating the colored acrylic resin film according to any one of [1] to [3] or the skin material according to claim 4 and a white retroreflective sheet.
[6] A method for producing a colored acrylic resin film, wherein a phthalocyanine-based colorant (for example, CI Pigment Green 7) and another colorant are combined with an acrylic resin so as to satisfy the following conditions when the thickness is 50 to 100 μm. Including mixing into:
(1) The total light transmittance is 22 to 35% when measured by the method specified in ISO 13468-1.
(2) The haze is 2.0 to 4.0% when measured by the method specified in ISO 14782-1.
(3) The colored acrylic resin film is superposed on a mouse-colored oil-colored paper whose Munsell symbol is N5.5, and the colored acrylic resin film side is illuminated and received in geometric conditions a (45 °) as defined in JIS Z8722. The chromaticity coordinates (x, y) in the XYZ color system when measured under the conditions of the standard light D65 by illumination and vertical light reception are (0.016, 0.381), (0.185, 0 .340), (0.317,0.436) and (0.224,0.806), and the Y value is 3-5.
[7] A method for producing a retroreflective material, in which a colored acrylic resin film is obtained by the method described in [6] above, and the obtained film or a skin material including the same is laminated on a white retroreflective sheet. Including the method.

  The colored acrylic resin film of the present invention has high visibility when laminated on a retroreflective sheet, particularly when laminated on a white retroreflective sheet. The colored acrylic resin film of the present invention satisfies the required reflection performance when applied to a retroreflective sheet.

It is a graph which shows the range of the chromaticity coordinate (x, y) in the XYZ color system which the colored acrylic resin film for retroreflective sheet | seats of this invention should have fundamentally.

<Colored acrylic resin film>
The colored acrylic resin film of the present invention has a thickness of 50 μm to 100 μm, and the colored acrylic resin film is superposed on a gray-colored oily colored paper having a Munsell symbol of N5.5, and the colored acrylic resin film side is defined in JIS Z8722. The chromaticity coordinates (x, y) in the XYZ color system when measured under the condition of the standard light D65 under the illumination and light reception geometric condition a (45 ° illumination, vertical light reception) is (0.016). , 0.381), (0.185, 0.340), (0.317, 0.436) and (0.224, 0.806).
Here, “the range of (0.016, 0.381), (0.185, 0.340), (0.317, 0.436) and (0.224, 0.806)” is a figure. 1, (0.016, 0.381), (0.185, 0.340), (0.317, 0.436), (0.224, chromaticity coordinates (x, y)) 0.806) and the first (0.016, 0.381) coordinates are connected to each other by a straight line in order (that is, a region defined by a quadrangle having the four points as vertices).
When a colored acrylic resin film having chromaticity coordinates (x, y) in this range is used as the skin material of the retroreflective sheet, the retroreflective sheet can satisfy the hue described in, for example, JIS Z9117, and reflect The visibility of the sheet can be increased.
Preferred chromaticity coordinate (x, y) ranges are (0.016, 0.381), (0.185, 0.340), (0.317, 0.436) and (0.224, 0. 806), more preferably in the range of (0.056, 0.389), (0.166, 0.364), (0.286, 0.446) and (0.219, 0.720), Most preferably, it is in the range of (0.100, 0.410), (0.166, 0.400), (0.260, 0.500) and (0.230, 0.620).
Note that the illumination and light receiving geometric conditions a defined in JIS Z8722 amended on March 20, 2009 are defined as follows. Geometric condition a [symbol: when the direction of irradiation light is one direction (45 ° x: 0 °), when there are multiple directions (45 ° c: 0 °), when it is all directions (45 ° a: 0 °). The sample is irradiated with one or more beam bundles having an angle of 45 ± 2 ° with respect to the normal of the sample surface, and the reflected light is received in a direction whose angle to the normal of the sample is 10 ° or less. In this case, the irradiated and received light bundles should not contain rays having an inclination of 8 ° or more with respect to the respective center lines. It is desirable that the direction of light reception does not coincide with the normal line of the sample.

  As an oily colored paper with a Munsell symbol of N5.5, the mouse color (Munsell symbol: N5.5) of the standard color card 230 of Nippon Color Research Co., Ltd. can be used. In the present invention, the color of the transparent colored acrylic resin film is evaluated by superimposing the oil-colored paper.

The Y value of the colored acrylic resin film of the present invention is such that the colored acrylic resin film is superposed on an oily colored paper with a Munsell symbol of N5.5 and the colored acrylic resin film side is illuminated and received by JIS Z8722. It is a value (Y value of tristimulus values XYZ) measured under the condition of standard light D65 under geometric condition a (45 ° illumination, vertical light reception), and this Y value must be 3-5 .
If the Y value is 3 or more, when the colored acrylic resin film is used as the skin material of the retroreflective sheet, the hue of the retroreflective sheet can satisfy the standard of ASTM D4956 and used for road signs and the like. In this case, the visibility becomes good. In addition, when the Y value is 5 or less, the contrast becomes strong particularly when superimposed on a white retroreflective sheet. Therefore, when used for a road sign or the like, the visibility is improved.
A preferred Y value range is in the range of 3-5, more preferably in the range of 3.2-4.8, and most preferably in the range of 3.2-4.6. According to JIS Z9117, white has chromaticity coordinates (x, y) in the XYZ color system of (0.274, 0.329), (0.303, 0.300), (0. 368, 0.366) and (0.340, 0.393), and the lower limit of the β value is 0.27%.

The total light transmittance of the colored acrylic resin film of the present invention is 22 to 35% as measured by ISO 13468-1 (JIS K7361-1). When the total light transmittance is 22% or more, the retroreflective sheet manufactured using the colored acrylic resin film as a skin material can satisfy the reflection performance. Moreover, if the total light transmittance is 35% or less, the contrast of the retroreflective sheet manufactured using the colored acrylic resin film as a skin material can be increased.
A preferable range of the total light transmittance is in the range of 22 to 35%, more preferably in the range of 23 to 34%, and most preferably in the range of 24 to 33%.
In addition, in ISO 13468-1 (JIS K7361-1) in 1996, measurement is performed using a single beam photometer equipped with a light source and a photo detector specified by the CIE standard. The measuring device consists of a stabilized light source, an optical system combined therewith, and an integrating sphere with a photometer and an aperture.

The haze of the colored acrylic resin film of the present invention is 2.0 to 4.0% when measured by the method specified in ISO 14782-1 (JIS K7136). When the haze is 2.0% or more, the contrast of the retroreflective sheet produced using the colored acrylic resin film as a skin material can be increased. If the haze is 4.0% or less, the retroreflective sheet manufactured using the colored acrylic resin film as a skin material can satisfy the reflection performance.
A preferred haze range is 2.0-4.0%, preferably 2.4-4.0%, more preferably 2.5-3.7%, most preferably 2.8. Is in the range of ~ 3.5%.
Incidentally, ISO 14782-1 (JIS K7136) in 1999 stipulates how to obtain haze, which is a specific optical property relating to wide-angle scattering of light rays. The measuring device is composed of a stable light source, a connecting optical system, an integrating sphere having an aperture, and a photometer, and the photometer is composed of a light receiver, a signal processing device, a display device, and a recorder. The light source and photometer used are photopic standard luminous efficiency V (λ) (defined in IEC 60050-845) through which the combination characteristics are equal to the color matching function y (λ) according to ISO / CIE 10527. ) And an output corresponding to a combination of CIE standard light D65 defined in ISO / CIE 10526.

  As described above, the colored acrylic resin film of the present invention has a total light transmittance of 22 to 35% when measured with ISO 13468-1, and a haze measured with a method defined by ISO 14782-1 is 2.0 to 2.0. 4.0%, and colored acrylic resin film and a mule-colored oil-based colored paper with Munsell symbol N5.5 are overlapped, and the colored acrylic resin film side is geometrical conditions for illumination and light reception as defined in JIS Z8722 The chromaticity coordinates (x, y) in the XYZ color system when measured under standard light D65 conditions by a (45 ° illumination, vertical light reception) are (0.016, 0.381), (0. 185, 0.340), (0.317, 0.436), and (0.224, 0.806), and by setting the Y value to 3-5, the recursion was used as the skin material. Reflective sheet The phases can be strongly contrast while satisfying both standards of JIS Z9117 and ASTM D4956. Thereby, the colored acrylic resin film of this invention brings about favorable visibility, especially when laminated | stacked and used for a white retroreflection sheet. In a preferred embodiment, a colored acrylic resin film and a gray-colored oil-based colored paper having a Munsell symbol of N5.5 are used, wherein the total light transmittance is in the range of 24 to 33%, the haze is in the range of 2.4 to 4.0%. In the XYZ color system when the superimposed acrylic resin film side is measured under the conditions of standard light D65 under the illumination and light reception geometric conditions a (45 ° illumination, vertical light reception) specified in JIS Z8722. Chromaticity coordinates (x, y) of (0.016, 0.381), (0.185, 0.340), (0.317, 0.436) and (0.224, 0.806) Within the range, the Y value can be 3-5.

  Thus, the total light transmittance when measured with ISO 13468-1 is 24 to 33%, the haze measured with the method specified in ISO 14782-1 is within the range of 2.0 to 4.0%, and The colored acrylic resin film side is superposed on a mule-colored oil-colored paper with a Munsell symbol of N5.5, and the colored acrylic resin film side is standardized according to illumination and light reception geometric conditions a (45 ° illumination, vertical light reception) specified in JIS Z8722. By setting the Y value when measured under the condition of light D65 to 3 to 5, the colored acrylic resin film of the present invention provides good visibility when used by being laminated on a white retroreflective sheet.

  The chromaticity coordinates (x, y), Y value, total light transmittance, and haze in the XYZ color system described above are values when the thickness of the colored acrylic resin film is 50 μm to 100 μm.

<Acrylic resin>
The colored acrylic resin film of the present invention is a film made of an acrylic resin composition containing an acrylic resin as a main component and a colorant or the like added thereto. By using the acrylic resin, it is possible to impart excellent weather resistance to the film.
Although the preferable acrylic resin used for the colored acrylic resin film of this invention contains a rubber containing polymer, it is preferable that this rubber containing polymer is a rubber containing polymer (G) shown below.

Hereinafter, the acrylic resin of a preferable form is demonstrated concretely. In the following description, “alkyl acrylate” and “alkyl methacrylate” mean an alkyl ester of acrylic acid and an alkyl ester of methacrylic acid, respectively.
The “alkyl (meth) acrylate” means alkyl acrylate and / or alkyl methacrylate.

  The rubber-containing polymer (G) comprises a step of producing a rubber polymer (A) by polymerizing a monomer component (a) containing 30% by mass or more of an alkyl acrylate, and the rubber polymer (A). It is a polymer produced through a step of polymerizing a monomer component (b) containing 51% by mass or more of alkyl methacrylate in the presence. The monomer component (a) is preferably a component having a glass transition temperature (Tg) of −50 to 25 ° C. of a polymer obtained by polymerizing it alone. Moreover, it is preferable that a monomer component (b) is a component from which Tg of the polymer obtained by superposing | polymerizing it independently becomes 70-120 degreeC.

Prior to the polymerization of the monomer component (a), a step of emulsion polymerization of the component (s) having a Tg of 70 to 120 ° C. obtained by polymerizing the monomer component alone can be included. Moreover, the process of emulsion-polymerizing monomer component (c) etc. as needed is included between the emulsion polymerization process of monomer component (a) and the emulsion polymerization process of monomer component (b). Can do.
Moreover, the acrylic resin (A) containing the rubber-containing polymer used in the present invention can contain a thermoplastic polymer in addition to the rubber-containing polymer (G).

The thermoplastic polymer contains 50 to 100% by mass of an alkyl methacrylate unit having an alkyl group having 1 to 4 carbon atoms and 0 to 50% by mass of at least one other vinyl monomer unit. And a reduced viscosity of 0.1 L / g or less. The reduced viscosity is measured at 25 ° C. by dissolving 0.1 g of the polymer in 100 ml of chloroform.
The content of the alkyl methacrylate unit is preferably 70 to 100% by mass. The thermoplastic polymer preferably has a Tg of 80 to 110 ° C. Specific examples of such a thermoplastic polymer include “Acrypet VH”, “Acrypet MD”, and “Acrypet MF” (all trade names) manufactured by Mitsubishi Rayon Co., Ltd.
The ratio of the content of the rubber-containing polymer (G) and the thermoplastic polymer in the acrylic resin (A) is preferably 95: 5 to 5:95 (% by mass).

[Method for producing rubber-containing polymer (G)]
As a method for producing the rubber-containing polymer (G), the monomer component is first described, and then the polymerization method is described.

[Monomer component (a)]
The monomer component (a) is a monomer mixture containing 30% by mass or more of alkyl acrylate based on 100% by mass of the total amount of monomers, and is a monomer that is a raw material for the first stage polymerization It is a mixture. A rubber polymer (A) is produced by polymerizing the monomer component (a) as a raw material.
As the alkyl acrylate (hereinafter sometimes referred to as “monomer (a1)”), the alkyl group may be linear or branched. Examples include methyl acrylate, ethyl acrylate, n-, i-propyl acrylate, n-, i-, t-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate.
Of these, n-butyl acrylate is preferred. These may be used alone or in combination of two or more.

  As monomers other than alkyl acrylate in monomer component (a), alkyl methacrylate (hereinafter sometimes referred to as “monomer (a2)”), other monofunctional monomers ( Hereinafter, there may be mentioned “monofunctional monomer (a3)”) and polyfunctional monomer (hereinafter, sometimes referred to as “polyfunctional monomer (a4)”). .

  Examples of the alkyl methacrylate include those in which the alkyl group is linear or branched. Examples include methyl methacrylate, ethyl methacrylate, n-, i-propyl methacrylate and n-, i-, t-butyl methacrylate. These may be used alone or in combination of two or more.

  Examples of the monofunctional monomer (a3) include acrylic monomers such as 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 may be used alone or in combination of two or more.

Examples of the polyfunctional monomer (a4) include ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, di Di (meth) acrylate alkylene glycols such as propylene glycol (meth) acrylate; polyvinylbenzenes such as divinylbenzene and trivinylbenzene; cyanurate monomers such as triallyl cyanurate and triallyl isocyanurate; and allyl methacrylate And allyl, methallyl or crotyl esters of α, β-unsaturated carboxylic acids or dicarboxylic acids such as
These may be used alone or in combination of two or more.

The content of each component in the monomer component (a) is preferably in the following range.
The alkyl acrylate is 30 to 99.9% by mass, the alkyl methacrylate is 0 to 69.9% by mass, the monofunctional monomer (a3) is 0 to 20% by mass, and the polyfunctional monomer (a4) is 0.1 to 10% by mass.

The Tg of the rubber polymer (A) is preferably −50 to 25 ° C. from the viewpoint of flexibility as a film.
In the present invention, Tg refers to a value calculated from the FOX equation using the values described in the polymer handbook (J. Brandrup, Interscience, 1989).
In addition, the content of the rubber polymer (A) in the rubber-containing polymer (G) is preferably 5 to 70% by mass from the viewpoint of film formability as a film.
The monomer component (a) in the rubber-containing polymer (G) may be polymerized in two or more stages.

[Monomer component (b)]
The monomer component (b) is a monomer mixture serving as a raw material for the final stage polymerization, and is a component involved in the moldability and mechanical properties of the rubber-containing polymer (G).
As the alkyl methacrylate in the monomer component (b), one or more monomers listed as “monomer (a2)” in the description of the monomer component (a) can be used.
Other monomers in the monomer component (b) may be alkyl acrylate and other monofunctional monomers (hereinafter referred to as “monofunctional monomer (b3)”). .).
As the alkyl acrylate, one or more monomers listed as “monomer (a1)” can be used.
As the monofunctional monomer (b3), one or more kinds of monomers listed as “monofunctional monomer (a3)” can be used.

The step of emulsion polymerization of the monomer component (b) can be performed in two or more steps.
The content of each component in the monomer component (b) is preferably in the following range.
The alkyl methacrylate is 51 to 100% by mass, the alkyl acrylate is 0 to 20% by mass, and the monofunctional monomer (b3) is 0 to 49% by mass.

  The amount of the monomer component (b) used in the total amount of the monomer components used in all the steps of the polymerization method is preferably 30 to 95% by mass from the viewpoint of film formability as a film.

[Monomer component (s)]
Prior to the step of polymerizing the monomer component (a) to produce the rubber polymer (A), the component (s) having a Tg of 70 to 120 ° C. obtained by polymerizing it alone is emulsified. A step of polymerizing can be included. Examples of the monomer component (s) include the same as the monomer component (b).

[Monomer component (c)]
Between the step of polymerizing the monomer component (a) to produce the rubber polymer (A) and the step of polymerizing the monomer component (b) in the presence of the rubber polymer (A) The step of emulsion polymerization of the monomer component (c) can be included.
As monomer component (c), alkyl acrylate 9.9-90 mass%, alkyl methacrylate 0-90 mass%, other monofunctional monomer 0-20 mass%, and polyfunctional monomer The mixture containing 0.1-10 mass% of bodies is mentioned.

As the other monofunctional monomer and polyfunctional monomer used here, the above-mentioned monofunctional monomer (a3) and polyfunctional monomer (a4) can be used.
The step of emulsion polymerization of the monomer component (c) can be performed in two or more steps. When polymerizing in two or more stages, the composition of the monomer component (c) may be the same or different. The monomer component (c) may contain a surfactant, and may be further mixed and stirred with water and supplied as an emulsion into the polymerization vessel.

[Polymerization method]
Examples of the method for producing the rubber-containing polymer (G) include a sequential multi-stage emulsion polymerization method. As a method of polymerizing in three stages, the monomer component (a) for obtaining the rubber-like polymer (A), water and a surfactant are mixed to form an emulsified liquid and supplied into the polymerization vessel for polymerization. Then, the monomer component (c) is supplied into the polymerization vessel for polymerization, and the monomer component (b), water and a surfactant are mixed to form an emulsion and supplied into the polymerization vessel. And a method of polymerization.
In addition, the process of supplying and polymerizing the monomer component (c) in the polymerization vessel is a process performed as necessary.

  The polymer product obtained by using the rubber-containing polymer (G) produced by the above method has an advantage that there are few coarse particles in the finally obtained polymer latex. In particular, the film is preferable in that it has less fish eyes.

Examples of the surfactant used in the production by the sequential multi-stage emulsion polymerization method include anionic, cationic and nonionic surfactants. These may be used alone or in combination of two or more.
Examples of the anionic surfactant include rosin soap, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroylsarcosate, dipotassium alkenyl succinate; sodium lauryl sulfate, etc. Sulfate ester salts; sulfonates such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate; and phosphorus such as sodium polyoxyethylene alkylphenyl ether phosphate, sodium polyoxyethylene alkyl ether phosphate Examples include acid ester salts.
Examples of these commercially available products include Eleminol NC-718 manufactured by Sanyo Chemical Industries, Ltd .; Phosphanol LO-529, Phosphanol RS-610NA, and Phosphanol RS-620NA manufactured by Toho Chemical Industry Co., Ltd. , Phosphanol RS-630NA, Phosphanol RS-640NA, Phosphanol RS-650NA, and Phosphanol RS-660NA; Latemul P-0407.

Examples of a method for preparing an emulsion by mixing a monomer component, water and a surfactant include the following methods (1) to (3).
(1) A method of adding a surfactant after charging a monomer component in water, (2) a method of adding a monomer component after charging a surfactant in water, and (3) a monomer. A method in which water is added after a surfactant is charged into the ingredients.

  Examples of a mixing apparatus for preparing an emulsion by mixing monomer components with water and a surfactant include a stirrer equipped with a stirring blade; a forced emulsification apparatus such as a homogenizer and a homomixer; and a membrane emulsification apparatus. Can be mentioned.

The emulsified liquid may be either a W / O type in which water droplets are dispersed in the monomer component oil or an O / W type dispersion in which oil droplets of the monomer component are dispersed in water. .
It is O / W type, and the diameter of the oil droplets in the dispersed phase is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 15 μm or less.

The amount of the surfactant used for the preparation of the emulsion is preferably 0.5 to 1.6 parts by mass when the total amount of monomer components in all stages of polymerization is 100 parts by mass.
In adjusting the particle size of the sequential multistage polymer, the particle size is usually adjusted by the amount of the first-stage surfactant used. However, in the present invention, in addition to the surfactant to be added to the monomer component, a small amount of surfactant can be used by adding the surfactant to water (aqueous medium) charged in advance in the polymerization vessel. The particle size of the rubber-containing polymer can be reduced.

  Known polymerization initiators and chain transfer agents used when the monomer component (a) and the monomer component (b) are polymerized, or when the monomer component (c) is further polymerized. Can be used. Examples of the method for adding the polymerization initiator and the chain transfer agent include a method of adding to either one of the aqueous phase and the monomer phase, or a method of adding to both phases.

Examples of the polymerization initiator include peroxides, azo initiators, and redox initiators.
The redox initiator is an initiator that combines a peroxide and an oxidizing agent or a reducing agent, and an initiator that combines an azo initiator and an oxidizing agent or a reducing agent. Specific examples include a sulfoxylate-based initiator in which ferrous sulfate, disodium ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate and hydroperoxide are combined.

  Examples of the chain transfer agent include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol and carbon tetrachloride. These may be used alone or in combination of two or more. An example is n-octyl mercaptan.

As a method for producing a latex of the rubber-containing polymer (G), a monomer component (a), water and a surfactant are mixed to form an emulsified liquid and then fed into the reactor for polymerization. A method in which a body component (c) is supplied into a reactor for polymerization, and further a monomer component (b), water and a surfactant are mixed to form an emulsion and then supplied into the reactor for polymerization. The method of manufacturing by is mentioned.
In this case, after raising the aqueous solution in the reactor containing ferrous sulfate, disodium ethylenediaminetetraacetate and sodium formaldehyde sulfoxylate dihydrate to the polymerization temperature, the monomer component (a), water And the emulsion mixed with the surfactant is fed into the reactor for polymerization, then the monomer component (c) is fed into the reactor for polymerization, and further the monomer component (b), water and A method of polymerizing by supplying an emulsion mixed with a surfactant into the reactor is preferred.

The polymerization temperature for obtaining the latex of the rubber-containing polymer (G) varies depending on the type and amount of the polymerization initiator used, but is, for example, about 40 to 120 ° C.
The latex of the rubber-containing polymer (G) obtained by the above method can be treated using a filtration device provided with a filter medium as necessary.

  The rubber-containing polymer (G) latex thus obtained can be used in various applications in the latex state. Further, the rubber-containing polymer (G) is recovered from the latex by a known method such as a salting-out coagulation method, an acid precipitation coagulation method, a freeze coagulation method, a spray drying method, and the like. It can be used as the powder of (G). Furthermore, this powder can be melt extruded and pelletized.

  When the rubber-containing polymer (G) is recovered by a coagulation method by salting out using a metal salt, the residual metal content in the finally obtained rubber-containing polymer (G) should be 800 ppm or less. The residual metal content is preferably as small as possible.

<Colorant>
Examples of the colorant include a colorant masterbatch in which a colorant component is blended using an acrylic resin as a binder, and a dry color in which a dispersant and a colorant component are blended. The colorant masterbatch here is a colorant masterbatch in which a colorant component is blended in a high concentration in a resin, and examples of the form include pellets and soft plate shapes.
The resin used as the binder is preferably the same or similar to the acrylic resin used for the colored acrylic resin film.
The dry color refers to a dispersible powder colorant, which is a colorant that is mechanically made into a fine powder by adding an appropriate dispersant. Preferred examples of the dispersant include calcium stearate and magnesium stearate, and these may be used alone or in combination of two or more.

Examples of the colorant component include phthalocyanine colorants, condensed polycyclic colorants, and inorganic colorants.
Examples of the phthalocyanine colorant include CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, and CI Pigment Green 38.
Examples of the condensed polycyclic colorant include CI Pigment Green 47.
Examples of the inorganic colorant include CI Pigment Green 17, CI Pigment Green 19, and CI Pigment Green 50.

In particular, a phthalocyanine colorant is preferable in terms of transparency and sharpness necessary as a skin material of the retroreflective sheet, and CI Pigment Green 7 is more preferable.
The CI Pigment Green 7 is industrially available as “DYMIC MBR 510” manufactured by Dainichi Seika Kogyo Co., Ltd. These colorant components may be used alone or in combination of two or more.

For the purpose of complementary colors, one or more colorants such as yellow, red, orange and black (hereinafter also referred to as “complementary colorants”) may be used.
Examples of the yellow colorant include, for example, condensed azo colorants such as Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 128; CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 1 CI Pigment Yellow 24, CI Pigment Yellow 99, CI Pigment Yellow 108, CI Pigment Yellow 123, CI Pigment Yellow 147, CI Pigment Yellow 199, CI Solvent 16

  Examples of the red colorant include condensed azo colorants such as CI Pigment Red 4, CI Pigment Red 166, CI Pigment Red 214, and CI Pigment Red 221; CI Pigment Red 1, CI Pigment Red 2, and CI Pigment Red , CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red7, Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11C, CI Pigment Red 11, C Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 31, CI Pigment Red 37, CI Pigment Red 32 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 49: 2, CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pig 57 CI Pigment Red 7: 1, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 114 , CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 171, CI Pigment Red 171, CI Pigment Red 171, CI Pigment Red 171, CI Pigment Red 171, CI Pigment Red 171 , CI Pigment Red 18 CI Pigment Red 187, CI Pigment Red 193, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 243, CI Pigment Red 245, CI Sold Di 24 177, CI Pigment Red 216, CI Disperse Red 22, CI Disperse Red 57, CI Disperse Red 60, CI Solvent Red 4, CI Solvent Red 9, CI Solvent Red 11, CI Sol Sol Red 11, CI Sol Sol 15 ent Red 111, CI Solvent Red 168, CI Solvent Red 207 and other anthraquinone-based colorants; CI Solvent Red 135, CI Solvent Red 179 and other perinone colorants; CI Disperse Red 122, CI Disperse Red Crystal 202 Diketopyrrolopyrrole colorants such as CI Disperse Red 254, CI Disperse Red 255, CI Disperse Red 264, and CI Disperse Red 272;

  Examples of the orange colorant include isoindolinone colorants such as CI Pigment Orange 61; diketopyrrolopyrrole colorants such as CI Disperse Orange 71 and CI Disperse Orange 73.

Examples of black colorants include organic colorants and inorganic colorants.
Examples of the organic colorant include aniline black such as CI Pigment Black 1, and perylene black such as CI Pigment Black 31.
Examples of the inorganic colorant include carbon black such as CI Pigment Black 7, CI Pigment Black 9, CI Pigment Black 31, iron black such as CI Pigment Black 11, and cobalt oxide pigment such as CI Pigment Black 13. It is done.

  In particular, it is preferable to use a combination of yellow, red, and black colorants in terms of transparency and sharpness required as a skin material for the retroreflective sheet, and CI Solvent Yellow 163, CI Pigment Yellow 110, and CI Pigment Red 177. , CI Pigment Black 7 is more preferably used in combination.

  The CI Solvent Yellow 163 is industrially available as “DYMIC MBR D-05 Yellow” manufactured by Dainichi Seika Kogyo Co., Ltd. and “ORACET Yellow GHS” manufactured by Ciba Specialty Chemicals Co., Ltd.

  CI Pigment Red 110 is “DYMIC MBR 443 Yellow” manufactured by Dainichi Seika Kogyo Co., Ltd., “CROMOPHTAL Yellow 2RLTS”, “CROMOPHTAL Yellow 2RLTS”, “CROMOPHTAL YINIR 3RT” manufactured by Ciba Specialty Chemicals Co., Ltd. “Yellow 2RLT”, “IRGAZIN Yellow 3RLTN”, “MICROLITH Yellow 3R-K / KP”, “MICROLITH Yellow 3R-WA”, “MICROLITH Yellow 2R-WA”, “MICROLENY Yellow 2R-TS” ”,“ UNISPERSE Yellow 2RL It is industrially available as -S ".

  CI Pigment Black 7 is industrially manufactured as “DYMIC MBR 717 Black”, “MICROLITH Black CK / KP”, “MICROLEN Black B-MC”, “MICROLEN Black 782-MC” manufactured by Dainichi Seika Kogyo Co., Ltd. It is available.

  For the purpose of complementary colors, colorants of other colors such as quinacridone, isoindoline, perylene, perinone, thioindigo, and quinophthalone may be added.

  In the colored acrylic resin film of the present invention, the complementary colorant is composed of a colored acrylic resin film and a mouse-colored oil-based colored paper whose Munsell symbol is N5.5, and the colored acrylic resin film side is illuminated and received by JIS Z8722. Chromaticity coordinates (x, y) in the XYZ color system when measured under the condition of standard light D65 under the geometric condition a (45 ° illumination, vertical light reception) of (0.016, 0. 381), (0.185, 0.340), (0.317, 0.436), and (0.224, 0.806).

  The concentration of the colorant contained in the colored acrylic resin film of the present invention is defined in JIS Z8722 by superposing the colored acrylic resin film and a gray colored oily colored paper having a Munsell symbol of N5.5. The chromaticity coordinates (x, y) in the XYZ color system when measured under the condition of the standard light D65 by the geometric condition a (45 ° illumination, vertical light reception) of illumination and light reception to be (0. 016, 0.381), (0.185, 0.340), (0.317, 0.436) and (0.224, 0.806), and the Y value is 3 to 5. What is necessary is just to make such a density | concentration.

For example, when a green colorant is used as a base, a yellow colorant and a red colorant can be used together as a complementary colorant for complementary coloration. At this time, the mixing ratio of the green / yellow / red colorant is 60 to 97/2 to 25/1 to 15. The yellow colorant may be a combination of a dye and a pigment. The red colorant is preferably a pigment in terms of controlling transparency while maintaining chromaticity coordinates (x, y).
If it is a combination of CI Pigment Green 7 / CI Solvent Yellow 163 / CI Pigment Red 177 / CI Pigment Yellow 110, a mixing ratio of 60 to 97/1 to 15/1 to 10/1 to 15 is preferable. the total amount is preferably from ^{1g / m 2 ~3g / m 2} , 1.5g / m 2 ~2.5g / m 2 is more preferable.

Further, based on a green colorant, complementary colors can be obtained by using a yellow colorant and a black colorant in combination as a complementary colorant. At this time, the mixing ratio of the green / yellow / black colorant is 70 to 98/1 to 20/1 to 10.
If it is a combination of CI Pigment Green 7 / CI Solvent Yellow 163 / CI Pigment Black 7, a mixing ratio of 70 to 98/1 to 20/1 to 10 is preferable, and the total amount of the colorant is 1 g / m ^{2 to} 4 g. / m ² are preferred, more preferably 1.5 g / m ² ～3.5G / m ^2, more preferably 2 g / m ² to 3 g / m ^2.
When the density | concentration of a coloring agent is too high, not only Y value falls, but transparency also falls and there exists a tendency for reflective performance important for a retroreflection sheet to fall. In addition, when the colorant concentration is too low, the color visibility tends to decrease.
That is, as described above, by mixing another colorant (complementary colorant) with a phthalocyanine-based colorant (for example, CI Pigment Green 7), the acrylic resin film has a chromaticity as defined above. Coordinates can be set, the Y value can be 3-5, the total light transmittance can be 24% to 33%, and the haze can be 2.0% to 4.0%. The visibility when used by being laminated on a sheet can be remarkably improved. A person skilled in the art can appropriately determine the amount of the colorant according to the thickness of the film.

<Manufacture of colored acrylic resin film>
Examples of the method for forming the colored acrylic resin film of the present invention include a known solution casting method, a melt extrusion method such as a T-die method, and an inflation method. Among these, the T-die method is preferable from the viewpoint of economy.
In addition, the colored acrylic resin film of the present invention may contain general compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact aids, foaming agents, fillers, antibacterial agents, if necessary. An anti-mold agent, a foaming agent, a release agent, an antistatic agent, a matting agent, an ultraviolet absorber and the like can be included.
In particular, in terms of protecting the base material (retroreflective sheet), it is preferable to add an ultraviolet absorber in order to impart weather resistance. The molecular weight of the ultraviolet absorber used is preferably 300 or more, more preferably 400 or more. When an ultraviolet absorber having a molecular weight of less than 300 is used, it may volatilize on a transfer roll or the like when producing a film, thereby causing roll contamination.
The UV absorber is preferably a benzotriazole type having a molecular weight of 400 or more or a triazine type having a molecular weight of 400 or more. Specific examples of the former include Tinuvin 234 from BASF Japan Ltd. Specific examples of the latter include Tinuvin 1577 from BASF Japan.
As a method for adding the compounding agent, a method of supplying the film forming machine for forming a film using an acrylic resin together with the acrylic resin, and a mixture in which the compounding agent is added to the acrylic resin in advance using various kneaders. There is a method of kneading and mixing.
Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, and roll kneaders.

The thickness of the colored acrylic resin film for the retroreflective sheeting of the present invention is preferably 10 to 500 μm in terms of film properties. If it is 10-500 micrometers, it will become moderate rigidity, lamination property, secondary workability, etc. will become favorable, and also film forming property will become stable and manufacture of a film will become easy.
More preferably, it is 30-200 micrometers, More preferably, it is 40-150 micrometers.

According to the present invention, for example, a method for producing a colored acrylic resin film, wherein a phthalocyanine-based colorant (for example, CI Pigment Green 7) and other coloring are used so as to satisfy the following conditions when the thickness is 50 to 100 μm. Including mixing an agent (complementary colorant) with the acrylic resin:
(1) The total light transmittance is 22 to 35% when measured by the method specified in ISO 13468-1.
(2) The haze is 2.0 to 4.0% when measured by the method specified in ISO 14782-1.
(3) The colored acrylic resin film is superposed on a mouse-colored oil-colored paper whose Munsell symbol is N5.5, and the colored acrylic resin film side is illuminated and received in geometric conditions a (45 °) as defined in JIS Z8722. The chromaticity coordinates (x, y) in the XYZ color system when measured under the conditions of the standard light D65 by illumination and vertical light reception are (0.016, 0.381), (0.185, 0 .340), (0.317,0.436) and (0.224,0.806), and the Y value is 3-5. By doing in this way, a colored acrylic resin film with high visibility, especially when laminated on a white retroreflective sheet, is obtained.

<Retroreflective sheet>
The retroreflective sheet having the colored acrylic resin film of the present invention on the surface is mainly used for a road sign, a display board, or a safety device for the purpose of visibility.
The types of retroreflective sheets include capsule-type retroreflective sheets in which glass beads subjected to aluminum vapor deposition are embedded in the base material, and prism-type retroreflective sheets that use a prism-processed resin sheet as a reflector. The colored acrylic resin film of the present invention is used by being laminated on the surface of the retroreflective sheet.

For example, a capsule-type retroreflective sheet is manufactured as follows.
The upper half of the glass bead is temporarily embedded in the temporary support layer, and a metal film is deposited on the entire surface across the gap between the lower hemisphere of the bead and the beads, and then a support film made of a thermoplastic resin is applied in close contact therewith. Then, the surface is further covered with a film made of a heat resistant resin or the like, the temporary support layer on the opposite side is peeled off, and the colored acrylic resin film of the present invention is overlaid on the upper hemisphere portion of the exposed glass beads. , By a mold having a convex mesh pattern for creating a desired independent small compartment vacant space, heat-pressed from the film side made of heat-resistant resin, etc. The capsule-type retroreflective sheet is manufactured by forming the connecting wall according to the pattern and forming the independent small compartment vacancies.
At this time, when the contact area between the support film and the colored acrylic resin film is large, reflection performance important as a retroreflective sheet tends to be impaired.

  The present invention provides a retroreflective material in which the colored acrylic resin film of the present invention and a white retroreflective sheet are laminated. Such retroreflective materials can be used for road signs, road accessories, vehicles, lower poles and railroad crossings, for example, for traffic safety and traffic smoothing in roads, tracks, tunnels, etc. it can. Such re-reflecting materials are also specified in JIS M7001, as safety equipment for disaster prevention at night or in dark places, safety signs specified in JIS Z9107, and JIS M7001 in factories, mines, construction works or other establishments. It can also be used for mine safety signs and safety caps.

Hereinafter, the present invention will be described by way of examples.
Here, “part” in Examples and Comparative Examples represents “part by mass”, and “%” represents “mass%”.
Abbreviations in the preparation examples are as follows.
Methyl methacrylate: MMA
n-butyl acrylate: BA
Methyl acrylate: MA
Styrene: ST
Allyl methacrylate: AMA
1,3-butylene glycol dimethacrylate: 1,3-BD
t-Butyl hydroperoxide: tBH
Cumene hydroperoxide: CHP
n-octyl mercaptan: nOM

  In Examples and Comparative Examples, evaluation of the prepared multilayer structure polymer and measurement of various physical properties of the colored acrylic resin film were carried out by the following test methods.

1) Mass average particle diameter of multilayer polymer:
The polymer latex of the multilayer polymer obtained by emulsion polymerization was measured and determined by a dynamic light scattering method using a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd.

2) Total light transmittance of the colored acrylic resin film:
The measurement was performed according to ISO 13468-1.

3) Haze of colored acrylic resin film:
It measured based on ISO 14782-1.

4) Chromaticity coordinates (x, y) and Y value of the colored acrylic resin film:
The standard color card 230 of NIPPON KENKEN CO., LTD. (Mouse color with Munsell symbol N5.5) and a colored acrylic resin film are overlaid, and the colored acrylic resin film side is the geometry of illumination and light reception specified in JIS Z8722. The measurement was performed under the condition of standard light D65 under the general condition a (45 ° illumination, vertical light reception).

5) Visibility 20 cm square of commercially available capsule lens type retroreflective sheet (white) (Nikka Polymer Co., Ltd. (trade name: Nikkalite ULS)) was pasted with a 10 cm square colored acrylic resin film.
The retroreflective sheet was installed perpendicular to the ground, the automobile was stopped at a distance of about 50 m from the retroreflective sheet, and the retroreflective article was observed from the driver's seat. As the light for illuminating the retroreflective sheet, the headlight of the automobile was used.
Based on the following scores, the visibility of a retroreflective material obtained by laminating a colored acrylic resin film on a white retroreflective sheet was evaluated.

Visibility score : A colored portion can be confirmed.
Δ: The colored part appears blurred or the color of the colored part is difficult to recognize.
X: The color of a colored part cannot be recognized.

(Preparation Example 1)
Production of rubber-containing polymer (I) In Preparation Example 1, a rubber-containing polymer (I) corresponding to the rubber-containing polymer (G) was produced.
After charging 10.8 parts of deionized water in a container equipped with a stirrer, a mixture comprising 0.3 part of MMA, 4.5 parts of BA, 0.2 part of 1,3-BD, 0.05 part of AMA and 0.025 part of CHP (Monomer component (a)) was put into a container and stirred and mixed at room temperature.
Next, with stirring, 1.1 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “Phosphanol RS610NA”) is charged into the container, and stirring is continued for 20 minutes to prepare “Emulsion 1”. did.
Next, 155.8 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 75 ° C. Further, a mixture was prepared by adding 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 2.0 parts of deionized water, and this mixture was put into a polymerization vessel. Subsequently, a solution prepared by adding 0.20 part of sodium formaldehyde sulfoxylate to 0.8 part of deionized water was put into the polymerization vessel at once.
Next, the emulsion 1 was dropped into the polymerization vessel over 8 minutes while stirring in a nitrogen atmosphere. Thereafter, the reaction was continued for 15 minutes to complete the polymerization of the rubber polymer (also referred to as an elastic polymer) (I-a1).

Subsequently, a mixture consisting of 1.5 parts of MMA, 22.5 parts of BA, 1.0 part of 1,3-BD, 0.25 part of AMA and 0.016 part of CHP was dropped into the polymerization vessel over 90 minutes. Thereafter, the reaction was continued for 60 minutes to produce an elastic polymer (I-a2). Thus, the elastic polymer (IA) containing the elastic polymer (I-a1) and the elastic polymer (I-a2) was obtained.
In addition, when each mixture for elastic polymer (I-a1) and elastic polymer (I-a2) is separately polymerized under the same conditions as described above, the elastic polymer (I-a1), The Tg of the elastic polymer (I-a2) was -48 ° C.

Subsequently, a mixture consisting of 6 parts of MMA, 4 parts of BA, 0.075 part of AMA and 0.0125 part of CHP was dropped into the polymerization vessel over 45 minutes. Thereafter, the reaction was continued for 60 minutes to form an intermediate polymer (IC).
When the mixture for the intermediate polymer (IC) was polymerized separately under the same conditions as described above, the Tg of the intermediate polymer (IC) was 20 ° C.

Subsequently, a mixture (monomer component (b)) consisting of 55.2 parts of MMA and 4.8 parts of BA, 0.22 part of nOM and 0.075 part of tBH was dropped into the polymerization vessel over 140 minutes. Thereafter, the reaction was continued for 140 minutes to form a hard polymer (IB) to obtain a polymer latex of the rubber-containing polymer (I). The mass average particle diameter measured after polymerization was 0.12 μm.
The resulting polymer latex of the rubber-containing polymer (I) was filtered using a vibration type filtration device in which a SUS mesh (average opening: 54 μm) was attached to the filter medium. Then, it salted out in the aqueous solution containing 3.0 parts of calcium acetate, washed with water, and the polymer was collect | recovered. Then, it dried and obtained powdery rubber-containing polymer (I).

[Examples 1-6, Comparative Examples 1-2]
To 100 parts of the rubber-containing polymer (I) obtained in Preparation Example 1, “ADEKA STAB LA-31RG (trade name)” manufactured by ADEKA Co., Ltd. as an ultraviolet absorber, and HALS (hindered amine light stabilizer) "ADEKA STAB LA-57 (trade name)" manufactured by ADEKA, "Irganox 1076 (trade name)" manufactured by BASF as an antioxidant, and a coloring agent are added in the blending amounts shown in Table 1, and mixed using a Henschel mixer. The obtained mixture was extruded and cut with a twin-screw extruder (TEM35 manufactured by Toshiba Machine) into pellets.

Here, as coloring agents, DYMIC MBR 510 (trade name) manufactured by Dainichi Seika Kogyo Co., Ltd. (phthalocyanine colorant, CI Pigment Green 7), DYMIC MBR D-05 manufactured by Dainichi Seika Kogyo Co., Ltd. (product) Name) (Anthraquinone colorant), DYMIC MBR 165 (trade name) manufactured by Dainichi Seika Kogyo Co., Ltd. (Anthraquinone colorant), DYMIC MBR 443 (trade name) manufactured by Dainichi Seikagyo Co., Ltd. (iso) Indolinone colorant), DYMIC MBR 717 (trade name) (carbon black) manufactured by Dainichi Seika Kogyo Co., Ltd. was used.
The pellets produced by the above method were dried at 80 ° C. all day and night, using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T die, a cylinder temperature of 200 to 240 ° C., and a T die. A colored acrylic resin film having a thickness shown in Table 1 was formed at a temperature of 250 ° C. and a cooling roll temperature of 70 ° C.
The chromaticity coordinates (x, y), Y value, total light transmittance, and haze in the XYZ color system of the obtained colored acrylic resin film were determined according to the above methods, and the visibility was evaluated. The results are shown in Table 1.

From the examples and comparative examples, the following became clear.
The colored acrylic resin films in Examples 1 to 6 (particularly Examples 1 to 5) have higher visibility while satisfying the standard as a retroreflective sheet when used by being laminated on a white retroreflective sheet, Industrial value is high.
On the other hand, the colored acrylic resin films in Comparative Examples 1 and 2 are difficult to visually recognize the color when, for example, a retroreflective sheet is used, and the industrial utility value is low.

  The retroreflective sheet having the colored acrylic resin film of the present invention on the surface satisfies the standards of JIS Z9117 and ASTM D4956, and can be used for various displays such as road signs and construction signs. Thus, the colored acrylic resin film of the present invention has a very high industrial utility value.

Claims (7)

A colored acrylic resin film that satisfies the following conditions (1) to (3) when the thickness is 50 to 100 μm;
(1) The total light transmittance is 22 to 35% when measured by the method specified in ISO 13468-1.
(2) The haze is 2.0 to 4.0% when measured by the method specified in ISO 14782-1.
(3) The colored acrylic resin film is superposed on a mouse-colored oil-colored paper whose Munsell symbol is N5.5, and the colored acrylic resin film side is illuminated and received in geometric conditions a (45 °) as defined in JIS Z8722. The chromaticity coordinates (x, y) in the XYZ color system when measured under the conditions of the standard light D65 by illumination and vertical light reception are (0.016, 0.381), (0.185, 0 .340), (0.317,0.436), and (0.224,0.806), with a Y value of 3-5.   The colored acrylic resin film according to claim 1, comprising at least one selected from the group consisting of phthalocyanine colorants, condensed polycyclic colorants, and inorganic colorants.   The colored acrylic resin film according to claim 1 or 2, wherein the acrylic resin component comprises a rubber-containing polymer.   A skin material for a retroreflective sheet, comprising the colored acrylic resin film according to claim 1.   A retroreflective material in which the colored acrylic resin film according to any one of claims 1 to 3 or the skin material according to claim 4 and a white retroreflective sheet are laminated. A method for producing a colored acrylic resin film, wherein a phthalocyanine colorant (for example, CI Pigment Green 7) and another colorant are mixed in an acrylic resin so as to satisfy the following conditions when the thickness is 50 to 100 μm. Including:
(1) The total light transmittance is 22 to 35% when measured by the method specified in ISO 13468-1.
(2) The haze is 2.0 to 4.0% when measured by the method specified in ISO 14782-1.
(3) The colored acrylic resin film is superposed on a mouse-colored oil-colored paper whose Munsell symbol is N5.5, and the colored acrylic resin film side is illuminated and received in geometric conditions a (45 °) as defined in JIS Z8722. The chromaticity coordinates (x, y) in the XYZ color system when measured under the conditions of the standard light D65 by illumination and vertical light reception are (0.016, 0.381), (0.185, 0 .340), (0.317,0.436) and (0.224,0.806), and the Y value is 3-5.   A method for producing a retroreflective material, comprising: obtaining a colored acrylic resin film by the method according to claim 6; and laminating the obtained film or a skin material including the film on a white retroreflective sheet. ,Method.