Resin molded articles

Abstract

To provide a resin molded product which exhibits excellent jet black when turned off and, at the same time, can convert white light into a chromatic color in a target wavelength band with high excitation purity when a white light source is turned on. [Solution] The resin molded article contains a thermoplastic resin and two or more dyes. The two or more dyes include one or more first dyes selected from the group consisting of azomethine and anthraquinone yellow, and one or more second dyes selected from the group consisting of anthraquinone blue, anthraquinone green, and perinone. The total content of the first dye and the second dye per 100 parts by mass of the thermoplastic resin is 0.03 parts by mass or more and less than 0.2 parts by mass, and the lightness L of the reflected light under a 2-degree field of view using a D65 light source is 0.03 parts by mass or more and less than 0.2 parts by mass. * The value is 30 or less, the total light transmittance is 1% or less, and the excitation purity is 75% or more.

Description

[Technical Field]

[0001] The present invention relates to a resin molded product, particularly to a resin molded product that has excellent jet-black color and the ability to transmit light of specific wavelengths and display chromatic colors with high excitation purity on an xy chromaticity diagram. [Background technology]

[0002] In recent years, due to improvements in design and trends, there has been an increasing demand for thermoplastic resin molded products that exhibit a chromatic color tone when the light source is on, in the interior and exterior of automobiles, display signs, etc., which currently exhibit an achromatic color tone (jet black) when the light source is off.

[0003] There are two methods for giving thermoplastic resin molded products jet black when the light source is off and chromatic colors when the light source is on: (1) a multi-layer method in which a jet black molded product is layered on a chromatic molded product, and (2) a single-layer method in which an organic dye is blended into the thermoplastic resin.

[0004] (1) The method of realizing this by multi-layering is a well-known method. However, if it is desired to impart jet black when the light is off and chromatic color when the light is on, it is necessary to manufacture a multi-layer film by overlapping, for example, a jet black film and a chromatic color film. However, manufacturing a multi-layer film requires advanced technology and equipment, and tends to increase manufacturing costs.

[0005] On the other hand, (2) it has been thought difficult to impart the two different characteristics mentioned above to a single-layer resin molded product. Recently, Patent Document 1 proposed a method of using two or more organic dyes to impart jet black when the light source is off and chromatic color when the light source is on. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] WO2016 / 098746 publication Summary of the Invention [Problem to be solved by the invention]

[0007] However, after extensive research by the present inventors, it has been found that it is actually difficult for a single-layer resin molded product to have excellent jet black color when the light is off and to convert the white light into a chromatic color when a white light source is on. In particular, for automobile interiors and exteriors, signboards, and the like, it is essential from the standpoint of design to obtain vivid chromatic colors with high excitation purity when converting white light into a chromatic color when the white light source is on. However, it has been found that it is actually difficult for a single-layer resin molded product to not only exhibit jet black color when the light is off, but also to obtain vivid chromatic colors with high excitation purity when converting white light into a chromatic color when the white light source is on.

[0008] An object of the present invention is to provide a resin molded article that exhibits excellent jet black when the light is off and, at the same time, can convert white light from a white light source into a vivid chromatic color with high excitation purity when the white light source is on. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, according to the present invention, there is provided the following resin molded article.

[0010] [1] A resin molded product containing a thermoplastic resin and two or more dyes, The two or more dyes include a first dye composed of azomethine and a second dye composed of anthraquinone green, the total content of the first dye and the second dye relative to 100 parts by mass of the thermoplastic resin is 0.03 parts by mass or more and 0.17 parts by mass or less, the ratio of the content of the first dye to the content of the second dye (the content of the first dye / the content of the second dye) is 0.01 to 1.5, and the lightness L *a value of 30 or less, a total light transmittance of 1% or less, and an excitation purity of 75% or more on the CIE 1931 chromaticity coordinates for transmitted light when light emitted from a white light source passes through the resin molded product. [2] Brightness L under a 2-degree field of view with a D65 light source in reflected light * The resin molded product according to [1], wherein the value is 28 or less. [3] The resin molded article according to [1] or [2], characterized in that it has a solar radiation transmittance (for incident light with a wavelength of 300 to 2500 nm) of 39% or more. [4] The resin molded article according to any one of [1] to [3], characterized in that the C* value is 3 or less. [5] The resin molded article according to any one of [1] to [4], which is a film, a sheet, a molded part, or a fiber. [6] The resin molded product according to any one of [1] to [5], which is an automobile interior / exterior display, a display board, a fiber material, a door visor, or synthetic leather. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a resin molded product that exhibits excellent jet black when the light is off, and at the same time, when a white light source is on, can convert the white light into a chromatic color in a target wavelength band with high excitation purity. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0013] The resin molded article of the present invention is a resin molded article containing a thermoplastic resin and a plurality of dyes.

[0014] (thermoplastic resin) The thermoplastic resin may be any thermoplastic resin used to produce general resin molded products. Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; carbonate resins such as polycarbonate; vinyl chloride resins such as polyvinyl chloride; styrene resins such as polystyrene; ABS; polyamide; acrylic resins such as polymethyl methacrylate; polyurethane; polyphenylene ether; and the like. These thermoplastic resins may be amorphous thermoplastic resins, and may be used alone or in combination of two or more.

[0015] The thermoplastic resin is preferably a transparent resin. A transparent resin is generally known as a resin that has little reflection or absorption of visible light and allows visible light to pass through the resin without diffusing. From the viewpoint of transparency, carbonate-based resins, acrylic-based resins, styrene-based resins, and vinyl chloride-based resins are preferred, and carbonate-based resins and acrylic-based resins are more preferred.

[0016] (dye) The resin molded article of the present invention contains multiple dyes. The multiple dyes include one or more first dyes selected from the group consisting of azomethine and anthraquinone yellow, and one or more second dyes selected from the group consisting of anthraquinone blue, anthraquinone green, and perinone. This combination allows for the production of a resin molded article with high excitation purity, in which reflected light is black but transmitted light from a white light source is the desired color. Even with dye combinations outside the present invention, it may be possible to obtain equivalent excitation intensity by increasing the dye concentration, but it has been found that it is difficult to obtain equivalent excitation purity at concentrations as low as those used in the resin molded article of the present invention.

[0017] The first dye is one or more dyes selected from the group consisting of azomethine and anthraquinone yellow, although two or more first dyes may be used, and both azomethine and anthraquinone yellow may be used. Azomethine dyes are imines in which a hydrocarbon group is bonded to a nitrogen atom. Examples of azomethine dyes include CI Solvent Red 212 and CI Solvent Violet 49. Anthraquinone yellow dyes are yellow dyes that have an anthraquinone structure in the molecule. Examples of anthraquinone yellow dyes include CI Solvent Yellow 163 and CI Solvent Yellow 167.

[0018] The second dye is one or more dyes selected from the group consisting of anthraquinone blue, anthraquinone green, and perinone. Two or more second dyes may be used. Also, anthraquinone blue and anthraquinone green may be used in combination, anthraquinone blue and perinone may be used in combination, or anthraquinone green and perinone may be used in combination.

[0019] Anthraquinone blue dyes are blue dyes having an anthraquinone structure in the molecule. Examples of anthraquinone blue dyes include CI Disperse Blue 60, CI Solvent Blue 122, CI Solvent Blue 35, CI Solvent Blue 36, CI Solvent Blue 78, and CI Solvent Blue 97. Anthraquinone green dyes are green dyes having an anthraquinone structure in the molecule. Examples of anthraquinone green dyes include CI Solvent Green 28 and CI Solvent Green 3.

[0020] Perinone dyes are dyes that contain a perinone structure in their molecules. Examples of perinone dyes include perimidino[1”,2”:1’,2’]pyrrolo[3’,4’:5,6]isoindolo[2,1-a]perimidine, CI Solvent Red 135, and CI Solvent Red 179.

[0021] (dye content) In the resin molded article of the present invention, the total content of the first dye and the second dye per 100 parts by mass of thermoplastic resin is set to 0.03 parts by mass or more. This makes it possible to obtain a resin molded article having suitable brightness, total light transmittance, and excitation purity. Also, in the present invention, the total content of the first dye and the second dye per 100 parts by mass of thermoplastic resin is set to 0.03 parts by mass or more. 0.17 Mass part below Even when the amount is reduced to , a high stimulation intensity can be obtained.

[0022] The ratio of the content of the first dye to the content of the second dye (content of the first dye / content of the second dye) is preferably 0.01 to 1.5, and more preferably 0.015 to 1.2.

[0023] It is preferable to use two or more types of dyes in molded products, and three or more are even more preferable. For example, even if only one type of dye (especially green, blue, or purple dyes) is used, if the concentration is high, the transmittance will decrease and the reflected light will turn black, making it possible to transmit only specific wavelengths. However, by using three or even more types of dyes rather than two, the same effect can be achieved with a smaller amount added. Furthermore, by selectively controlling the absorption and transmission of specific wavelengths, the range of color reproduction can be expanded. Adding too much dye is undesirable, as it can cause bleed-out in resin molded products and reduce mechanical strength.

[0024] (Lightness L * Value and Saturation C * value) The general method of expressing color is the CIE L color space, which was established by the International Commission on Illumination (CIE) and expresses colors that can be seen with the naked eye. * a * b * There is a color space (CIE L) * a * b * In the color system, color is expressed by three coordinates, and lightness is "L * ", red (magenta) to green is "a * (positive is magenta, negative is greenish), yellow to blue is "b* " (positive corresponds to yellowish, negative corresponds to bluish). L * The value is an index that indicates the lightness (brightness) of a color, and is shown in the range from 0 to 100, with 0 representing perfect black (no reflection) and 100 representing perfect white (total reflection). In order to obtain a molded product with excellent jet black color, the lightness L * The value is set to 30 or less, preferably 28 or less, and more preferably 27.8 or less.

[0025] The saturation C* value is an index that indicates the low saturation of reflected light from a resin molded product, and indicates that the reflected light is not colored. It is expressed as the distance between the point indicated by a* and b* and the origin. The higher the value, the more vivid the color, and the lower the value, the lower the saturation of the reflected light and the more jet black it is. The C* value is preferably 3 or less, more preferably 2 or less, and even more preferably 1.5 or less. In addition, the lightness L of the resin molded product * Value and Saturation C * The method for measuring the values ​​is described in the Examples section.

[0026] (Total light transmittance) The total light transmittance Y value is an index that indicates the proportion of light that passes through a material, film, etc. If the total light transmittance is 1% or less, the influence of the color of the base can be reduced and the jet-black color can be maintained when the reflected color of the molded article is jet black. Furthermore, if the total light transmittance is 0.01% or more, light emitted from a light source, such as an LED white light source, that passes through the molded article can exhibit a specific color tone. The total light transmittance is more preferably 0.02% or more and 0.5% or less, and even more preferably 0.03% or more and 0.2% or less. If it is less than 0.01%, visible light will not be transmitted, and the effects of the present invention cannot be achieved. On the other hand, if it exceeds 1%, the color of the transmitted light will be pale, and the desired color will not be obtained.

[0027] (dominant wavelength and complementary dominant wavelength) The dominant wavelength and complementary wavelength are used to associate the hue of monochromatic light with its wavelength, and refer to the wavelength at the point where a line extending from the chromaticity coordinates (x=0.3333, y=0.3333) of white light on the CIE (Commission Internationale de l'Eclairage) 1931 chromaticity diagram to the chromaticity coordinates (x, y) of the emitted color of the light-emitting device intersects with the spectral locus. This molded product can exhibit a specific color tone by selectively transmitting light with wavelengths within the range of the dominant wavelength and complementary wavelength.

[0028] (stimulus purity) Excitation purity on a chromaticity diagram is an index that indicates the vividness and saturation of a color. Specifically, it is the value obtained by dividing the linear distance between the chromaticity coordinates (x=0.3333, y=0.3333) of white light in the chromaticity coordinate system of the chromaticity diagram and the chromaticity coordinates (x, y) of the color emitted by the light-emitting device by the linear distance from the chromaticity of the white light, through the chromaticity of the light emitted by the light-emitting device, to the chromaticity where it intersects with the spectral locus. The larger this value, the more vivid and pure the color. Conversely, the smaller the value, the closer the color is to achromatic color and the lower its saturation.

[0029] In a preferred embodiment, the excitation purity of the transmitted light when light emitted from a white light source passes through a resin molded article is 75% or more on the CIE 1931 chromaticity coordinates. This excitation purity is preferably 85% or more, and more preferably 95% or more. The method for measuring the excitation purity of the resin molded article is described in the Examples section.

[0030] (solar transmittance) Solar transmittance refers to the proportion of sunlight that passes through a particular material or device. The resin molded article of the present invention uses a dye that has excellent infrared transmittance and does not use a pigment such as carbon black that absorbs wavelengths in the infrared region, thereby enabling it to have a high solar transmittance. As a result, the resin molded article is less likely to accumulate heat and is less likely to deform or deteriorate due to heat. In a preferred embodiment, the resin molded article has a solar radiation transmittance (for incident light with a wavelength of 300 to 2500 nm) of 39% or more.

[0031] (additives) The resin molded product of the present invention may contain other additives within the scope of the present invention. For example, dispersants, antioxidants, stabilizers, UV absorbers, lubricants, processing aids, antistatic agents, impact resistance aids, fillers, matting agents, etc. When the amount of resin contained in the resin molded product is taken as 100 parts by mass, the content of other additives is preferably 5 parts by mass or less, and may be 0 parts by mass.

[0032] (Manufacturing method of resin molded products) The resin molded article of the present invention can generally be obtained by melt-mixing and dispersing at least the thermoplastic resin, the first dye, and the second dye using a Banbury mixer, a Nauta mixer, a kneading roll, or a single-screw or twin-screw extruder, etc. Furthermore, for the purpose of achieving uniform dispersion before kneading, preliminary dispersion may be carried out using a tumbler mixer, a blender, or a high-speed mixer.

[0033] The molding method of the obtained resin molded product is not limited, but it can be molded into a predetermined shape by known methods such as injection molding, injection compression molding, pressure molding, blow molding, vacuum molding, foam molding, and extrusion molding. At this time, additives such as heat stabilizers, weather stabilizers, lubricants, pigment dispersants, and antistatic agents can be added depending on the purpose. Furthermore, other pigments and dyes can be added depending on the purpose required for the molded product, such as high designability.

[0034] (Thickness of resin molded product) The thickness of the resin molded article is preferably 0.2 to 10 mm from the viewpoint of maintaining blackness and excitation purity.

[0035] The suitable total content of dyes per 100 parts by mass of the total mass of the resin molded article varies depending on the thickness of the molded article. For example, when the thickness of the molded article is 0.2 mm or more and less than 1 mm, the total content of dyes per 100 parts by mass of the total mass is preferably 0.2 parts by mass or more and less than 0.5 parts by mass. When the thickness of the molded article is 1 mm or more and less than 3 mm, the content is preferably 0.03 part by mass or more and less than 0.2 part by mass. When the thickness of the molded article is 3 mm or more and 10 mm or less, the content is preferably 0.01 part by mass or more and less than 0.1 part by mass. By increasing the total dye content above the above range, the L* value of the reflected light decreases, resulting in a jet-black hue and further improving the excitation purity of the transmitted light under a white light source. This makes it easier to obtain a resin molded product with any desired color tone. On the other hand, by decreasing the total dye content below the above range, the transmittance increases, making it easier to visually distinguish the transmitted color. Furthermore, there is less concern about bleed-out and reduced mechanical strength.

[0036] (Application) The form of the resin molded article of the present invention is not limited and may be a film, sheet, molded part, or fiber. Furthermore, the resin molded article of the present invention may be used for automobile interior / exterior displays and display covers, signage boards, fiber materials, door visors, and synthetic leather. The resin molded article of the present invention exhibits a jet black color when the light source is off and a chromatic color when it is on, and can be used to improve design and visibility. Furthermore, as a material for infrared transmission, it can be used as a material for films and resin molded articles for LiDAR, which irradiates near-infrared light or the like with a laser and measures the scattered light to analyze the distance to a distant object and the properties of that object. For example, by using it in a case for storing an irradiation device, the device can be protected without losing performance by transmitting near-infrared light despite its black appearance.

[0037] (white light source) Examples of white light sources that can be placed on the back of a resin molded product to obtain transmitted light include incandescent lamps, fluorescent lamps, LED lamps, and HID lamps. Here, white light refers to light that appears white due to the mixture of light of multiple wavelengths, and colored light refers to light of a specific wavelength in the visible light wavelength range (e.g., red light, blue light, etc.). One type of white light source may be used alone, or two or more types may be used in combination. [Example]

[0038] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by mass unless otherwise specified.

[0039] (Examples 1 to 12, Comparative Examples 1 to 5) The colorants and polycarbonate resin were mixed according to the formulations shown in Tables 1, 2, and 3. The polycarbonate resin used was "Panlite L1225," a product of Teijin Limited. After blending, the mixture was kneaded using a single-screw extruder at a molding temperature of 290°C to obtain pellets of a thermoplastic resin composition. The obtained pellets of the thermoplastic resin composition were injection-molded using an injection molding machine at a cylinder temperature of 290°C and a mold temperature of 40°C to produce test resin molded products (size: length 90 mm x width 50 mm x thickness 2 mm).

[0040] (L * Value, C * (measurement of values) The reflectance of the test molded product was measured using a spectrophotometer (product name "CM-36dG", manufactured by Konica Minolta), and the L* and C* values ​​were calculated under a D65 light source and a 2° field of view. The results are shown in Tables 1, 2, and 3.

[0041] (Measurement of dominant wavelength, complementary wavelength, excitation purity and color xy values ​​on the chromaticity diagram) White light (LED lamp, trade name "Slim Work Light PL012", manufactured by TAKENOW) was transmitted through the back of the resin molded product, and the light transmitted through the surface of the resin molded product was measured using a spectroradiometer (trade name "CL-500A", manufactured by Konica Minolta) to obtain excitation purity at a 2° field of view. The results are shown in Tables 1, 2, and 3.

[0042] (Measurement of total light transmittance) The resin molded article was measured for total light transmittance (Y value at a light source of D65 and a visual field of 2°) using a spectrophotometer (product name "CM-36dG", manufactured by Konica Minolta). The results are shown in Tables 1, 2 and 3.

[0043] (Measurement of solar transmittance) The solar transmittance of the test molded product was measured using a spectrophotometer (product name "Solidspec-3700", manufactured by Shimadzu Corporation) in accordance with JIS R 3106. The results are shown in Tables 1, 2 and 3.

[0044] (Visual evaluation method) For the test molded product, white light (LED lamp, product name "Slim Work Light PL012", manufactured by TAKENOW) was passed through the back of the test molded product, and the color of the light transmitted through the surface of the test molded product was observed visually. The results are shown in Tables 1, 2, and 3.

[0045] [Table 1]

[0046] [Table 2]

[0047] [Table 3]

[0048] The product names of the ingredients in the table are as follows: (coloring agent) S.BL-122: CISolvent Blue 122 (dye, product name "POLYSYNTHREN BLUE R", manufactured by Heubach) SR-212: CISolvent Red 212 (dye, product name "POLYSYNTHREN RED GG", manufactured by Heubach) SR-179: CISolvent Red 179 (dye, product name "PLAST RED 8370", manufactured by Arimoto Chemical Co., Ltd.) SY-163: CISolvent Yellow 163 (dye, product name "PLAST YELLOW DY-443", manufactured by Arimoto Chemical Co., Ltd.) SG-28: CISolvent Green 28 (dye, product name "SOLVAPERM GREEN G", manufactured by Heubach) Perimidino[1”,2”:1',2']pyrrolo[3',4':5,6]isoindolo[2,1-a]perimidine (dye, trade name "VIOLET 7", manufactured by Arimoto Chemical Co., Ltd.) ·D.BL-60: CIDisperse Blue 60 (dye, product name "PLAST BLUE DB-367", manufactured by Arimoto Chemical Co., Ltd.) SV-49: CISolvent Violet 49 (dye, product name "PLAST VIOLET DV-604", manufactured by Arimoto Chemical Co., Ltd.) P.BK-7: CI Pigment Black 7 (pigment, product name "Carbon Black #30", manufactured by Mitsubishi Chemical Corporation)

[0049] (resin) PC: Polycarbonate resin (trade name "Panlite L1225", manufactured by Teijin Ltd.)

[0050] When CI Pigment Black 7 (carbon black), the pigment of Comparative Example 1, was used alone as a colorant, the excitation purity was 74.82%, which did not reach 75% or more, and the solar transmittance was also low at 2.22%. Comparative Example 2, in which the total dye content was 0.011%, below the lower limit, had a low excitation purity of 44.8%. In Comparative Example 3, in which the total dye content was 0.535%, which exceeded the upper limit, the LED white light source did not transmit through, so transmitted light could not be distinguished. Comparative Example 4, which uses one type of dye, had a high excitation purity of 98.2%, but * Value, C * The value and Y value were also high, and the color of the reflected light was yellow. Furthermore, Comparative Example 5, which used perimidino[1”,2”:1′,2′]pyrrolo[3′,4′:5,6]isoindolo[2,1-a]perimidine, a dye with lower brightness, also had a low excitation purity of 28.9% and the color of the reflected light was reddish purple. On the other hand, the molded articles of the present invention in Examples 1 to 12 satisfied all the criteria. Furthermore, in terms of the xy values ​​on the chromaticity diagram, as shown in Tables 1, 2 and 3, molded articles with high excitation purity were obtained at each dominant wavelength.

[0051] The resin molded products of the examples of the present invention all have a reflected light brightness L * The value is 30 or less, the total light transmittance is 1% or less, and C * Although the value was 3 or less and the jet blackness was extremely high, the excitation purity of the transmitted light was extremely high at 75% or more. Moreover, it was possible to provide such a resin molded product with a small total content of the first dye and the second dye of less than 0.2 parts by mass.

[0052] In contrast, the resin molded articles of the comparative examples did not have such desired physical properties.

Claims

1. A resin molded article containing a thermoplastic resin and two or more dyes, The two or more dyes include a first dye composed of azomethine and a second dye composed of anthraquinone green, the total content of the first dye and the second dye relative to 100 parts by mass of the thermoplastic resin is 0.03 parts by mass or more and 0.17 parts by mass or less, the ratio of the content of the first dye to the content of the second dye (the content of the first dye / the content of the second dye) is 0.01 to 1.5, and the lightness L of reflected light in a 2-degree field of view using a D65 light source is 0.03 to 0.17 parts by mass. ＊ a value of 30 or less, a total light transmittance of 1% or less, and an excitation purity of 75% or more on the CIE 1931 chromaticity coordinates for transmitted light when light emitted from a white light source is transmitted through the resin molded product.

2. Brightness L under 2-degree field of view with D65 light source of reflected light ＊ 2. The resin molded article according to claim 1, wherein the value is 28 or less.

3. 2. The resin molded article according to claim 1, wherein the resin molded article has a solar radiation transmittance (for incident light having a wavelength of 300 to 2500 nm) of 39% or more.

4. C ＊ 2. The resin molded article according to claim 1, wherein the value is 3 or less.

5. The resin molded article according to any one of claims 1 to 4, which is a film, a sheet, a molded part or a fiber.

6. 6. The resin molded article according to claim 5, which is an automobile interior / exterior display, a display board, a fiber material, a door visor, or synthetic leather.

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