Resin molded articles

Abstract

The present invention provides a resin molded product that exhibits excellent jet-blackness when the light is off, and at the same time, when a white light source is turned on, it can convert that white light into chromatic colors of a target wavelength band with high stimulating purity. [Solution] The resin molded product 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 and second dyes 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 brightness L of the reflected light in a D65 light source at a 2-degree field of view. * The value is 30 or less, the total light transmittance is 1% or less, and the irritation purity is 75% or more.

Description

[Technical Field]

[0001] The present invention relates to a resin molded article. In particular, it relates to a resin molded article that has excellent blackness and the function of transmitting light of a specific wavelength to display highly stimulating chromatic colors on an xy chromaticity diagram. [Background technology]

[0002] In recent years, due to improvements in design and current trends, there has been a growing demand for thermoplastic resin molded products that exhibit achromatic colors (jet black) when the light source is off, but display chromatic colors when the light source is on, for use in automotive interiors and exteriors, signage, and other applications.

[0003] As a method for imparting jet blackness to thermoplastic resin molded products when the light source is off and colored when the light source is on, there are (1) a multi-layer method achieved by layering a jet black molded product and a colored molded product, and (2) a single-layer method achieved by blending organic dyes into the thermoplastic resin.

[0004] (1) The method of achieving this through multi-layering is a known method. However, if it is desired to provide jet blackness when the light is off and color when the light is on, it is necessary to manufacture a multi-layer film by layering a jet black film and a colored film, for example. However, the manufacture of multi-layer films requires advanced technology and equipment, and the manufacturing cost tends to be high.

[0005] On the other hand, (2) it has been considered difficult to impart the two aforementioned heterogeneous properties to a single-layer resin molded product. Recently, Patent Document 1 proposed a method for imparting jet blackness when the light source is off and chromatic color when the light source is on, using two or more organic dyes. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] WO2016 / 098746 publication [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, after repeated investigations by the inventors, it was found that it is actually difficult to obtain a single-layer resin molded product that exhibits excellent jet blackness when the light is off and converts the white light from a white light source into a chromatic color when the white light source is turned on. In particular, for automotive interiors and exteriors and display signs, from a design perspective, it is essential to obtain vivid chromatic colors with high stimulating purity when converting white light from a white light source into a chromatic color. However, it has become clear that it is difficult for a single-layer resin molded product to not only exhibit jet blackness when the light is off, but also to obtain vivid chromatic colors with high stimulating purity when converting white light from a white light source into a chromatic color when the white light source is turned on.

[0008] The object of the present invention is to provide a resin molded product that exhibits excellent jet blackness when the light is off, and at the same time can convert the white light of a white light source into vivid chromatic colors with high stimulating purity when the white light source is turned on. [Means for solving the problem]

[0009] The inventors, in order to solve the above problems, diligently conducted research and have now completed the present invention. That is, according to the present invention, the following resin molded product is provided.

[0010] [1] A resin molded article containing 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, and the total content of the first and second dyes 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 brightness L of the reflected light in a D65 light source at a 2-degree field of view *The resin molded product has a value of 30 or less, a total light transmittance of 1% or less, and a stimulation purity of 75% or more on the CIE1931 chromaticity coordinates for the transmitted light when the light emitted from a white light source passes through the resin molded product. [2] Luminance L in a 2-degree field of view of the D65 light source for the reflected light * The resin molded product according to [1], having a value of 28 or less. [3] The resin molded product according to [1] or [2], characterized in that the solar transmittance (incident light with wavelengths of 300 to 2500 nm) is 39% or more. [4] The resin molded product according to [1] to [3], characterized in that the C* value is 3 or less. [5] The resin molded product according to [1] to [4], characterized in that it is a film, sheet, molded part, or fiber. [6] The resin molded product according to [1] to [5], characterized in that it is an automotive interior or exterior display, display board, fiber material, 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 pitch blackness when turned off and, at the same time, can convert the white light into a chromatic color in a target wavelength band with high stimulation purity when the white light source is turned on.

Modes for Carrying Out 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 product of the present invention is a resin molded product containing a thermoplastic resin and a plurality of types of dyes.

[0014] (Thermoplastic resin) As the thermoplastic resin, a thermoplastic resin used for manufacturing a general resin molded product can be used. 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] As the thermoplastic resin, a transparent resin is preferred. A transparent resin is generally known as a resin with less reflection and absorption of visible light and through which visible light is transmitted without diffusion inside the resin. From the viewpoint of transparency, carbonate resins, acrylic resins, styrene resins, and vinyl chloride resins are preferred, and carbonate resins and acrylic resins are more preferred.

[0016] (Dye) The resin molded product of the present invention contains a plurality of types of dyes. The plurality of types of dyes include at least one first dye selected from the group consisting of azomethine and anthraquinone yellow, and at least one second dye selected from the group consisting of anthraquinone blue, anthraquinone green, and perinone. With such a combination, a resin molded product with high stimulus purity can be obtained, in which the reflected light is black while the transmitted light of a white light source is the desired color. Even for a combination of dyes outside the present invention, equivalent stimulus intensity may be obtained by increasing the dye concentration, but it has been found that it is difficult to obtain equivalent stimulus purity at a low concentration such as that of the resin molded product of the present invention.

[0017] The first dye is at least one dye selected from the group consisting of azomethine and anthraquinone yellow. However, two or more types of the first dye 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 CISolvent Red 212 and CISolvent Violet 49. Anthraquinone yellow dyes are yellow dyes that have anthraquinone structures in their molecules. Examples of anthraquinone yellow dyes include CISolvent Yellow 163 and CISolvent 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, and anthraquinone green and perinone may be used in combination.

[0019] Anthraquinone blue dyes are blue dyes that contain anthraquinone structures within their molecules. Examples of anthraquinone blue dyes include CDisperse Blue 60, CISolvent Blue 122, CISolvent Blue 35, CISolvent Blue 36, CISolvent Blue 78, and CISolvent Blue 97. Anthraquinone green dyes are green dyes that contain anthraquinone structures within their molecules. Examples of anthraquinone green dyes include CISolvent Green 28 and CISolvent Green 3.

[0020] Perinone dyes are dyes that have a perinone structure within their molecule. Examples of perinone dyes include perimidino[1”,2”:1',2']pyrrolo[3',4':5,6]isoindro[2,1-a]perimidine, CISolvent Red 135, and CISolvent Red 179.

[0021] (Dye content) In the resin molded product of the present invention, the total content of the first dye and the second dye with respect to 100 parts by mass of the thermoplastic resin is set to 0.03 parts by mass or more. By this, a resin molded product having suitable lightness, total light transmittance, and excitation purity can be obtained. Further, in the present invention, even when the total content of the first dye and the second dye with respect to 100 parts by mass of the thermoplastic resin is reduced to less than 0.2 parts by mass, a high excitation intensity can be obtained. From the viewpoint of the present invention, it is more preferable that the total content of the first dye and the second dye with respect to 100 parts by mass of the thermoplastic resin is 0.19 parts by mass or less.

[0022] Moreover, 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 kinds of dyes for the molded product, and more preferably three or more kinds. For example, even when only one kind of dye (particularly green, blue, or purple dye) is used, if the concentration is high, the transmittance decreases and the reflected light becomes black, and it is possible to transmit only a specific wavelength. However, by using three or more kinds of dyes rather than two kinds, the same effect can be obtained with a smaller addition amount. Furthermore, by selectively controlling the absorption and transmission of specific wavelengths, the reproducible range of hue can also be expanded. If the addition amount of the dye is too large, bleeding out occurs in the resin molded product and the mechanical strength decreases, which is not preferable.

[0024] (Lightness L * value and chroma C * value) Generally, as a method of expressing color tone, there is the CIE L * a * b * color system (color space) formulated by the International Commission on Illumination (CIE) to represent visible colors as a color space. In this CIE L * a * b * color system, a color is represented by three coordinates, and the 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 to bluish.) L * The value is one of the indicators that represents the lightness (brightness) of a color, and is shown in the range of 0 to 100, where 0 represents perfect black (no reflection) and 100 represents perfect white (total reflection). In order to obtain a molded product with excellent jet blackness, the lightness L of the reflected light from a D65 light source at a 2-degree field of view is * The value should be 30 or less, preferably 28 or less, and more preferably 27.8 or less.

[0025] The saturation C* value is an indicator of low saturation of reflected light from a resin molded product, indicating that the reflected light is not colored. It is expressed by the distance between the points indicated by a* and b* and the origin. A higher value indicates a more vivid color, while a lower value indicates lower saturation of the reflected light, resulting in a jet black color. A C* value of 3 or less is preferable, more preferably 2 or less, and even more preferably 1.5 or less. Note that the brightness 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 indicator that shows the proportion of light that passes through a material or film. If the total light transmittance is 1% or less, the influence of the base color can be reduced when the reflected color of a molded product is jet black, and the jet blackness can be maintained. Furthermore, if the total light transmittance is 0.01% or more, the light emitted from a light source that has passed through the molded product, such as an LED white light source, can exhibit a specific hue. A total light transmittance of 0.02% to 0.5% is more preferable, and 0.03% to 0.2% is even more preferable. If it is less than 0.01%, visible light will not be transmitted, and the effects of the present invention cannot be obtained. On the other hand, if it is greater than 1%, the color of the transmitted light will be lighter, and the desired color cannot be obtained.

[0027] (Primary wavelength and complementary primary wavelength) The dominant wavelength and complementary dominant wavelength are used to associate the hue of monochromatic light with wavelength. They refer to the wavelength at which the spectral locus intersects with the extension of a line drawn connecting the chromaticity coordinates of white light (x=0.3333, y=0.3333) and the chromaticity coordinates of the emitted color of the light-emitting device (x, y) in the CIE (International Commission on Illumination) 1931 chromaticity diagram. This molded product can exhibit a specific hue by selectively transmitting light of wavelengths within the range of the dominant wavelength and complementary dominant wavelength.

[0028] (stimulus purity) Stimulus purity on the chromaticity diagram is an indicator of the vividness and saturation of a color. Specifically, it is the value obtained by dividing the straight-line distance between the chromaticity coordinates of white light (x=0.3333, y=0.3333) and the chromaticity coordinates of the emitted color of the light-emitting device (x, y) by the straight-line 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 the spectral locus. A larger value indicates a more vivid and pure color. Conversely, a smaller value indicates a color that is closer to achromatic and has lower saturation.

[0029] In a preferred embodiment, the transmitted light, when light emitted from a white light source passes through the resin molded product, has a stimulating purity of 75% or more on the CIE1931 chromaticity coordinate system. This stimulating purity is preferably 85% or more, and more preferably 95% or more. The method for measuring the stimulating purity of the resin molded product is described in the Examples section.

[0030] (Solar transmittance) Solar transmittance refers to the proportion of light that passes through a particular material or device. The resin molded product of the present invention uses a dye with excellent infrared transmittance and does not use pigments such as carbon black that absorb wavelengths in the infrared region, thus enabling high solar transmittance. As a result, the resin molded product is less prone to heat accumulation and less susceptible to deformation or deterioration due to heat. In a preferred embodiment, the solar transmittance (incident light with wavelengths of 300 to 2500 nm) of the resin molded product is 39% or more.

[0031] (Additives) The resin molded articles of the present invention may contain other additives without departing from the spirit of the present invention. For example, they may contain dispersants, antioxidants, stabilizers, ultraviolet absorbers, lubricants, processing aids, antistatic agents, impact-resistant aids, fillers, matting agents, etc. When the amount of resin contained in the resin molded article is 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] (Method of manufacturing resin molded products) The resin molded articles of the present invention can generally be obtained by melt-mixing and dispersing at least a thermoplastic resin, a first dye, and a second dye using a Banbury mixer, Nauter mixer, kneading roll, or a single-screw or twin-screw extruder. Alternatively, pre-dispersion may be performed using a tumbler mixer, blender, or high-speed mixer to ensure uniform dispersion before kneading.

[0033] The resulting resin molded product can be molded into a predetermined shape using known methods such as injection molding, injection compression molding, pressure molding, blow molding, vacuum molding, foam molding, or extrusion molding, although these methods are not limited to those described above. Additives such as heat stabilizers, weather stabilizers, lubricants, pigment dispersants, and antistatic agents may be added depending on the purpose. Furthermore, other pigments and dyes may be added depending on the requirements of the molded product, such as for high aesthetic appeal.

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

[0035] The preferred total content of dye per 100 parts by mass of the resin molded product varies depending on the thickness of the molded product. For example, when the thickness of the molded product is 0.2 mm or more and less than 1 mm, the preferred total content of dye per 100 parts by mass is 0.2 parts by mass or more and less than 0.5 parts by mass. When the thickness of the molded product is 1 mm or more and less than 3 mm, it is preferable that the amount is 0.03 parts by mass or more and less than 0.2 parts by mass. When the thickness of the molded product is 3 mm or more and 10 mm or less, it is preferable that the amount is 0.01 parts by mass or more and less than 0.1 parts by mass. By increasing the total dye content beyond the above-mentioned amount, the L* value of reflected light decreases, resulting in a more jet-black hue and further improving the stimulating purity of transmitted light under a white light source. Therefore, it becomes easier to obtain resin molded products with any desired color tone. On the other hand, by decreasing the total dye content beyond the above-mentioned amount, the transmittance increases, making it easier to visually distinguish transmitted colors. Furthermore, concerns about bleed-out and a decrease in mechanical strength are reduced.

[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 applications of the resin molded article of the present invention may include automotive interior and exterior displays and display covers, display panels, fiber materials, door visors, and synthetic leather. The resin molded article of the present invention exhibits jet black when the light source is off and chromatic color when the light source is on, so it can be used to improve design and visibility. Furthermore, as an application that transmits infrared light, it can be used as a material for films and resin molded articles for LiDAR, which irradiates near-infrared light with a laser and measures the scattered light to analyze the distance to an object at a distance and the properties of that object. For example, by using it in a case that houses an irradiation device, the exterior is black but transmits near-infrared light, so the device can be protected without reducing its performance.

[0037] (white light source) Examples of white light sources used to obtain transmitted light when installed on the back of a resin molded product include incandescent lamps, fluorescent lamps, LED lamps, and HID lamps. Here, white light refers to light that appears white due to the mixture of multiple wavelengths, while colored light refers to light of a specific wavelength within the visible light wavelength range (for example, red light, blue light, etc.). A single white light source may be used alone, or two or more types may be used in combination. [Examples]

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

[0039] (Examples 1-12, Comparative Examples 1-5) The colorants and polycarbonate resins of the formulations shown in Tables 1, 2, and 3 were mixed. The polycarbonate resin used was "Panlite L1225," manufactured by Teijin Corporation. After mixing, the mixture was kneaded at a molding temperature of 290°C using a single-screw extruder to obtain pellets of the thermoplastic resin composition. The obtained thermoplastic resin composition pellets were then 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: 90mm x 50mm x 2mm).

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

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

[0042] (Measurement of total light transmittance) The total light transmittance (Y value at a light source D65 and field of view of 2°) of the resin molded product was measured 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 radiation transmittance) For the test molded products, the solar transmittance was measured in accordance with JIS R 3106 using a spectrophotometer (product name "Solidspec-3700", manufactured by Shimadzu Corporation). The results are shown in Tables 1, 2, and 3.

[0044] (Measurement by visual evaluation method) For the test molded product, white light (LED lamp, product name "Slim Work Light PL012", manufactured by TAKENOW) was transmitted 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 for each ingredient listed 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]isoindro[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: CIPigment Black 7 (Pigment, product name "Carbon Black #30", manufactured by Mitsubishi Chemical Corporation)

[0049] (resin) PC: Polycarbonate resin (product name "Panlight L1225", manufactured by Teijin Corporation)

[0050] When only CIPigment Black 7 (carbon black), the pigment used in Comparative Example 1, was used as the coloring agent, the irritation purity was 74.82%, failing to reach 75% or higher. Furthermore, the solar transmittance was low at 2.22%. Comparative Example 2, which had a total dye content of 0.011% (below the lower limit), had a low irritation purity of 44.8%. Comparative Example 3, in which the total dye content exceeded the upper limit at 0.535%, did not transmit the LED white light source, making it impossible to distinguish the transmitted light. Comparative Example 4, which used only one type of dye, had a high irritation purity of 98.2%, but L * Value, C * The values ​​and Y-values ​​were high, and the reflected light was yellow. Furthermore, Comparative Example 5, which used the lower brightness dye perimidino[1”,2”:1',2']pyrrolo[3',4':5,6]isoindro[2,1-a]perimidine, also had a low irritation purity of 28.9% and the reflected light color was reddish-purple. On the other hand, the molded articles of the present invention in Examples 1 to 12 met all the criteria. Furthermore, as shown in Tables 1, 2, and 3, molded articles with high irritation purity were obtained at each major wavelength in the xy chromaticity diagram.

[0051] The resin molded articles of the embodiments of the present invention all have a reflected light brightness L * The value is 30 or less, and the total light transmittance is 1% or less, C * Despite having a value of 3 or less and an extremely high degree of blackness, the transmitted light stimulation purity was very high at 75% or more. Moreover, it was possible to provide such a resin molded product with a total content of less than 0.2 parts by mass of the first and second dyes.

[0052] In contrast, the resin molded product of the comparative example did not possess these desired physical properties.

Claims

1. A resin molded article containing 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, and the total content of the first and second dyes 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 brightness L of the reflected light in a D65 light source at a 2-degree field of view ＊ A resin molded product characterized in that the value is 30 or less, the total light transmittance is 1% or less, and the transmitted light when light emitted from a white light source passes through the resin molded product has a stimulating purity of 75% or more on the CIE 1931 chromaticity coordinate system.

2. Brightness L of a D65 light source in a 2-degree field of view (reflected light) ＊ A resin molded article according to claim 1, wherein the value is 28 or less.

3. The resin molded article according to claim 1, characterized in that the solar transmittance (incident light with a wavelength of 300 to 2500 nm) is 39% or more.

4. C ＊ A resin molded article according to claim 1, characterized in that the value is 3 or less.

5. A resin molded article according to any one of claims 1 to 4, characterized in that it is a film, a sheet, a molded part, or a fiber.

6. The resin molded article according to claim 5, characterized in that it is a display, signboard, textile material, door visor, or synthetic leather for the interior or exterior of an automobile.

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