Resin molded article

Abstract

[Problem] The present invention addresses the problem of achieving, in a resin molded article, an achromatic color that has low dependence on concentration and thickness and has both uniform spectral reflectance and uniform spectral transmittance, which are difficult to be achieved by a black dye alone, and suppressing metamerism. [Solution] Provided is a resin molded article which contains: a first coloring agent that has a maximum absorption wavelength within the wavelength range of 420 nm to 450 nm inclusive; a second coloring agent that has a maximum absorption wavelength within the wavelength range of more than 450 nm but not more than 500 nm; a third coloring agent that has a maximum absorption wavelength within the wavelength range of more than 500 nm but not more than 570 nm; a fourth coloring agent that has a maximum absorption wavelength within the wavelength range of more than 570 nm but not more than 650 nm; and a fifth coloring agent that has a maximum absorption wavelength within the wavelength range of more than 650 nm but not more than 700 nm. The resin molded article is colored by subtractive color mixing of the first coloring agent, the second coloring agent, the third coloring agent, the fourth coloring agent, and the fifth coloring agent. The lightness L* in a 10-degree field of view of a D65 light source is 45 to 55, and C* is 1.0 or less. Each spectral transmittance measured at a wavelength interval of 10 nm in the wavelength range of 420 nm to 700 nm inclusive is within ± 5% from the average spectral transmittance in the wavelength range of 420 nm to 700 nm inclusive.

Description

resin molded products

[0001] The present invention relates to a resin molded product, and more particularly to a resin molded product in which the transmitted color is an achromatic color in which both the spectral reflectance and the spectral transmittance remain substantially constant even when the density or thickness is changed, and in which metamerism of the reflected color is suppressed.

[0002] Carbon black has traditionally been used as a pigment in black paints and resin molded products. However, depending on the type of carbon black, reflected or transmitted light can appear yellowish or reddish in black, which can also cause metamerism. For this reason, it has been difficult to achieve achromatic black using carbon black alone.

[0003] Furthermore, in a method for obtaining an achromatic resin molded product by subtractive color mixing using chromatic dyes and pigments, color matching is performed using a specific light source and field of view, but the spectral reflectance and spectral transmittance in the visible light wavelength range of 420 nm to 700 nm are not flat. Therefore, if a light source other than the one used for color matching is used, if the concentration during color matching is changed, or if the thickness of the resin molded product during color matching is changed, the product may appear to be tinted chromatically, and the transmitted light source color may appear to be tinted a color different from the original light source color.

[0004] Therefore, in order to express the achromatic color black, for example, Patent Document 1 describes a method for manufacturing a light amount adjusting member by applying an ink made by mixing a black dye or carbon black with other dyes onto a transparent substrate. Also, Patent Document 2 describes a black film made of a thermoplastic resin using two or more dyes other than black.

[0005] JP 2005-070752 A International Publication No. 2017 / 217429 A

[0006] In Patent Document 1, a light amount adjusting member having substantially constant spectral characteristics in the range of 400 to 700 nm, particularly 600 to 700 nm, is manufactured by printing a coloring liquid on a transparent substrate, by including at least one coloring material whose absorption spectrum has a maximum absorption wavelength in the range of 630 nm to 750 nm. However, although Patent Document 1 aims to adjust the amount of light and the spectral transmittance of visible light is considered to be constant to a certain extent, it does not describe spectral reflected light over the entire visible light range, nor does it describe or suggest subtractive color mixing.

[0007] The invention in Patent Document 2 is aimed at decorative molding and aims to solve the problems of color tone differences occurring within the same decorative molding and the difficulty of expressing deep, clear, jet black. ＊ and b ＊ Although the absolute value of is 2.0 or less, the study was conducted on a system with low total light transmittance and high density, and there is no issue regarding the representation of achromatic black when the density is low. Furthermore, although the study mentions color tone differences within the same decorated molding, no study has been conducted on metamerism.

[0008] The objective of the present invention is to obtain an achromatic color in a resin molded product that is less dependent on concentration and thickness and has uniform spectral reflectance and transmittance, which is difficult to achieve with a black dye or pigment alone, and to suppress metamerism.

[0009] The present inventors have conducted extensive research to solve the above problems and have completed the present invention.

[0010] That is, according to the present invention, there is provided the following resin molded article: [1] A resin molded article containing a first colorant having a maximum absorption wavelength in a wavelength range of 420 nm or more and 450 nm or less, a second colorant having a maximum absorption wavelength in a wavelength range of more than 450 nm and less than 500 nm, a third colorant having a maximum absorption wavelength in a wavelength range of more than 500 nm and more than 570 nm, a fourth colorant having a maximum absorption wavelength in a wavelength range of more than 570 nm and less than 650 nm, and a fifth colorant having a maximum absorption wavelength in a wavelength range of more than 650 nm and less than 700 nm, wherein the resin molded article is colored by subtractive color mixing of the first colorant, the second colorant, the third colorant, the fourth colorant, and the fifth colorant, and D ６５ Light source 10 degree field of view brightness L ＊ is 45-55, C ＊ a spectral transmittance of 1.0 or less, and each spectral transmittance measured at wavelength intervals of 10 nm in the wavelength range of 420 nm or more and 700 nm or less is within ±5% of the average spectral transmittance in the wavelength range of 420 nm or more and 700 nm or less.

[0011] [2] Metamerism index M defined in JIS Z8719-1996 １０ (D ６５ : F11 (W １０ )) is 1.5 or less.

[0012] [3] Conditional color matching index M １０ (D ６５ : A (W １０ )), M １０ (D ６５ : C (W １０ )), M １０ (D ６５ :D ５０ (W １０ )), M １０ (D ６５ : F2 (W １０ )), M １０ (D ６５ : F6 (W １０ )), M １０ (D ６５ : F7 (W １０ )), M １０ (D ６５ : F8 (W１０ )), M １０ (D ６５ : F10 (W １０ )) and M １０ (D ６５ : F12 (W １０ )) are each 1.5 or less.

[0013] [4] The resin molded product according to any one of [1] to [3], characterized in that it contains carbon black as the colorant.

[0014] [5] L ＊ a ＊ b ＊ a in color system measurement ＊ The value is -0.5 or more and 0.5 or less, and b ＊ The resin molded product according to any one of [1] to [3], wherein the value is -0.5 or more and 0.5 or less.

[0015] [6] The resin molded product according to any one of [1] to [3], which is an ND filter, a black panel, a fiber material, a door visor, a toner, an infrared transmitting film, or synthetic leather.

[0016] According to the present invention, it is possible to provide a resin molded article that has low dependency on concentration and thickness, that expresses an achromatic color with nearly uniform spectral reflectance and spectral transmittance in the visible light region of 420 to 700 nm, and that suppresses metamerism, thereby making it possible to provide a transparent resin molded article in which the transmitted color of a light source transmitted through the resin molded article can be adjusted to a slight change in color tone.

[0017] Graphs (a), (b), and (c) show the spectral transmittance of blue dye 1, blue dye 2, and green dye 1 used in the examples. Graphs (a), (b), and (c) show the spectral transmittance of purple dye 1, purple dye 2, and yellow dye 1 used in the examples. Graphs (a), (b), and (c) show the spectral transmittance of yellow dye 2, red dye 1, and red dye 2 used in the examples. Graphs (a) and (b) show the spectral transmittance of black mixed dye 1 and black mixed dye 2. Graphs (a), (b), and (c) show the spectral transmittance of red pigment 1, yellow pigment 1, and black pigment 1. Graphs (a) and (b) show the spectral transmittance of black pigment 2 and carbon. Graphs (a) and (b) show the spectral transmittance of resin molded products of Examples 1 and 2. Graphs (a) and (b) show the spectral transmittance of resin molded products of Example 3 and Comparative Example 1. Graphs (a) and (b) show the spectral transmittance of the resin molded articles of Comparative Examples 2 and 3. Graphs (a) and (b) show the spectral transmittance of the resin molded articles of Comparative Examples 4 and 5. Graphs (a) and (b) show the spectral transmittance of the resin molded articles of Comparative Examples 6 and 7. Graphs (a) and (b) show the spectral transmittance of the resin molded articles of Example 4 and Comparative Example 8. Graphs (a) and (b) show the spectral transmittance of the resin molded articles of Example 9 and Comparative Example 10.

[0018] (Resin) The resin molded article of the present invention contains a resin. This resin is preferably a thermoplastic resin. As such a thermoplastic resin, a thermoplastic resin used for producing a general resin molded article 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; polycarbonate; polystyrene; ABS; polyamide; polymethyl methacrylate; polyurethane; polyphenylene ether, etc. These thermoplastic resins may be amorphous thermoplastic resins, and may be used alone or in combination of two or more.

[0019] The resin constituting the resin component of the present invention may be a thermosetting resin other than a thermoplastic resin, such as a urethane resin, an epoxy resin, a phenolic resin, an unsaturated polyester resin, a vinyl ester resin, an alkyd resin, a melamine resin, an imide resin, a styrene-based resin obtained by polymerizing a monomer having a difunctional or higher vinyl polymerizable functional group, or a (meth)acrylate resin.

[0020] (Colorant) The resin molded article of the present invention contains five or more colorants. Specifically, the colorants include a first colorant having a maximum absorption wavelength in the wavelength range of 420 nm or more and 450 nm or less, a second colorant having a maximum absorption wavelength in the wavelength range of more than 450 nm and less than 500 nm, a third colorant having a maximum absorption wavelength in the wavelength range of more than 500 nm and less than 570 nm, a fourth colorant having a maximum absorption wavelength in the wavelength range of more than 570 nm and less than 650 nm, and a fifth colorant having a maximum absorption wavelength in the wavelength range of more than 650 nm and less than 700 nm.

[0021] The resin molded article of the present invention has optical properties that absorb light across the entire visible light range. Specifically, the inventors discovered that the spectral transmittance of the resin molded article must be in the wavelength range of 420 to 700 nm, which effectively absorbs most visible light radiation. The wavelength range of 420 to 700 nm is then divided as described above, and five colorants with maximum absorption wavelengths within each wavelength range are blended and adjusted to achieve subtractive color mixing. Subtractive color mixing is a technique for reducing brightness by mixing colorants with different absorption wavelengths. This allows for the production of a resin molded article with low dependency on concentration and thickness, achromatic colors in which both spectral reflectance and spectral transmittance are nearly uniform across the visible light range of 420 to 700 nm, and reduced metamerism.

[0022] In the visible light wavelength range of 420 to 700 nm, the spectral transmittance at each 10-nm wavelength interval is ±5% or less, preferably ±3% or less, and more preferably ±2% or less, relative to the average transmittance calculated by averaging the spectral transmittances at 10-nm wavelength intervals. If this value exceeds ±5%, the metamerism index is likely to exceed 1.5, making metamerism more likely to occur. Furthermore, the wavelength range below 420 nm is excluded from the wavelength range because absorption often occurs depending on the resin used, such as polyvinyl chloride resin, and this has little impact on metamerism in resin molded products. Furthermore, the desired achromatic color can also be obtained by using the 420 to 700 nm range as a reference, excluding the range below 420 nm.

[0023] However, the maximum absorption wavelength of each colorant is measured as follows. That is, the spectral transmittance is measured at 10 nm intervals from 420 nm to 700 nm. The wavelength at which the spectral transmittance is maximum is defined as the maximum absorption wavelength. Therefore, the maximum absorption wavelength can be a value in 10 nm increments from 420 nm to 700 nm. Furthermore, when measuring the spectral transmittance of each colorant at each wavelength, each colorant is mixed with PET-G resin under the conditions described in the Examples and roll-molded to produce a resin molded product with a thickness of 0.5 mm. Then, the spectral transmittance is measured at five points on the resin molded product at each measurement wavelength, and the average value is used as the measured spectral transmittance.

[0024] (Spectral Transmittance Distribution of Resin Molded Article) In the resin molded article of the present invention, each spectral transmittance measured at 10 nm wavelength intervals in the wavelength range of 420 nm to 700 nm is within ±5% of the average spectral transmittance in the wavelength range of 420 nm to 700 nm. This allows achromatic colors to be expressed through subtractive color mixing. As a result, transmitted light with unchanged saturation can be obtained, and a resin molded article with suppressed metamerism can be produced.

[0025] In this case, the spectral transmittance of the resin molded product is measured at wavelength intervals of 10 nm in the range of 420 nm to 700 nm. At each wavelength point, the spectral transmittance is measured once at five locations on the resin molded product, and the average of the five measurements is taken as the spectral transmittance at each wavelength interval. The average value of the spectral transmittances at 29 measurement wavelengths in the range of 420 nm to 700 nm is taken as the average spectral transmittance. Commercially available spectral colorimeters, such as stationary colorimeters or portable (handy) colorimeters, can be used to measure the spectral transmittance.

[0026] Each colorant includes a dye or a pigment, and the dye or pigment may be used alone or in combination. As the dye or pigment, known dyes, organic pigments, and inorganic pigments conventionally used for coloring printing inks, paints, and thermoplastic resins may be used. From these dyes and pigments, a colorant having the aforementioned maximum absorption wavelength is selected.

[0027] The resin molded article of the present invention contains at least the five or more types of colorants described above. The number of types of colorants is five or more. There is no particular upper limit to the number of types of colorants. However, since there are 29 wavelength points in 10 nm increments in the wavelength range of 420 to 700 nm, there is no need to use more than 29 types of colorants. Therefore, the number of types of colorants may be 29 or less.

[0028] It is preferable to select the type, particle size, and processing method of dyes and pigments depending on the application. For example, when imparting transparency to a colored product, the type and particle size of the dye or pigment can be appropriately selected. Luminescent pigments are effective pigments that impart retroreflective and light-scattering properties to the surface of the resulting molded product, changing color tone depending on the viewing angle. Pearl mica pigments can be natural mica or synthetic mica coated with metal oxides such as titanium oxide, zinc oxide, tin oxide, aluminum oxide, silicon oxide, iron oxide, copper oxide, nickel oxide, and cobalt oxide. Colorants can be selected by manual color matching or by calculation using computer color matching (CCM).

[0029] Examples of dyes include anthraquinones, azo dyes, anthrapyridones, perylenes, anthracenes, perinones, indanthrones, quinacridones, xanthenes, thioxanthenes, oxazines, oxazolines, indigoids, thioindigoids, quinophthalones, naphthalimides, cyanines, methines, pyrazolones, lactones, coumarins, bis-benzoxazolylthiophenes, naphthalenetetracarboxylic acids, phthalocyanines, triarylmethanes, aminoketones, bis(styryl)biphenyls, azines, rhodamines, derivatives of the aforementioned compounds, and mixtures thereof. From the viewpoints of high heat resistance, weather resistance, etc., perinones, perylenes, azo dyes, methines, and quinolines are preferred, and anthraquinones are more preferred. In particular, mixtures of anthraquinones and perinones are preferred.

[0030] Examples of organic pigments include monoazo, disazo, condensed azo, phthalocyanine, quinacridone, anthraquinone, isoindolinone, dioxane, and indigo pigments. More specifically, examples of the pigments include insoluble azo pigments such as disazo yellow, toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, and pyrazolone red; soluble azo pigments such as lithol red, heliobordeaux, pigment yellow, pigment scarlet, and permanent red 2B; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; quinacridone pigments such as quinacridone red and quinacridone magenta; perylene pigments such as perylene red and perylene scarlet; isoindolinone pigments such as isoindolinone yellow and isoindolinone orange; pyranthrone pigments such as pyranthrone red and pyranthrone orange; thioindigo pigments; condensed azo pigments; benzimidazolone pigments; quinophthalone yellow; nickel azo yellow; perinone orange; anthrone orange; dianthronequinonyl red; and dioxazine violet.

[0031] Examples of inorganic pigments include extender pigments, titanium oxide pigments, iron oxide pigments, and spinel pigments. More specific examples include carbon black, titanium oxide, red iron oxide, yellow iron oxide, black iron oxide, ferrite, chromium oxide, aluminum oxide, zirconium oxide, manganese oxide, cobalt oxide, nickel oxide, antimony oxide, lanthanum oxide, cerium oxide, copper oxide, magnesium oxide, bismuth oxide, barium sulfate, zinc oxide, zinc sulfide, zinc hydroxide, cerium hydroxide, lanthanum hydroxide, cobalt hydroxide, nickel hydroxide, manganese hydroxide, vanadium oxide, zinc carbonate, cobalt carbonate, barium carbonate, calcium carbonate, magnesium carbonate, titanium yellow, cobalt green, titanium cobalt green, cobalt blue, cobalt aluminum chrome blue, cobalt chrome green, cerulean blue, cobalt zinc silica blue, copper chrome black, copper-iron manganese black, chrome tin pink, chrome alumina pink, vanadium blue, praseodymium yellow, bismuth vanadate yellow, Victoria green, cobalt silicate, zirconium silicate, talc, kaolin, and zeolite.

[0032] The average primary particle size of the pigment is usually 10 μm or less, preferably 1 to 1,000 nm, and more preferably 10 to 100 nm.

[0033] When the amount of resin contained in a resin molded article having a thickness of about 0.5 mm is taken as 100 parts by mass, the total concentration of the colorants contained in the resin molded article is preferably 0.001 to 2.0 parts by mass. From the viewpoint of the present invention, the total concentration of the colorants is more preferably 0.005 parts by mass or more, and even more preferably 0.5 parts by mass or less.

[0034] Furthermore, when the amount of resin contained in the resin molded article is taken as 100 parts by mass, the concentrations of the colorants contained in the resin molded article are preferably in the following ranges: First colorant: 0.0001 to 10.00 parts by mass (more preferably 0.0005 to 5.00 parts by mass; particularly preferably 0.001 to 1.00 parts by mass) Second colorant: 0.0001 to 10.00 parts by mass (more preferably 0.0005 to 5.00 parts by mass; particularly preferably 0.001 to 1.00 parts by mass) Third colorant: 0.0001 to 10.00 parts by mass (more preferably 0.0005 to 5.00 parts by mass; particularly preferably 0.001 to 1.00 parts by mass) Fourth colorant: 0.0001 to 10.00 parts by mass (more preferably 0.0005 to 5.00 parts by mass; particularly preferably 0.001 to 1.00 parts by mass) Fifth colorant: 0.0001 to 10.00 parts by mass (more preferably 0.0005 to 5.00 parts by mass; particularly preferably 0.001 to 1.00 parts by mass)

[0035] (L of resin molded products ＊ a ＊ b ＊ Colorimetric measurement) The resin molded product of the present invention is measured by L ＊ a ＊ b ＊ In colorimetric measurement, L ＊ (brightness) is 45 to 55, C ＊ is 1.0 or less. ＊ is more preferably 0.5 or less.

[0036] Generally, the method of expressing color tone is CIE L, which is a color space established by the International Commission on Illumination (CIE) to express colors that can be seen with the naked eye. ＊ a ＊ b ＊ There is a color system (color space) called the CIE L*a*b* color system. In this system, color is expressed using three coordinates: lightness is "L*," red (magenta) to green is "a*" (positive is magenta, negative is greenish), and yellow to blue is "b*" (positive is yellowish, negative is blueish). Ideally, a neutral gray tone will be displayed when both the a* and b* values ​​are close to 0.

[0037] The resin molded article of the present invention may be, for example, ＊ a＊ b ＊ L in the color space (standard light source D65, viewing angle 10 degrees) ＊ When the value is between 45 and 55, C ＊ The resin molded article of the present invention also has the effect of a color (neutral gray) required in response to diversifying needs. ＊ The value is −0.5 to +0.5, and b ＊ The value is between -0.5 and +0.5.

[0038] (Metamerism Index) In a preferred embodiment, the metamerism index M defined in JIS Z8719-1996 is １０ (D ６５ : F11 (W １０ ) is 1.5 or less, preferably 1.0 or less. When the metamerism index is 1.5 or less, the resin molded article of the present invention has a high degree of color matching when visually inspected (by human vision) and exhibits little metamerism when visually inspected. The lower limit of the metamerism index of the resin molded article is not particularly limited, but may be 0.0. When the metamerism index of the resin molded article exceeds 1.5, the resin molded article may appear colored rather than neutral gray depending on the light source. Therefore, the resin molded article of the present invention has extremely high designability.

[0039] Metamerism index M defined in JIS Z8719-1996 １０ (D ６５ : F11 (W １０ )) is measured by measuring the color of the resin molded product in accordance with JIS Z8722:2009, and F11 and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ６５ The measurements were performed using a light source, a 10° field of view, and wavelength intervals of 10 nm.

[0040] In a preferred embodiment, the metamerism index M of the resin molded product １０ (D ６５ : A (W １０ )), M １０ (D ６５ : C (W １０ )), M １０ (D ６５ :D ５０(W １０ )), M １０ (D ６５ : F2 (W １０ )), M １０ (D ６５ : F6 (W １０ )), M １０ (D ６５ : F8 (W １０ )), M １０ (D ６５ : F10 (W １０ )), M １０ (D ６５ : F7 (W １０ )) and M １０ (D ６５ : F12 (W １０ )) are each 1.5 or less, preferably 1.0 or less. When each of these metamerism indices is 1.5 or less, the resin molded article of the present invention has a high degree of visual (human visual) match in color and exhibits little visual metamerism. The lower limit of each metamerism indices is not particularly limited, but may be 0.0.

[0041] M １０ (D ６５ : A (W １０ )) is measured by measuring the color of the resin molded product in accordance with JIS Z8722:2009, and is graded A and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ６５ The measurements were performed using a 10° field of view and wavelength intervals of 10 nm. １０ (D ６５ : C (W １０ )) is measured by measuring the color of the resin molded product in accordance with JIS Z8722:2009, and C and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ６５ The measurements were performed using a 10° field of view and wavelength intervals of 10 nm. １０ (D ６５ :D ５０ (W １０ )) is measured by measuring the color of the resin molded product in accordance with JIS Z8722:2009, and measuring the color of the resin molded product in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ５０ and D ６５ The measurements were performed using a 10° field of view and wavelength intervals of 10 nm.１０ (D ６５ : F2 (W １０ )) is measured by measuring the color of the resin molded product in accordance with JIS Z8722:2009, and F2 and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ６５ The measurements were performed using a light source, a 10° field of view, and wavelength intervals of 10 nm.

[0042] M １０ (D ６５ : F6 (W １０ )) is measured by measuring the color of the resin molded product in accordance with JIS Z8722:2009, and F6 and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ６５ The measurements were performed using a 10° field of view and wavelength intervals of 10 nm. １０ (D ６５ : F8 (W １０ )) is measured by measuring the color of the resin molded product in accordance with JIS Z8722:2009, and F8 and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ６５ The measurements were performed using a 10° field of view and wavelength intervals of 10 nm. １０ (D ６５ : F10 (W １０ )) is measured by measuring the color of a resin molded product in accordance with JIS Z8722:2009, and measuring F10 and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ６５ The measurements were performed using a light source, a 10° field of view, and wavelength intervals of 10 nm.

[0043] M １０ (D ６５ : F7 (W １０ )) is measured by measuring the color of the resin molded product in accordance with JIS Z8722:2009, and F7 and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ６５ The measurements were performed using a 10° field of view and wavelength intervals of 10 nm. １０ (D ６５ : F12 (W １０ )) is measured by measuring the color of a resin molded product in accordance with JIS Z8722:2009, and measuring F12 and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. ６５The measurements were performed using a light source, a 10° field of view, and wavelength intervals of 10 nm.

[0044] The above metamerism indices are preferably values ​​calculated from the transmittance measured using a colorimetric optical system with diffuse illumination and 0° light reception, which allows for color matching and suppression of metamerism to be achieved with a sensation closer to human vision (visual perception).

[0045] (Other Additives) The resin molded article 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. may be contained. 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 even be 0 parts by mass.

[0046] (Production of Resin Molded Article) The resin molded article of the present invention can generally be obtained by melt-mixing and dispersing the resin and colorant using a Banbury mixer, a Nauta mixer, a kneading roll, or a single-screw or twin-screw extruder, etc. Furthermore, for the purpose of uniformly dispersing the resin and colorant before kneading, preliminary dispersion may be performed using a tumbler mixer, a blender, or a high-speed mixer.

[0047] The molding method of the obtained resin molded article 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, lustrous pigments, as well as pigments and dyes other than lustrous pigments, can be added depending on the purpose required for the molded article, such as high designability.

[0048] A film- or sheet-shaped molded product can be produced by molding a colored resin molded product using a molding machine according to a general film molding method or sheet molding method. Examples of molding machines that can be used include extrusion molding machines, blow molding machines, vacuum molding machines, pressure molding machines, compression molding machines, and calendar molding machines. The thickness of the film-shaped molded product and sheet-shaped molded product can be adjusted appropriately depending on the application. Specifically, the thickness is preferably 0.1 to 500 μm, and more preferably 1 to 100 μm.

[0049] When a laminated film is coextruded, the resins constituting each layer are heated and melted, and then fed to an extrusion die through separate flow paths from different extruders, pumps, etc., and are extruded into a multilayer structure from the extrusion die, after which they are bonded together. Examples of the extrusion die that can be used include a multi-manifold die and a T-die such as a feed block.

[0050] Furthermore, a fibrous molded product can be produced by spinning a colored resin molded product using a spinning machine. The fiber diameter of the fibrous molded product can be adjusted appropriately depending on the application. Specifically, it is preferably 1 to 1,000 μm, more preferably 1 to 500 μm, and particularly preferably 5 to 200 μm. The fibrous molded product can be cut to an appropriate length or bundled into a fiber bundle. Furthermore, it can be processed into cloth or nonwoven fabric.

[0051] (Suitable Uses of the Resin Molded Article of the Present Invention) There are several uses for the resin molded article. For example, there are light-absorbing ND filters in which a light-absorbing organic dye or pigment is mixed and kneaded into a substrate. Various plastic materials are used for the substrate, and examples include thermoplastic resins such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), and PO (polyolefin). The resin molded article of the present invention transmits achromatic light, making it suitable for the function of an ND filter.

[0052] Furthermore, as a material that transmits infrared rays, it can be used as a material for films and resin molded products for LiDAR, which irradiates near-infrared rays 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 for a case that stores an irradiation device, the device can be protected without losing its performance by transmitting near-infrared rays despite its black appearance.

[0053] In addition, from the viewpoint of achromatic color and reduced metamerism, it can be used for various products with high design value, such as vehicle-related products such as door visors, textile materials such as clothing, printing applications such as toner, and monitors.

[0054] <Dye> Each of the dyes listed below and PET-G resin were molded at a dye concentration of 0.02% by mass at a roll temperature of 185°C, a roll diameter of 6 inches, and a press temperature of 190°C to produce a resin molded product with a thickness of 0.5 mm. The spectral transmittance of each resin molded product is shown in Figures 1 to 4. Blue dye 1 (maximum absorption wavelength 590 nm, C.I. Solvent Blue 122) Blue dye 2 (maximum absorption wavelength 680 nm, C.I. Disperse Blue 60) Green dye 1 (maximum absorption wavelength 700 nm, C.I. Solvent Green 28) Violet dye 1 (maximum absorption wavelength 540 nm, perinone dye) Violet dye 2 (maximum absorption wavelength 570 nm) Yellow dye 1 (maximum absorption wavelength 450 nm) Yellow dye 2 (maximum absorption wavelength 450 nm, C.I. Solvent Yellow 163) Red dye 1 (maximum absorption wavelength 420 nm, C.I. Solvent Orange 63) Red dye 2 (maximum absorption wavelength 480 nm, C.I. Solvent Red 179) Black mixed dye 1 (maximum absorption wavelength 610 nm) Black mixed dye 2 (maximum absorption wavelength 640 nm)

[0055] <Pigments> Each of the following pigments was roll-molded using PET-G resin at a roll temperature of 185°C, a roll diameter of 6 inches, and a press temperature of 190°C at a pigment concentration of 0.02% by mass, to obtain resin molded articles with a thickness of 0.5 mm. The spectral transmittance curves of the obtained resin molded articles are shown in Figures 5 and 6. Red Pigment 1 (maximum absorption wavelength 480 nm, C.I. Pigment Red 149) Yellow Pigment 1 (maximum absorption wavelength 430 nm, C.I. Pigment Yellow 110) Black Pigment 1 (maximum absorption wavelength 610 nm, copper-iron-manganese oxide) Black Pigment 2 (maximum absorption wavelength 530 nm, perylene pigment) Carbon 1 (maximum absorption wavelength 420 nm, C.I. Pigment Black 7)

[0056] <Resin> "PET-G" (manufactured by Eastman Chemical Company)

[0057] (Experiment A) (Production of resin molded articles of examples of the present invention and comparative examples) Each resin molded article was produced by mixing a colorant and PET-G resin in the formulations shown in Tables 1, 2, and 3, and roll-molding the mixture. Specifically, a resin molded article having a thickness of 0.5 mm was produced by roll-molding each formulation of colorant and resin at a roll temperature of 185°C, a roll diameter of 6 inches, and a press temperature of 190°C.

[0058]

[0059]

[0060]

[0061] Each resin molded product was measured for transmission using a Konica Minolta CM-3600A. ６５ Light source, L at 10 degrees field of view ＊ a ＊ b ＊ C ＊ The measurement results are shown in Table 4.

[0062]

[0063] Furthermore, the transmittance of each resin molded product was measured using a Konica Minolta CM-3600A to obtain the spectral transmittance. Graphs of the spectral transmittance are shown in Figures 7 to 11. In Figures 7 to 11, the solid lines indicate the spectral transmittance at each wavelength point. The dotted lines above the solid lines indicate that the spectral transmittance at each measured wavelength point is the average spectral transmittance +5.0%. The dotted lines below the solid lines indicate that the spectral transmittance at each measured wavelength point is the average spectral transmittance -5.0%.

[0064] Furthermore, for the resin molded articles of each example, the difference between the maximum value of the spectral transmittance and the average transmittance, and the difference between the minimum value of the spectral transmittance and the average transmittance in the wavelength range of 420 nm to 700 nm are shown in Table 5. Furthermore, the metamerism index was measured and is shown in Tables 6 and 7.

[0065]

[0066]

[0067]

[0068] Six types of dyes were used in Example 1, five types of dyes in Example 2, and six types of colorants including carbon in Example 3. Examples 1, 2, and 3 each contained a first to fifth colorant, and subtractive color mixing was performed. As a result, the spectral transmittance measured at 10 nm wavelength intervals in the wavelength range of 420 nm or more and 700 nm or less was within ±5% of the average spectral transmittance in the wavelength range of 420 nm or more and 700 nm or less, and C ＊ is 1.0 or less, various metamerism indices are 1.5 or less, and L ＊ a ＊ b ＊ a in color system measurement ＊ The value is -0.5 or more and 0.5 or less, and b ＊ The value is between −0.5 and 0.5.

[0069] On the other hand, Comparative Example 1 is a toned blend of four dye colors that were subtractively mixed to reduce metamerism. In this case, some of the spectral transmittances measured at 10 nm intervals in the wavelength range of 420 nm to 700 nm were outside the range of ±5% from the average spectral transmittance, and two metamerism indices exceeded 1.5, indicating metamerism. Comparative Example 2 is a toned blend of four dye colors with different wavelength ranges of maximum absorption wavelengths. In this case, some of the spectral transmittances measured at 10 nm intervals in the wavelength range of 420 nm to 700 nm were outside the range of ±5% from the average spectral transmittance, and many metamerism indices exceeded 1.5, indicating metamerism.

[0070] Comparative Example 3 is D ６５ Only at 10 degree field of view ＊ b ＊ The color-matched blend contains three dyes, each of which has been matched to reduce the absolute value of the spectral transmittance. In this case, some of the spectral transmittances measured at 10 nm intervals in the wavelength range of 420 nm to 700 nm were outside the range of ±5% from the average spectral transmittance, and many of the metamerism indices exceeded 1.5, indicating that metamerism was observed. Comparative Example 4 is a blend in which the lightness is approximated using a general carbon black pigment. In this case, some of the spectral transmittances measured at 10 nm intervals in the wavelength range of 420 nm to 700 nm were outside the range of ±5% from the average spectral transmittance, and many of the metamerism indices exceeded 1.5, indicating that metamerism was observed.

[0071] Comparative Example 5 is an example in which the lightness was reduced by using perylene black, and Comparative Examples 6 and 7 are examples in which the lightness was reduced by using a commercially available black dye. In these cases, some of the spectral transmittances measured at wavelength intervals of 10 nm in the wavelength range of 420 nm to 700 nm were outside the range of ±5% of the average spectral transmittance, and many of the metamerism indices exceeded 1.5, indicating that metamerism was observed.

[0072] (Experiment B) In the same manner as in Experiment A, resin molded articles of each composition were prepared, and the spectral transmittance, L ＊ a ＊ b ＊a in color system measurement ＊ value, b ＊ Value, C ＊ , and each metamerism index were measured.

[0073] Specifically, the colorant of each formulation example shown in Table 8 was mixed with PET-G resin, and the mixture was injection molded using a 1-ounce vertical injection molding machine at a heater temperature of 250°C to produce a resin molded product with a thickness of 2.0 mm.

[0074] In addition, for the resin molded products of each example, D was measured by transmission using a Konica Minolta CM-3600A. ６５ L at 10 degrees of light source ＊ a ＊ b ＊ C ＊ is shown in Table 9.

[0075]

[0076]

[0077] Furthermore, graphs of the spectral transmittance of each resin molded product are shown in Figures 12 and 13. In Figures 12 and 13, the solid lines indicate the spectral transmittance at each wavelength point. The dotted lines above the solid lines indicate that the spectral transmittance at each measured wavelength point is the average spectral transmittance +5.0%. The dotted lines below the solid lines indicate that the spectral transmittance at each measured wavelength point is the average spectral transmittance -5.0%.

[0078] Furthermore, for the resin molded articles of each example, the difference between the maximum value of the spectral transmittance and the average transmittance, and the difference between the minimum value of the spectral transmittance and the average transmittance in the wavelength range of 420 nm to 700 nm are shown in Table 10. Furthermore, each metamerism index was measured and is shown in Table 11.

[0079]

[0080]

[0081] In Example 4, seven types of dyes were used. The first to fifth colorants were each included in Example 4, and subtractive color mixing was performed. As a result, the spectral transmittances measured at 10 nm wavelength intervals in the wavelength range of 420 nm to 700 nm were each within ±5% of the average spectral transmittance in the wavelength range of 420 nm to 700 nm. ＊ is 1.0 or less, various metamerism indices are 1.5 or less, and L ＊ a ＊ b ＊ a in color system measurement ＊ The value is -0.5 or more and 0.5 or less, and b ＊ The value is between −0.5 and 0.5.

[0082] Comparative Example 8 is D ６５ Only at 10 degree field of view ＊ b ＊ In this case, some of the spectral transmittances measured at wavelength intervals of 10 nm in the wavelength range of 420 nm or more and 700 nm or less were outside the range of ±5% of the average spectral transmittance, and many of the metamerism indices exceeded 1.5.

[0083] In Comparative Example 9, only the lightness was approximated using a general carbon black pigment. In this case, a part of the spectral transmittance measured at wavelength intervals of 10 nm in the wavelength range of 420 nm or more and 700 nm or less was outside the range of ±5% from the average spectral transmittance, and two metamerism indices exceeded 1.5. ＊ , b ＊ has become more expensive.

[0084] In Comparative Example 10, only the lightness was approximated using a commercially available black dye. In this case, some of the spectral transmittances measured at wavelength intervals of 10 nm in the wavelength range of 420 nm or more and 700 nm or less were outside the range of ±5% from the average spectral transmittance, and many of the metamerism indices exceeded 1.5. ＊ , b ＊ has become more expensive.

[0085] As is clear from the above examples, the resin molded articles of the examples of the present invention, which have flat spectral transmittance, also have small metameric indices, and it is understood that color changes due to light sources are suppressed.

Claims

1. A resin molded product containing a first colorant having a maximum absorption wavelength in the wavelength range of 420 nm or more and 450 nm or less, a second colorant having a maximum absorption wavelength in the wavelength range of more than 450 nm and less than 500 nm, a third colorant having a maximum absorption wavelength in the wavelength range of more than 500 nm and less than 570 nm, a fourth colorant having a maximum absorption wavelength in the wavelength range of more than 570 nm and less than 650 nm, and a fifth colorant having a maximum absorption wavelength in the wavelength range of more than 650 nm and less than 700 nm, wherein the product is colored by subtractive mixing of the first colorant, the second colorant, the third colorant, the fourth colorant, and the fifth colorant, and D ６５ Light source 10 degree field of view brightness L ＊ 45-55, C ＊ a spectral transmittance of 1.0 or less, and each of the spectral transmittances measured at wavelength intervals of 10 nm in the wavelength range of 420 nm or more and 700 nm or less is within ±5% of an average spectral transmittance in the wavelength range of 420 nm or more and 700 nm or less.

2. Metamerism index M defined in JIS Z8719-1996 １０ (D ６５ : F11 (W １０ 2. The resin molded product according to claim 1, wherein the ratio of the surface area to the surface area of ​​the resin molded product is 1.5 or less.

3. Conditional color matching index M １０ (D ６５ : A (W １０ ) ) M １０ (D ６５ :C(W １０ ) ) M １０ (D ６５ :D ５０ (W １０ ) ) M １０ (D ６５ : F2 (W １０ ) ) M １０ (D ６５ : F6 (W １０ ) ) M １０ (D ６５ : F7 (W １０ ) ) M １０ (D ６５ : F8 (W １０ ) ) M １０ (D ６５ : F10 (W １０ )) and M １０ (D ６５ : F12 (W １０ 3. The resin molded product according to claim 2, wherein each of the above ratios is 1.5 or less.

4. A resin molded product according to any one of claims 1 to 3, characterized in that it contains carbon black.

5. L ＊ a ＊ b ＊ In color system measurement, ＊ The value is -0.5 or more and 0.5 or less, and b ＊ The resin molded product according to any one of claims 1 to 3, wherein the value is -0.5 or more and 0.5 or less.

6. The resin molded product according to any one of claims 1 to 3, which is an ND filter, a black panel, a fiber material, a door visor, a toner, an infrared transmitting film or synthetic leather.

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