Resin molding

Abstract

To provide a resin molding which has low dependency on concentration and thickness, can obtain spectral reflectance and spectral transmittance that are difficult for a single black dye / pigment and uniform achromatic color, and suppresses metamerism.SOLUTION: A resin molding contains: a first coloring agent having a maximum absorption wavelength within the wavelength range of 420 nm or more and 450 nm or less; a second coloring agent having a maximum absorption wavelength within the wavelength range of more than 450 nm and 500 nm or less; a third coloring agent having a maximum absorption wavelength within the wavelength range of more than 500 nm and 570 nm or less; a fourth coloring agent having a maximum absorption wavelength within the wavelength range of more than 570 nm and 650 nm or less; and a fifth coloring agent having a maximum absorption wavelength within the wavelength range of more than 650 nm and 700 nm or less. The resin molding is colored by subtractive color mixture of the first to fifth coloring agents, brightness L* in D65 light source 10-degree visual field is 45 to 55, and C* is 1.0 or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Carbon black has traditionally been used as a pigment to be added to black paints and resin molded products. However, depending on the type of carbon black, reflected or transmitted light may appear black with a yellowish or reddish tinge, and metamerism may occur. For this reason, it has been difficult to express the achromatic color black using carbon black alone.

[0003] In addition, in a method of obtaining an achromatic resin molded product by subtractive color mixing using chromatic dyes and pigments, the color is adjusted using a specific light source and field of view, but the spectral reflectance and spectral transmittance at visible light wavelengths of 420 nm to 700 nm are not flat. Therefore, if a light source other than the one used for color adjustment is used, if the concentration during color adjustment is changed, or if the thickness of the resin molded product during color adjustment is changed, the product may appear to be colored chromatically, and the transmitted light source color may appear to be colored in 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 of manufacturing a light amount adjustment member by applying an ink in which a black dye or carbon black and other dyes are mixed onto a transparent substrate. Also, Patent Document 2 describes a black film made of a thermoplastic resin that uses two or more dyes other than black. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2005-070752 A [Patent Document 2] International Publication No. 2017 / 217429 Summary of the Invention [Problem to be solved by the invention]

[0006] In Patent Document 1, a light amount adjusting member having almost 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 having a maximum absorption wavelength in the absorption spectrum in the range of 630 nm to 750 nm. However, Patent Document 1 is intended for the purpose of adjusting the amount of light, and although the spectral transmittance of visible light is considered to be constant to a certain extent, there is no description of the spectral reflected light in the entire visible light range, and there is no description or suggestion of subtractive color mixing.

[0007] In Patent Document 2, the invention is aimed at solving the problem of color tone differences occurring within the same decorative molding and the difficulty of expressing a deep, clear, jet black color, mainly for decorative molding. * 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 expression of achromatic black when the density is low. In addition, although the color tone difference within the same decorative molding is mentioned, metamerism is not considered.

[0008] The object of the present invention is to obtain an achromatic color in a resin molded product that has low dependency 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. [Means for solving the problem]

[0009] Means for Solving the Problems The present inventors have conducted extensive research to achieve the above object 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 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 more 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, D is colored by subtractive mixing of the first colorant, the second colorant, the third colorant, the fourth colorant, and the fifth colorant; 65 Light source luminosity L at 10 degrees * 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 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 greater than or equal to -0.5 and less than or equal to 0.5, 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] A resin molded product according to any one of [1] to [3], which is an ND filter, a black panel, a textile material, a door visor, a toner, an infrared-transmitting film, or synthetic leather. Effect of the Invention

[0016] According to the present invention, it is possible to provide a resin molded product that has low dependency on concentration or thickness, expresses an achromatic color in which both the spectral reflectance and the spectral transmittance are almost uniform in the visible light region of 420 to 700 nm, and suppresses metamerism. This makes it possible to provide a transparent resin molded article in which the transmitted color of light from a light source transmitted through the resin molded article can be adjusted to a slight change in color tone. [Brief description of the drawings]

[0017] [Figure 1] Graphs (a), (b), and (c) show the spectral transmittance of blue dye 1, blue dye 2, and green dye 1 used in the examples. [Diagram 2]Graphs (a), (b), and (c) show the spectral transmittance of purple dye 1, purple dye 2, and yellow dye 1 used in the examples. [Diagram 3] Graphs (a), (b), and (c) show the spectral transmittance of Yellow Dye 2, Red Dye 1, and Red Dye 2 used in the examples. [Figure 4] 2(a) and 2(b) are graphs showing the spectral transmittance of black mixed dye 1 and black mixed dye 2. [Diagram 5] Graphs (a), (b), and (c) show the spectral transmittance of Red Pigment 1, Yellow Pigment 1, and Black Pigment 1. [Figure 6] Graphs (a) and (b) show the spectral transmittance of black pigment 2 and carbon. [Figure 7] 2(a) and 2(b) are graphs showing the spectral transmittance of the resin molded articles of Examples 1 and 2. [Figure 8] 6(a) and 6(b) are graphs showing the spectral transmittance of the resin molded articles of Example 3 and Comparative Example 1. [Figure 9] 6(a) and 6(b) are graphs showing the spectral transmittance of the resin molded articles of Comparative Examples 2 and 3. [Figure 10] 6(a) and 6(b) are graphs showing the spectral transmittance of the resin molded articles of Comparative Examples 4 and 5. [Figure 11] 6(a) and 6(b) are graphs showing the spectral transmittance of the resin molded articles of Comparative Examples 6 and 7. [Figure 12] 5(a) and 5(b) are graphs showing the spectral transmittance of the resin molded articles of Example 4 and Comparative Example 8. [Figure 13] 6(a) and 6(b) are graphs showing the spectral transmittance of the resin molded articles of Example 9 and Comparative Example 10. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0019] The resin constituting the resin component of the present invention may be a thermosetting resin other than a thermoplastic resin. Examples of the thermosetting resin include conventionally known thermosetting resins such as urethane resin, epoxy resin, phenol resin, unsaturated polyester resin, vinyl ester resin, alkyd resin, melamine resin, imide resin, styrene resin obtained by polymerizing a monomer having a vinyl polymerizable functional group having two or more functional groups, and (meth)acrylate resin.

[0020] (Coloring agent) The resin molded article of the present invention contains five or more colorants. Specifically, the resin molded article contains 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 product of the present invention has optical properties that absorb light over the entire visible light range. Specifically, the inventors have found that the spectral transmittance of the resin molded product must be in the wavelength range of 420 to 700 nm, which can effectively absorb most visible light radiation. The wavelength range of 420 to 700 nm is divided as described above, and five types of colorants having maximum absorption wavelengths in each wavelength range are mixed and adjusted to perform subtractive color mixing. Subtractive color mixing is a method of lowering brightness by mixing colorants with different absorption wavelengths. This allows the resin molded product to be provided that has low dependency on concentration and thickness, and that expresses an achromatic color in which both the spectral reflectance and the spectral transmittance are almost uniform in the visible light range of 420 to 700 nm, thereby suppressing metamerism.

[0022] In the visible light wavelength range of 420 to 700 nm, the spectral transmittance at 10 nm wavelength intervals is ±5% or less, preferably ±3% or less, more preferably ±2% or less, relative to the average transmittance calculated by averaging the spectral transmittance at 10 nm wavelength intervals. If this exceeds ±5%, the possibility of the metamerism index exceeding 1.5 increases, making metamerism more likely to occur. In addition, in the wavelength range of less than 420 nm, absorption often occurs depending on the resin used, such as polyvinyl chloride resin, and the influence on metamerism of resin molded products is small, so this range is excluded from the wavelength range. Furthermore, the desired achromatic color can be obtained even if the range of 420 to 700 nm, excluding the range of less than 420 nm, is used as the standard.

[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 take values ​​at 10 nm intervals from 420 nm to 700 nm. 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-formed to produce a resin molded product with a thickness of 0.5 mm. Then, the spectral transmittance of five points of the resin molded product is measured at each measurement wavelength point, and the average value is adopted as the measured value of the spectral transmittance.

[0024] (Spectral transmittance distribution of resin molded products) The resin molded product of the present invention has a spectral transmittance measured at 10 nm intervals in the wavelength range of 420 nm to 700 nm that 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 by subtractive color mixing. As a result, transmitted light with no change in saturation can be obtained, and a resin molded product 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 each of five locations on the resin molded product, and the average of the five measured values ​​is taken as the spectral transmittance at each wavelength interval. In addition, the average of the spectral transmittances at 29 measurement wavelengths in the range of 420 nm to 700 nm is taken as the average spectral transmittance. As a measuring device for the spectral transmittance, a commercially available spectral color measuring device such as a stationary type color measuring device or a portable (handy type) type can be used.

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

[0027] The resin molded product of the present invention contains at least the above-mentioned five or more kinds of colorants. The types of colorants are five or more. There is no particular upper limit to the types of colorants. However, since there are 29 wavelength points in 10 nm intervals in the wavelength range of 420 to 700 nm, it is not necessary to use more than 29 types of colorants. Therefore, the types of colorants may be 29 or less.

[0028] It is preferable to select the type, particle size, and processing method of the dye or pigment depending on the application. For example, when transparency is to be imparted to a colored product, the type and particle size of the dye or pigment may be appropriately selected. The shining agent is an effective pigment that imparts retroreflective properties and light scattering properties to the surface of the molded product obtained, and changes color depending on the viewing angle. As the pearl mica pigment, 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 can be used. Colorants may be selected by manual mixing or by calculation using computer color matching (CCM) or other methods.

[0029] Examples of dyes include anthraquinones, azos, 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 above compounds, and mixtures thereof. From the viewpoint of high heat resistance, weather resistance, etc., perinones, perylenes, azos, methines, and quinolines are preferred, and anthraquinones are more preferred. In particular, a mixture of anthraquinones and perinones is 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, helio bordeaux, 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; dianthraquinonyl red; and dioxazine violet.

[0031] Examples of inorganic pigments include extender pigments, titanium oxide pigments, iron oxide pigments, and spinel pigments. More specifically, examples of the pigment 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 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 more preferably 0.5 parts by mass or less.

[0034] When the amount of resin contained in the resin molded product is taken as 100 parts by mass, the concentration of each colorant contained in the resin molded product is preferably in the following range. 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 * color system measurement) The resin molded product of the present invention is L conforming to JIS Z 8781-4. * a * b * In colorimetric measurements, L * (Brightness) is 45~55, C * is less than or equal to 1.0. * is more preferably 0.5 or less.

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

[0037] The resin molded article of the present invention is, for example, * a * b *L in color space (standard light source D65, viewing angle 10 degrees) * When the value is between 45 and 55, C * The value is 1.0 or less (preferably 0.5 or less). The resin molded article of the present invention also has the effect of a color (neutral gray) required in response to diversifying needs. In a preferred embodiment, the a * The value is -0.5 to +0.5, and b * The value is between -0.5 and +0.5.

[0038] (conditional color matching index) In a preferred embodiment, the metamerism index M defined in JIS Z8719-1996 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 product of the present invention has a high degree of color consistency when visually inspected (by human vision) and has little metamerism when visually inspected. The lower limit of the metamerism index of the resin molded product is not particularly limited, but may be 0.0. When the metamerism index of the resin molded product exceeds 1.5, the resin molded product may appear colored rather than neutral gray depending on the light source. Therefore, the resin molded product 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 for resin molded products 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 taken 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 (D65 :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 color consistency when visually observed (by human vision) and has low metamerism when visually observed. The lower limit of each metamerism index is not particularly limited, but may be 0.0.

[0041] M 10 (D 65 :A(W 10 )) is measured for resin molded products in accordance with JIS Z8722:2009, and graded A and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. 65 The measurements were taken using a light source, a 10° field of view, and wavelength intervals of 10 nm. M 10 (D 65 :C(W 10 )) is measured for resin molded products in accordance with JIS Z8722:2009, and graded C and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. 65 The measurements were taken using a light source, a 10° field of view, and wavelength intervals of 10 nm. M 10 (D 65 :D 50 (W 10 )) is a resin molded product measured in accordance with JIS Z8722:2009, and D is measured in accordance with JIS Z8781-4:2013 and JIS Z8719-1996.50 and D. 65 The measurements were taken using a light source, a 10° field of view, and wavelength intervals of 10 nm. M 10 (D 65 :F2(W 10 )) is measured for resin molded products 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 taken 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 for resin molded products 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 taken using a light source, a 10° field of view, and wavelength intervals of 10 nm. M 10 (D 65 :F8(W 10 )) is measured for resin molded products 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 taken using a light source, a 10° field of view, and wavelength intervals of 10 nm. M 10 (D 65 :F10(W 10 )) is measured for resin molded products in accordance with JIS Z8722:2009, and F10 and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. 65 The measurements were taken 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 for resin molded products 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 taken using a light source, a 10° field of view, and wavelength intervals of 10 nm. M10 (D 65 :F12(W 10 )) is measured for resin molded products in accordance with JIS Z8722:2009, and F12 and D in accordance with JIS Z8781-4:2013 and JIS Z8719-1996. 65 The measurements were taken using a light source, a 10° field of view, and wavelength intervals of 10 nm.

[0044] Each of the metamerism indices is preferably a value calculated from the transmittance measured by a color measurement optical system with diffuse illumination and 0° light receiving direction, thereby achieving color matching and suppression of metamerism with a sensation closer to human vision (visual perception).

[0045] (Other 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. may be contained. When the amount of resin contained in the resin molded product 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.

[0046] (Manufacturing of resin molded products) The resin molded product 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 product is not limited, but it is molded into a predetermined shape by a known method such as injection molding, injection compression molding, compressed air molding, blow molding, vacuum molding, foam molding, extrusion molding, etc. At this time, additives such as heat stabilizers, weather stabilizers, lubricants, pigment dispersants, and antistatic agents can be added depending on the purpose. In addition, lustrous materials and other pigments and dyes other than lustrous materials can be added depending on the purpose required for the molded product, 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 by a general film molding method or sheet molding method. Examples of the molding machine that can be used include an extrusion molding machine, a blow molding machine, a vacuum molding machine, a pressure molding machine, a compression molding machine, and a calendar molding machine. The thickness of the film-shaped molded product and the sheet-shaped molded product may be appropriately adjusted 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 co-extruded, the resins constituting each layer are heated and melted, and then fed to an extrusion die through respective flow paths from different extruders, pumps, etc., and bonded together after being extruded in multiple layers from the extrusion die. As the extrusion die, for example, a T-die such as a multi-manifold die or a feed block can be used.

[0050] In addition, a fibrous molded product can be produced by spinning the colored resin molded product using a spinning machine. The fiber diameter of the fibrous molded product may be appropriately adjusted 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 may be cut to an appropriate length or bundled into a fiber bundle. Furthermore, it can be processed into a cloth or nonwoven fabric.

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

[0052] In addition, 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 target and the properties of that target. 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 achromaticity and reduced metamerism, it can be used for products with high design value, such as door visors for vehicles, textile materials for clothing, printing applications such as toner, and monitors. EXAMPLES

[0054] <dye> The following dyes 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 resin molded products with a thickness of 0.5 mm. The spectral transmittance of each resin molded product is shown in FIGS. 1 to 4. Blue dye 1 (maximum absorption wavelength 590 nm, CI Solvent Blue 122) Blue dye 2 (maximum absorption wavelength 680 nm, CI Disperse Blue 60) Green dye 1 (maximum absorption wavelength 700 nm, CI Solvent Green 28) Purple dye 1 (maximum absorption wavelength 540 nm, perinone dye) Purple dye 2 (maximum absorption wavelength 570 nm) Yellow dye 1 (maximum absorption wavelength 450 nm) Yellow dye 2 (maximum absorption wavelength 450 nm, CI Solvent Yellow 163) Red dye 1 (maximum absorption wavelength 420 nm, CI Solvent Orange 63) Red dye 2 (maximum absorption wavelength 480 nm, CI Solvent Red 179) · Black mixed dye 1 (maximum absorption wavelength 610nm) · Black mixed dye 2 (maximum absorption wavelength 640nm)

[0055] <Pigments> Each of the pigments listed below was roll-molded using PET-G resin at a pigment 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 obtain resin molded products with a thickness of 0.5 mm. The spectral transmittance curves of the obtained resin molded products are shown in Figures 5 and 6. Red pigment 1 (maximum absorption wavelength 480 nm, CI Pigment Red 149) Yellow Pigment 1 (maximum absorption wavelength 430 nm, CI 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, CI Pigment Black 7)

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

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

[0058] [Table 1]

[0059] [Table 2]

[0060] [Table 3]

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

[0062] [Table 4]

[0063] Furthermore, each resin molded product was subjected to transmission measurement using a Konica Minolta CM-3600A to obtain the spectral transmittance. Graphs of the spectral transmittance are shown in Figs. 7 to 11. 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, Table 5 shows 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 range of 420 nm to 700 nm, for the resin molded product of each example. Furthermore, the metamerism index was measured and is shown in Tables 6 and 7.

[0065] [Table 5]

[0066] [Table 6]

[0067] [Table 7]

[0068] Six types of dyes were used in Example 1, five types of dyes were used in Example 2, and six types of colorants including carbon were used 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 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, respectively, 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 greater than or equal to -0.5 and less than or equal to 0.5, and b * The value is between -0.5 and 0.5.

[0069] On the other hand, Comparative Example 1 is a color-matching blend of four dye colors that are subtractively mixed to reduce metamerism. In this case, 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% from the average spectral transmittance, and two types of metamerism indexes exceeded 1.5, indicating metamerism. Comparative Example 2 is a toning blend of four dyes with different maximum absorption wavelength ranges. 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 that metamerism was observed.

[0070] Comparative Example 3 is D 65 Light source 10 degree field of view only a * b * In this case, some of the spectral transmittances measured at 10 nm wavelength 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. In Comparative Example 4, the lightness was approximated by using a general carbon black pigment. In this case, some of the spectral transmittances measured at 10 nm wavelength 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 that metamerism was observed.

[0071] Comparative Example 5 is an example in which the brightness was reduced by using perylene black, and Comparative Examples 6 and 7 are examples in which the brightness 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% from the average spectral transmittance, and many of the metamerism indices exceeded 1.5, indicating that metamerism was observed.

[0072] (Experiment B) As in Experiment A, resin molded products 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 colorants of each formulation example shown in Table 8 were mixed with PET-G resin, and 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, the resin molded products of each example were measured for transmission D using a Konica Minolta CM-3600A. 65 L at 10 degree field of view * a * b * C * are shown in Table 9.

[0075] [Table 8]

[0076] [Table 9]

[0077] Furthermore, the spectral transmittance graphs of each resin molded product are shown in Figs. 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 products of each example, Table 10 shows 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 range of 420 nm to 700 nm. Furthermore, each metamerism index was measured and is shown in Table 11.

[0079] [Table 10]

[0080] [Table 11]

[0081] Seven types of dyes were used in Example 4. In Example 4, each of the first to fifth colorants was included, and subtractive color mixing was performed. As a result, the spectral transmittance measured at 10 nm 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, respectively, 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 greater than or equal to -0.5 and less than or equal to 0.5, and b * The value is between -0.5 and 0.5.

[0082] Comparative Example 8 is D 65 Light source 10 degree field of view only a * 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% from the average spectral transmittance, and many of the metamerism indices exceeded 1.5.

[0083] In Comparative Example 9, only the lightness was approximated by 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 to 700 nm 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 by 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 to 700 nm 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 products of the examples of the present invention having flat spectral transmittance also have small metamerism indices, and it is understood that color changes due to light sources are suppressed.

Claims

1. A resin molded product comprising: 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 not more than 500 nm; a third colorant having a maximum absorption wavelength in a wavelength range of more than 500 nm and not more than 570 nm; a fourth colorant having a maximum absorption wavelength in a wavelength range of more than 570 nm and not more than 650 nm; and a fifth colorant having a maximum absorption wavelength in a wavelength range of more than 650 nm and not more than 700 nm, The first colorant, the second colorant, the third colorant, the fourth colorant, and the fifth colorant are mixed in a subtractive manner to produce a color; 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. The resin molded article according to any one of claims 1 to 3, further comprising 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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