Black resin composition, molded article, and multilayer body

Abstract

Provided are: a black resin composition that has high stability over time, excellent design properties, and jet blackness; a molded article; and a multilayer body. The black resin composition contains a colorant (P) and a thermoplastic resin (R). The colorant (P) contains a perylene black pigment (p1) and a complementary color pigment (p2). The complementary color pigment (p2) is one or more pigments selected from the group consisting of perylene red pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, dioxazine pigments, diketopyrrolopyrrole pigments, and carbon black pigments. The colorant (P) may additionally contain an inorganic black reflective pigment (p3). When a carbon black pigment is included, the mass ratio of the carbon black pigment and the perylene black pigment (p1) is equal to or less than a specific value, and the content of the inorganic black reflective pigment (p3) is 0.9 parts by mass or less per 100 parts by mass of the perylene black pigment (p1).

Description

Black resin composition, molded articles and laminates 【0001】 This disclosure relates to a black resin composition, molded articles, and laminates containing perylene black. 【0002】 Technological development of photovoltaic power generation systems, which convert sunlight into electrical energy, is being advanced. Photovoltaic power generation systems incorporate multiple solar cell modules, each containing a power generation element. In the gaps between the multiple power generation elements within the solar cell module, a white sheet is installed on the back side of the power generation elements to increase power generation efficiency by approximately 3-5%. However, since power generation elements are usually black, there is a demand to make the gaps between them black as well. 【0003】 One method for making the gaps between power generation elements black is to make the sealing material or back protective sheet of the power generation elements black. Patent Document 1 proposes a black barrier sealing film consisting of a laminate of a black barrier layer containing a first matrix resin and a black masterbatch having a melt index and surface tension within a specific range, and a white barrier layer containing a second matrix resin and a white masterbatch having a melt index and surface tension within a specific range. The black barrier layer is described as using 80 to 92 parts by mass of polyethylene resin, 5 to 10 parts of a highly infrared-transmitting pigment, 1 to 5 parts of carbon oxide black with a particle size of 20 to 50 nm, 1 to 5 parts of titanium dioxide with a particle size of 10 to 50 nm, 0.5 to 1 part of a dispersant, and 0.1 to 0.5 parts of an antioxidant. Patent Document 2 also discloses an insulating layer used in a solar cell module, with the objective of improving the power generation efficiency of the solar cell module, having a reflectance of 55 to 80% and a transmittance of 3 to 20% at 750 to 1100 nm. 【0004】Patent Document 3 discloses a black photoconductive toner sensitive to semiconductor laser wavelengths, comprising a binder resin such as a styrene-acrylic copolymer, a photoconductive material, a perylene-based black pigment, and a magenta pigment. Patent Document 4 discloses a thermoplastic resin composition containing perylene black pigment as an infrared-transmitting black pigment for a thermoplastic aromatic resin, which is used as the laser light transmitting side during laser welding and is capable of laser marking. Furthermore, Patent Document 5 discloses a composite sealing adhesive film comprising a black infrared-transmitting layer and an infrared-reflective layer, and describes an example in which a perylene-based pigment is used in the black infrared-transmitting layer. Patent Document 6 discloses a gap synergistic film for photovoltaic modules in which a functional layer and a composite substrate layer are sequentially laminated on an adhesive layer, and shows an example in which a perylene-based pigment is used in the functional layer. Furthermore, Patent Document 7 discloses an adhesive sealing film comprising an infrared-high transmittance adhesive film layer and an infrared-high reflectance adhesive film layer. Among these, the infrared high transmittance adhesive film layer has a transmittance of over 55% for 700-1100 nm and a transmittance of less than 2% for 400-700 nm, and an example in which perylene black is used for this layer has been disclosed. 【0005】 Chinese Patent Application Publication No. 116494620 Specification Chinese Patent Application Publication No. 118281099 Specification JP Publication No. P3-168755 JP Publication No. 2020-50822 Chinese Patent Application Publication No. 118440615 Specification Chinese Patent Application Publication No. 119119893 Specification International Publication No. 2023 / 115943 【0006】Since solar power generation systems are usually installed outdoors, rain and high humidity can cause the glass surface to get wet, lowering the resistance of the surface glass and increasing the potential difference between the glass and the power generation element. Furthermore, in recent years, the increased voltage due to large-scale power generation has led to a larger potential difference between the frame within the solar cell module and the semiconductor of the power generation element. As a result, the PID (Potential Induced Degradation) phenomenon is more likely to occur than before, leading to a problem of reduced solar cell output. In the market, there is a demand for jet black finishes with superior aesthetic appeal, and the black barrier sealing film described in Patent Document 1 and the insulating layer described in Patent Document 2 have shortcomings in terms of aesthetic appeal and resistance to PID (stability over time). 【0007】 While the above discussion focused on the challenges of using this material as a encapsulant for solar cells, similar challenges may arise in any application requiring jet blackness and long-term stability. 【0008】 This disclosure is made in view of the above background, and aims to provide a black resin composition, molded article, and laminate that have high stability over time and also possess excellent design qualities due to their jet-black color. 【0009】After diligent research by the present inventors, they have found that the problems of this disclosure can be solved in the following embodiments, and have completed this disclosure. [1]: A black resin composition comprising a colorant (P) and a thermoplastic resin (R), wherein the colorant (P) comprises a perylene black pigment (p1) and a complementary pigment (p2), and the complementary pigment (p2) is one or more selected from the group consisting of perylene red pigment, anthraquinone pigment, quinacridone pigment, phthalocyanine pigment, dioxazine pigment, diketopyrrolopyrrole pigment and carbon black pigment, and in the case of containing the carbon black pigment, the mass ratio of the carbon black pigment to the perylene black pigment (p1), [carbon black pigment] / [perylene black pigment (p1)], is less than 0.1. [2]: The black resin composition according to [1], wherein the glass transition temperature of the thermoplastic resin (R) is 0°C or less. [3]: The black resin composition according to [1] or [2], wherein the complementary pigment (p2) satisfies (I) below. (I) The complementary pigment (p2) is a complementary pigment prepared by blending 0.3 parts by mass of the complementary pigment (p2) with 100 parts by mass of low-density polyethylene resin, and in a test piece with a thickness of 250 μm, the average transmittance at wavelengths of 800 to 1100 nm in accordance with ASTM-E424-71-2023 is 50% or more. [4]: ​​The complementary pigment (p2) is a complementary organic pigment (p2-a), and of 100% by mass of the complementary organic pigment (p2-a), the complementary organic pigment (p2-a) which is a nitrogen-containing compound is 55% by mass or more, according to any one of [1] to [3]. [5]: The complementary pigment (p2) content is 0.5 to 20 parts by mass per 100 parts by mass of perylene black pigment (p1), according to any one of [1] to [4]. [6]: The black resin composition according to any one of [1] to [5], wherein the thermoplastic resin (R) contains polyolefin wax (WO) and the mass ratio [complementary pigment (p2)] / [polyolefin wax (WO)] is 0.01 to 100. [7]: The black resin composition according to any one of [1] to [6], wherein the colorant (P) may further contain an inorganic black reflective pigment (p3), and the content of the inorganic black reflective pigment (p3) is 0.9 parts by mass or less per 100 parts by mass of perylene black pigment (p1).[8]: A molded article formed from either (i) a black resin composition according to any one of [1] to [7], or (ii) a moldable black composition obtained by adding at least the black resin composition to a diluted resin. [9]: A laminate having a white layer and a black layer formed from either (i) a black resin composition according to any one of [1] to [7], or (ii) a moldable black composition obtained by adding at least the black resin composition to a diluted resin. 【0010】 This disclosure provides excellent advantages, including the ability to provide black resin compositions, molded articles, and laminates that have high stability over time and, furthermore, possess excellent design qualities due to their jet-black color. 【0011】 A schematic plan view showing an example of a solar cell module of this embodiment. A schematic cross-sectional view of a power generation element along the II-II cutting line in Figure 1. A schematic cross-sectional view of a solar cell module along the III-III cutting line in Figure 1. A schematic cross-sectional view illustrating an example of the manufacturing process of the solar cell module of this embodiment. A schematic cross-sectional view of the solar cell module of the embodiment. 【0012】 The present disclosure will be described in detail below. Other embodiments are also included in the scope of this disclosure, insofar as they are consistent with the spirit of this disclosure. Numerical ranges specified using "~" in this specification include the numbers before and after "~". Also, "film" and "sheet" are synonymous and are not distinguished by thickness. Furthermore, unless otherwise noted, each component may be used independently or in combination of two or more. Also, the numerical values ​​described herein refer to values ​​obtained by the methods described in the [Examples] section below. 【0013】1. Black Resin Composition The black resin composition of this disclosure (hereinafter also referred to as "this black resin composition") comprises a colorant (P) and a thermoplastic resin (R). The colorant (P) comprises a perylene black pigment (p1) (hereinafter also referred to as "PB pigment (p1)") and a complementary pigment (p2). The complementary pigment (p2) is one or more selected from the group consisting of perylene red pigment, anthraquinone pigment, quinacridone pigment, phthalocyanine pigment, dioxazine pigment, diketopyrrolopyrrole pigment and carbon black pigment (hereinafter also referred to as "CB pigment"). If a CB pigment is included, the mass ratio of the CB pigment to the PB pigment (p1), i.e., [CB pigment] / [PB pigment (p1)], is less than 0.1 in this black resin composition. 【0014】 This black resin composition may further contain an inorganic black reflective pigment (p3) (hereinafter also referred to as IBR pigment (p3)) as a coloring agent (P). From the viewpoint of enhancing design aesthetics, the content of IBR pigment (p3) shall be 0.9 parts by mass or less per 100 parts by mass of PB pigment (p1). This black resin composition does not need to contain IBR pigment (p3). 【0015】 In this specification, a black resin composition refers to a resin composition having a thermoplastic resin (R) as a matrix component and a colorant (P) as a coloring component, which appears black to the human eye. The black resin composition can be used for various applications. In one embodiment, the black resin composition can be used as a masterbatch. In this case, the black resin composition is added to a diluted resin to prepare a moldable black composition, and a molded product is obtained by molding the composition. Here, "molding black composition" means a molding composition that exhibits a black color, and is distinguished from the "black resin composition" as a masterbatch. In another embodiment, the black resin composition can be used directly as a molding black composition without going through a masterbatch. In this case, the "black resin composition" functions as a molding black composition. That is, "black resin composition" refers to the masterbatch itself or a composition used directly for molding. On the other hand, "molding black composition" means a molding composition prepared by adding a diluted resin and optional components to the masterbatch (black resin composition). 【0016】 The black resin composition may contain any components. For example, it may contain a crosslinking agent, a crosslinking aid, or a silane coupling agent. In addition to a thermoplastic resin, it may also contain a thermosetting resin or a photocurable resin as the resin. It may also contain a solvent to adjust the viscosity, etc., for forming a molded product. Furthermore, it may contain various additives such as a dispersant (W), an inorganic filler, an ion scavenger, a porous adsorbent, a light stabilizer, an antioxidant, an antistatic agent, an ultraviolet absorber, a flame retardant, a light diffuser, and a wavelength converter. In one preferred embodiment, the black resin composition may contain a thermoplastic resin (R) and a colorant (P); a thermoplastic resin (R), a colorant (P), and a crosslinking agent; a thermoplastic resin (R), a colorant (P), a crosslinking agent, and a crosslinking aid; or a thermoplastic resin (R), a colorant (P), a crosslinking agent, a crosslinking aid, and a silane coupling agent. Similarly, the black molding composition of this disclosure (hereinafter also referred to as the black molding composition) may contain any components. Any components and a preferred embodiment are provided by reference to the description of the Black Resin Composition above. When preparing the Black Resin Composition for Molding, any component may be added to the Black Resin Composition used as the masterbatch, when the masterbatch is added, or after the masterbatch has been added. 【0017】This black resin composition provides a black resin composition with high stability over time by using a PB pigment (p1) and a complementary color pigment (p2) in combination as the coloring agent (P), with a CB pigment / PB pigment (p1) ratio of less than 0.1, and further, 0 to 0.9 parts by mass of IBR pigment (p3) per 100 parts by mass of perylene black pigment (p1). Furthermore, it provides a black resin composition with excellent jet blackness. When this black resin composition, or a moldable black composition to which the above composition is added as a masterbatch, is used, for example, as a solar cell encapsulant in a solar cell module or for laser welding applications, it provides molded products and laminates with high stability over time and excellent jet blackness. Furthermore, when used as a solar cell encapsulant in a solar cell module, it provides highly reliable molded products and laminates with excellent PID resistance. Also, when used for laser welding applications, it provides highly reliable molded products and laminates with excellent PCT resistance. The components of this black resin composition will be described in detail below. 【0018】 1-1. Coloring Agent (P) Perylene black pigment (p1) is used as the main component of the black pigment of the coloring agent (P), and one or more complementary pigments (p2) selected from perylene red pigment, anthraquinone pigment, quinacridone pigment, phthalocyanine pigment, dioxazine pigment, diketopyrrolopyrrole pigment, and carbon black pigment are combined with it. However, when carbon black pigment is used, the mass ratio of carbon black pigment to perylene black pigment (p1), [carbon black pigment] / [perylene black pigment (p1)], shall be less than 0.1. In addition, the coloring agent (P) may also contain an inorganic black reflective pigment (p3). However, the content of the inorganic black reflective pigment (p3) shall be 0.9 parts by mass or less per 100 parts by mass of perylene black pigment (p1). The black resin composition may contain other pigments to the extent that it does not depart from the spirit of this disclosure. 【0019】The upper limit of the [CB pigment] / [PB pigment (p1)] (mass ratio) is preferably 0.05, more preferably 0.01, even more preferably 0.005, and even more preferably 0.001, from the viewpoint of further improving stability over time and, when applied to the solar cell encapsulant described later, from the viewpoint of effectively improving PID resistance. The lower limit of the CB pigment / PB pigment (p1) is 0, which is the case when no CB pigment is present. 【0020】 IBR pigment (p3) is an inorganic reflective pigment that, when a composition is prepared by blending 3 parts by mass of the inorganic black reflective pigment (p3) with 100 parts by mass of low-density polyethylene resin, and a test piece with a thickness of 250 μm is measured in accordance with ASTM-E424-71-2023, exhibits an average reflectance of 10% or less at wavelengths of 380 to 780 nm, appears black in the visible light range, and has an average reflectance of 20% or more at wavelengths of 780 to 2500 nm, exhibiting the property of reflecting near-infrared light. 【0021】 By adding IBR pigment (p3), when applied as a encapsulant for solar cell modules, light in the above wavelength range can be reflected and reused in the solar cell elements. As a result of diligent research by the inventors, it was found that by setting the amount of IBR pigment (p3) to 0.9 parts by mass or less per 100 parts by mass of PB pigment (p1), when this black resin composition is applied as a encapsulant for solar cell modules, the phenomenon of chromium, iron, etc. contained in IBR pigment (p3) moving to the solar cell element side as cations, even when exposed to high voltage for a long period of time, can be effectively suppressed. In other words, by setting the upper limit of IBR pigment (p3) to 0.9 parts by mass, the effect of increasing the reflectivity of the black layer becomes more dominant than the effect of decreasing the transmittance of the black layer, resulting in excellent reflectivity. As a result, it is possible to achieve high jet blackness while suppressing the decrease in PID resistance over time. From the viewpoint of more effectively improving PID resistance, the upper limit of the IBR pigment (p3) content is preferably 0.8 parts by mass or 0.7 parts by mass per 100 parts by mass of PB pigment (p1), and this value may also be 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.1 parts by mass, or 0.01 parts by mass. The lower limit of the IBR pigment (p3) content is 0. 【0022】This black resin composition, by using a PB pigment (p1) with excellent infrared transmittance, can suppress temperature rise in outdoor applications, for example. Furthermore, by combining the PB pigment (p1) with a complementary pigment (p2), the jet blackness can be enhanced, and excellent design properties can be achieved. Moreover, by setting the content of the IBR pigment (p3) to below the predetermined level (including zero), both excellent jet blackness and PID resistance can be achieved. 【0023】 From the viewpoint of providing excellent jet blackness to this black resin composition, it is preferable that the amount of inorganic white pigment such as titanium dioxide, zinc oxide, or barium sulfate be 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, and even more preferably not included, per 100 parts by mass of PB pigment (p1). Furthermore, from the viewpoint of PID resistance, conductive fillers such as indium tin oxide or zirconium carbide are preferably 1 part by mass or less, more preferably 0.1 parts by mass or less, and even more preferably not included, per 100 parts by mass of PB pigment (p1). 【0024】 1-1-a. Perylene Black Pigment (p1) PB pigment (p1) is a black organic pigment having a perylene structure, and is used alone or in combination of two or more types. PB pigment (p1) is a compound containing the substructure shown in the following formula (A). In formula (A), the dotted lines indicate positions where the structure can bond with other atoms or groups of atoms. The two nitrogen-containing heterocycles in the structure may each be independently bonded to carbon atoms adjacent to their nitrogen atoms, and the two dotted lines in the formula may be double bonds. Furthermore, these nitrogen-containing heterocycles may form fused ring structures with other aromatic rings, heterocycles, or alicycles. 【0025】 Specific examples of PB pigments (p1) include the compounds with the following chemical formulas (1) to (4). 【0026】Examples of commercially available PB pigments (p1) include Lumogen® Black FK4280 (BASF), Spectrasense Black K0087, Spectrasense Black K0088; Paliogen® Black S0084 (BASF / CIPigment Black 31), Spectrasense Black L0086 (BASF / CIPigment Black 32), and Spectrasense Black S0084. Among these, Spectrasense Black L0086 (BASF / CIPigment Black 32) and Spectrasense Black K0087 are preferred based on their near-infrared light transmittance, with Spectrasense Black L0086 (BASF / CIPigment Black 32) being particularly preferred. "CI" stands for Color Index. 【0027】 The shape of the PB pigment (p1) is not limited. For example, spherical particles, needle-shaped particles, flake-shaped particles, and dendritic particles can be selected. Particles of different shapes may also be combined. 【0028】 The average primary particle size of the PB pigment (p1) is not particularly limited. From the viewpoint of improving the dispersibility of the PB pigment (p1), it is preferably 5 nm or larger, more preferably 10 nm or larger, even more preferably 20 nm or larger, and even more preferably 25 nm or larger. From the viewpoint of improving jet blackness, the upper limit of the average primary particle size of the PB pigment (p1) is preferably 500 nm, more preferably 480 nm, even more preferably 430 nm, and even more preferably 410 nm. 【0029】 In this specification, the average primary particle size of PB pigment (p1) is determined by directly measuring the size of the primary particles from electron microscope images of the PB pigment (p1) particles. Specifically, the short axis diameter and long axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of that pigment particle. Next, for 100 or more pigment particles, the volume (mass) of each particle was approximated to a cube with the measured particle size, and the volume-average particle size was taken as the average primary particle size. A transmission electron microscope (TEM) was used. 【0030】 1-1-b. Complementary Pigments (p2) Complementary pigments (p2) can be classified into complementary organic pigments (p2-a) selected from perylene red pigment, anthraquinone pigment, quinacridone pigment, phthalocyanine pigment, dioxazine pigment, and diketopyrrolopyrrole pigment, and complementary inorganic pigments (p2-b) such as carbon black pigment. 【0031】 From the viewpoint of achieving superior jet blackness, it is preferable that the complementary pigment (p2) satisfies the following (I). If the complementary pigment (p2) consists of a blend of two or more types, it is sufficient that the mixed complementary pigment (p2) incorporated into this black resin composition satisfies (I), and each pigment does not need to satisfy (I). From the viewpoint of more effectively enhancing jet blackness, it is even more preferable that each pigment used as the complementary pigment (p2) satisfies the following (I). (I) The complementary pigment (p2) is a complementary pigment in which, when a composition is prepared by incorporating 0.3 parts by mass of the complementary pigment (p2) per 100 parts by mass of low-density polyethylene resin and the test piece is 250 μm thick, the average transmittance at wavelengths of 800 to 1100 nm in accordance with ASTM-E424-71-2023 is 50% or more. 【0032】 The average transmittance of (I) above is more preferably 60% or more, and even more preferably 70% or more. From the viewpoint of high transmittance, the complementary pigment (p2) preferably contains at least one of dioxazine pigment, quinacridone pigment, perylene red pigment, phthalocyanine pigment, and diketopyrrolopyrrole pigment, and more preferably contains at least one of dioxazine pigment, phthalocyanine pigment, and diketopyrrolopyrrole pigment. Among these, dioxazine pigment and phthalocyanine pigment are even more preferred, and dioxazine pigment is particularly preferred. 【0033】From the viewpoint of obtaining a jet black color with excellent stability over time and a more aesthetically pleasing design, the complementary color pigment (p2) preferably contains a complementary organic pigment (p2-a), and the complementary organic pigment (p2-a) more preferably contains a pigment that is a nitrogen-containing compound. Even more preferably, the complementary color pigment (p2) is a complementary organic pigment (p2-a), and more preferably contains 55% by mass or more of a complementary organic pigment (p2-a) that is a nitrogen-containing compound, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 100% by mass. By using a complementary organic pigment (p2-a) having a nitrogen-containing compound, the dispersibility of the complementary color pigment (p2) in this black resin composition can be improved, and bleeding out over time can be appropriately prevented. The position of the nitrogen in the nitrogen-containing compound is not limited, but from the viewpoint of stability, a compound having nitrogen in the aromatic ring is more preferable. 【0034】 Perylene red pigments are pigments that have a perylene skeleton and whose color index name is classified as red. Examples include CI Pigment Red 88, CI Pigment Red 181, CI Pigment Red 149, CI Pigment Red 123, CI Pigment Red 179, CI Pigment Red 178, and CI Pigment Red 190. Pigments with a perylene skeleton include CI Pigment Violet 29, which exhibits a purple color, and CI Pigment Black 31 and CI Pigment Black 32, which exhibit a black color, but their color index names are not classified as red, and therefore they do not belong to the category of perylene red pigments. 【0035】Anthraquinone pigments are condensed polycyclic pigments having an anthraquinone skeleton, and include anthraquinone-based pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthantrone, indanthrone, pyrantrone, and biolanthrone. Examples include CI Pigment Yellow 24, CI Pigment Yellow 108, CI Pigment Red 168, CI Pigment Red 177, and CI Pigment Blue 60. Among these, CI Pigment Yellow 24, CI Pigment Yellow 108, CI Pigment Red 168, and CI Pigment Red 177, whose color index names are classified as yellow or red, are preferred from the viewpoint of obtaining a more aesthetically pleasing jet black color, and CI Pigment Red 168 and CI Pigment Red 177, whose color index names are classified as red, are more preferred. 【0036】 Quinacridone pigments are pigments that have a quinacridone skeleton. Examples include CI Pigment Violet 19, CI Pigment Red 122, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, and CI Pigment Orange 48. Among these, from the viewpoint of obtaining a more aesthetically pleasing jet black, CI Pigment Violet 19, CI Pigment Red 122, CI Pigment Red 206, CI Pigment Red 207, and CI Pigment Red 209, whose color index names are classified as purple or red, are preferred, and CI Pigment Red 122, CI Pigment Red 206, CI Pigment Red 207, and CI Pigment Red 209, whose color index names are classified as red, are more preferred. 【0037】Phthalocyanine pigments are pigments having a phthalocyanine skeleton and include phthalocyanines coordinated with various metals such as copper phthalocyanine pigments and zinc phthalocyanine pigments. Examples include CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, CI Pigment Green 63, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16. Among these, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16 are preferred from the viewpoint of obtaining a more aesthetically pleasing jet black color, as their color index names are classified as blue. 【0038】 Dioxazine pigments are pigments that have a dioxazine skeleton. Examples include CI Pigment Violet 23, CI Pigment Violet 29, and CI Pigment Violet 37. 【0039】Diketopyrrolopyrrole pigments are pigments that have a diketopyrrolopyrrole pigment skeleton. Examples include CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 272, CI Pigment Orange 71, and CI Pigment Orange 73. Among these, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, and CI Pigment Red 272 are preferred from the viewpoint of obtaining a more aesthetically pleasing jet black color, as their color index names are classified as red. 【0040】 CB pigments are carbon-based fine particles that may have functional groups such as carboxyl groups and hydroxyl groups on their surface. Alternatively, oxidized carbon black obtained by oxidizing carbon black may be used. Examples of carbon black include furnace black, gas black, thermal black, lamp black, as well as carbon fibers, carbon plates, activated carbon, glassy carbon, charcoal, graphite, and combinations thereof. Carbon black may be crystalline or amorphous. Furthermore, the carbon material may be waste or by-products of carbon materials obtained by thermal decomposition. 【0041】 Examples of commercially available CB pigments include Black 582, Irgaphor® Black S0100CF (manufactured by BASF), MA7, MA8, MA100, MA600, MCF-88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #52, #85, #95, #240, #850, #900, #950, #960, #970, #980, #1000, #2300, #2350, #2600, and #2650 (manufactured by Mitsubishi Chemical Corporation). 【0042】The average primary particle size of the CB pigment is not limited, but is, for example, 3 to 500 nm. The lower limit of the average primary particle size of the CB pigment is preferably 5 nm, more preferably 10 nm. The upper limit of the average primary particle size of the CB pigment is more preferably 400 nm, even more preferably 300 nm, and even more preferably 250 nm. The method for measuring the average primary particle size of the complementary pigment (p2) containing the CB pigment is the same as that for the PB pigment (p1) described above. 【0043】 Among the complementary pigments (p2), one or more selected from perylene red pigment, anthraquinone pigment, quinacridone pigment, phthalocyanine pigment, dioxazine pigment, and diketopyrrolopyrrole pigment are more preferred, and one or more selected from phthalocyanine pigment, dioxazine pigment, and diketopyrrolopyrrole pigment are even more preferred. 【0044】 1-1-d. Inorganic Black Reflective Pigments (p3) IBR pigments (p3) are black inorganic pigments that have reflective properties in the wavelength band of 700 to 1100 nm. Examples of IBR pigments (p3) include composite oxides obtained by calcining two or more oxides containing metal elements such as iron, copper, chromium, cobalt, titanium, manganese, nickel, bismuth, and calcium. Examples include chromium iron oxide, chromium copper oxide, and iron titanium oxide. Alternatively, black near-infrared reflective pigments containing calcium, titanium, manganese, and bismuth, with a perovskite phase as the main phase, as disclosed in International Publication No. 2018 / 168596, may also be used. Among these, chromium iron oxide is more preferred. 【0045】 From the viewpoint of maintaining appropriate transmittance in the black layer, the average particle size of the IBR pigment (p3) is preferably 50 nm to 100 μm, more preferably 100 nm to 10 μm, and even more preferably 500 nm to 5 μm. The average particle size can be measured according to the laser diffraction scattering method in accordance with JIS Z8825, and represents the particle size at which the cumulative volume calculated from the smallest diameter side accounts for 50% of the measured particle size distribution (volume basis). 【0046】1-1-e. Other Colorants (P) The black resin composition may contain other colorants (P) that do not fall under the categories of perylene black pigment (p1), complementary pigment (p2), and IBR pigment (p3), without departing from the spirit of this disclosure. Examples of such other colorants (P) include pigments and dyes that do not fall under the categories of perylene black pigment (p1), complementary pigment (p2), and IBR pigment (p3). 【0047】 1-2. Thermoplastic Resin (R) This black resin composition contains a thermoplastic resin (R). The type of thermoplastic resin (R) is not limited and can be selected according to the application. Examples of thermoplastic resins (R) include (meth)acrylic resins, polystyrene resins including styrene-maleic acid copolymers, polycarbonate resins, polyester resins, polyamide resins, polyimide resins, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, vinyl resins, polyolefin resins, butyral resins, polyurethane resins, alkyd resins, rubber resins, cyclorelated rubber resins, celluloses, and polyacetal resins. The thermoplastic resin (R) can be used alone or in a mixture of two or more types. 【0048】 When this black resin composition is used, for example, as a encapsulant for solar cells, polyolefin resins are preferred. Examples of polyolefin resins include polyethylene resin, ethylene-α-olefin copolymer, ethylene-unsaturated ester copolymer, and polypropylene resin. 【0049】 Examples of polyolefin resins include polyethylene resin, ethylene-α-olefin copolymer, ethylene-unsaturated ester copolymer, and polypropylene-based resin. 【0050】 Examples of polyethylene resins include high-density polyethylene (HDPE) and low-density polyethylene (LDPE). 【0051】Examples of ethylene-α-olefin copolymers include ethylene-α-olefin copolymers. Specific examples of ethylene-α-olefin copolymers include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-4-methylpentene-1 copolymer. 【0052】 The α-olefin content in the ethylene-α-olefin copolymer is preferably 5 to 40 mol%, more preferably 10 to 35 mol%, and even more preferably 10 to 30 mol%. By setting the α-olefin content to the above 5 to 40 mol%, the flexibility and transparency of the sealant are improved, the crosslinking rate is appropriate, and the blocking properties are excellent. Combinations of two or more ethylene-α-olefin copolymers are also suitable. 【0053】 Among ethylene-α-olefin copolymers, polyolefin elastomers (hereinafter also referred to as POE (Polyolefin Elastomer)) are preferred in terms of transparency and flexibility. Suitable POEs include ethylene-propylene copolymer, ethylene-1-butene copolymer, and ethylene-1-octene copolymer. 【0054】 From the viewpoint of transparency, it is preferable that the POE includes ethylene-1-butene copolymer and ethylene-1-octene copolymer. From the viewpoint of more effectively enhancing transparency, it is even more preferable that it includes ethylene-1-octene copolymer. 【0055】Ethylene-unsaturated ester copolymers are obtained by copolymerizing monomers containing ethylene and unsaturated ester monomers as monomers. Examples of unsaturated ester monomers include alkyl (meth)acrylates such as methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, and isobutyl methacrylate; alkyl unsaturated carboxylates such as dimethyl maleate and diethyl maleate; and vinyl carboxylates such as vinyl acetate and vinyl propionate. In ethylene-unsaturated ester copolymers, the unsaturated ester monomer may be a single type or two or more types may be used in combination. Vinyl acetate and methyl methacrylate are more preferred as unsaturated ester monomers, and vinyl acetate is even more preferred. Furthermore, ethylene-unsaturated ester copolymers may contain structural units derived from monomers other than ethylene and unsaturated ester monomers, to the extent that they do not depart from the spirit of this disclosure. 【0056】 Specific examples of ethylene-unsaturated ester copolymers include ethylene vinyl acetate copolymer (EVA), ethylene (meth)acrylate methyl copolymer, ethylene (meth)acrylate ethyl copolymer, ethylene vinyl acetate-based multi-component copolymer, ethylene (meth)acrylate-based multi-component copolymer, and ethylene (meth)acrylate-based multi-component copolymer. A multi-component copolymer refers to a copolymer with three or more components. Among these, EVA is preferred in terms of transparency and lamination properties, EVA with a vinyl acetate content of 15 to 40 mol% is more preferred, and ethylene vinyl acetate copolymer with a vinyl acetate content of 25 to 35 mol% is even more preferred. In the black layer, the ethylene-unsaturated ester copolymer may be used alone or in combination of two or more types. 【0057】 Examples of the above-mentioned polypropylene resins include polypropylene (PP) such as isotactic polypropylene, syndiotactic polypropylene, and attackic polypropylene, as well as polypropylene copolymers. 【0058】When this black resin composition is used, for example, in laser welding applications, examples of suitable resins include (meth)acrylic resin, polystyrene resin, polycarbonate resin, polyamide resin, polyethylene terephthalate, and polyester resins such as polybutylene terephthalate. Laser resin welding refers to joining a resin to another component by melting the resin with heat generated by the absorption of laser light, either without or in combination with adhesives. This black resin composition enables strong bonding while maintaining high aesthetic appeal. 【0059】 Examples of (meth)acrylic resins include homopolymers such as polymethyl methacrylate and polymethyl acrylate, and copolymers obtained by polymerizing two or more (meth)acrylates. Examples of polycarbonate resins include aromatic homo or copolymers obtained by reacting aromatic divalent phenolic compounds with phosgene or diester carbonate. Examples of polyamide resins include nylon 6, nylon 66, nylon 6 / 66 copolymer, nylon 610, nylon 11, nylon 12, and nylon 13. 【0060】 Examples of polystyrene-based resins include polystyrene, styrene-(meth)acrylate copolymer containing 50 mol% or more of the styrene unit component, styrene-(meth)acrylate copolymer, styrene-(meth)acrylate copolymer, styrene-maleic anhydride copolymer, styrene-polyphenylene ether copolymer, styrene-acrylonitrile copolymer, styrene-methylstyrene copolymer, styrene-dimethylstyrene copolymer, styrene-ethylstyrene copolymer, and styrene-diethylstyrene copolymer. 【0061】Polybutylene terephthalate is a polymer obtained by polycondensation reaction of terephthalic acid or its ester-forming derivative with 1,4-butanediol or its ester-forming derivative. Polyethylene terephthalate is obtained by polycondensation using terephthalic acid as the acid component and ethylene glycol as the glycol component. In addition to the above components, isophthalic acid, adipic acid, and oxalic acid may be used as part of the acid component. Furthermore, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, and cyclohexanediol may be used as part of the glycol component. 【0062】 The glass transition temperature (Tg) of the thermoplastic resin (R) can be appropriately selected depending on the application. When used as a solar cell encapsulant, from the viewpoint of processability and adhesion, the Tg of the thermoplastic resin (R) is preferably 0°C or lower, more preferably -10°C or lower, and even more preferably -15°C or lower. In this case, the lower limit of the Tg of the thermoplastic resin (R) is preferably -100°C, and more preferably -90°C. On the other hand, when this black resin composition is used for applications such as laser welding, from the viewpoint of achieving both adhesion to the adherend and shape retention of the molded product of this black resin composition, the Tg of the thermoplastic resin (R) is preferably above 0°C, more preferably 20°C or higher, even more preferably 40°C or higher, and even more preferably 60°C or higher. In this case, the upper limit of the Tg of the thermoplastic resin (R) is preferably 280°C, and more preferably 200°C. 【0063】 1-3. Dispersant (W) It is preferable to prepare a dispersion of the complementary pigment (p2) in advance by dispersing it in a dispersant (W), and then mix the dispersion with a thermoplastic resin (R) and a PB pigment (p1) to prepare a black resin composition. By preparing a dispersion, the dispersibility of the complementary pigment (p2) in the black resin composition can be significantly improved. As a result, the jet blackness of the black resin composition can be made even better. The content of the complementary pigment (p2) in 100% by mass of the dispersion is not particularly limited, but is for example 5 to 95% by mass. 【0064】A preferred example of the dispersant (W) is polyolefin wax (WO), which is classified as a thermoplastic resin (R). Wax is an organic substance that is solid at room temperature (25°C) and becomes liquid when heated. The polyolefin wax (WO) in this disclosure refers to one with a melt flow rate (MFR) of more than 100 g / 10 min. In this specification, polyolefin resin refers to a polyolefin resin that does not fall under the category of polyolefin wax (WO) and has a melt flow rate (MFR) of 100 g / 10 min or less. That is, polyolefin resin is a polymer (homopolymer or copolymer) of raw material monomers containing olefin and has an MFR of 100 g / 10 min or less, while polyolefin wax (WO) is a polymer (homopolymer or copolymer) of raw material monomers containing olefin and has an MFR of more than 100 g / 10 min. The melt flow rate (MFR) can be measured under conditions of 190°C and 21.18 N of load, in accordance with JIS K-7210 (2014). 【0065】 The melting point of the polyolefin wax (WO) is preferably 130°C or lower, more preferably 120°C or lower, from the viewpoint of the dispersibility of the complementary pigment (p2). Furthermore, a melting point of 70°C or higher is preferable. Using polyolefin wax (WO) with a melting point within the above range improves the dispersibility of the complementary pigment (p2) in the black resin composition and also improves processability during melt-kneading. The melting point can be determined by differential scanning calorimeter. Specifically, for example, it can be measured using a differential scanning calorimeter DSC6200 manufactured by Seiko Instruments, with alumina as the standard substance, within a temperature range of 40 to 200°C and a heating rate of 10°C / min. 【0066】 Preferred examples of polyolefin wax (WO) include polymers of olefin monomers such as ethylene, propylene, and butylene. Also preferred examples include polymers of α-olefins such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polypropylene (PP). Polyolefin wax (WO) can be used alone or in combination of two or more types. Polyolefin wax (WO) may also be a block polymer, random copolymer, or terpolymer. 【0067】 The number-average molecular weight (Mn) of polyolefin wax (WO) is preferably 1,000 to 30,000, and more preferably 2,000 to 25,000. Mn can be measured by gel permeation chromatography (GPC) using polystyrene as the standard substance and tetrahydrofuran as the eluent. 【0068】 1-4. Blending Ratio, etc. The content of the colorant (P) in 100% by mass of this black resin composition can be appropriately designed depending on the application, but for example, it is 0.05 to 60% by mass. When this black resin composition is used as a masterbatch for the colorant (P), the content of the colorant (P) in 100% by mass of this black resin composition is preferably 0.5 to 55% by mass, more preferably 4 to 25% by mass, and even more preferably 4 to 15% by mass. When this black resin composition is used as is in molded products, the content of the colorant (P) in 100% by mass of this black resin composition is preferably 0.1 to 13% by mass. The lower limit of the above content may be 0.2% by mass or more, 0.3% by mass or more, or 0.4% by mass or more. The upper limit of the above content may be 10% by mass or less, 7% by mass or less, 5% by mass or less, 4.2% by mass or less, or 2% by mass or less. 【0069】 In this black resin composition, the content of PB pigment (p1) is preferably 50 to 99.5% by mass, and more preferably 70 to 97% by mass, based on 100% by mass of the coloring agent (P), from the viewpoint of enhancing jet blackness and design properties, as well as providing excellent dispersion stability and improved stability over time. The lower limit of the PB pigment (p1) content is more preferably 75% by mass or more, and even more preferably 80% by mass or more. From the viewpoint of enhancing jet blackness and UV resistance, the concentration of PB pigment (p1) in the molded article, i.e., the final concentration, is preferably 0.1% by mass or more, and more preferably 0.4% by mass or more. Furthermore, from the viewpoint of enhancing reflectivity and heat and humidity resistance, the final concentration is preferably 10% by mass or less, more preferably 4% by mass or less, and even more preferably 2% by mass or less. 【0070】In this black resin composition, the content of the complementary pigment (p2) is preferably 0.5 to 35% by mass, more preferably 1 to 25% by mass, and even more preferably 3 to 20% by mass, based on 100% by mass of the coloring agent (P), in order to enhance the jet blackness and design properties, as well as to improve dispersion stability and stability over time. 【0071】 From the viewpoint of further enhancing the jet-blackness, the content of the complementary pigment (p2) is preferably 0.5 to 50 parts by mass per 100 parts by mass of PB pigment (p1). The lower limit of the complementary pigment (p2) is preferably 0.7 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more. The upper limit of the complementary pigment (p2) is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. 【0072】 From the viewpoint of migration (PCT), plate-out resistance, and heat and humidity resistance, which will be explained in the examples described later, the content of the complementary pigment (p2) is preferably 12 parts by mass or less per 100 parts by mass of PB pigment (p1), and from the viewpoint of effectively bringing out the above characteristics, it may be 10 parts by mass or less, 7 parts by mass or less, 5 parts by mass or less, or 3 parts by mass or less. On the other hand, from the viewpoint of jet blackness and UV resistance, the content of the complementary pigment (p2) is preferably 10 to 20 parts by mass per 100 parts by mass of PB pigment (p1), and from the viewpoint of effectively bringing out the above characteristics, the content of the complementary pigment (p2) may be 12 parts by mass or more, or 15 parts by mass or more per 100 parts by mass of PB pigment (p1). 【0073】When using dioxazine pigment alone, from the viewpoint of jet blackness and UV resistance, 2 to 20 parts by mass, more preferably 3 to 15 parts by mass, even more preferably 4 to 13 parts by mass, and even more preferably 5 to 11 parts by mass are preferred per 100 parts by mass of PB pigment (p1). Furthermore, from the viewpoint of improving migration (PCT), plate-out resistance, and heat and humidity resistance, which will be described later, a combination of perylene black (p1) and dioxazine pigment is preferred. From the viewpoint of improving jet blackness, a combination of PB pigment (p1), dioxazine pigment as a complementary color pigment (p2), and IBR pigment (p3) is also suitable. However, from the viewpoint of improving stability over time in terms of PID resistance, it is more preferable that the amount of IBR pigment (p3) be 0.5 parts by mass or less, even more preferably 0.1 parts by mass or less, per 100 parts by mass of PB pigment (p1), and it may be omitted. 【0074】 When using a phthalocyanine pigment as the complementary pigment (p2), from the viewpoint of improving the migration properties, plate-out resistance, and heat and humidity resistance of the PCT, the content of the phthalocyanine pigment is preferably 9 parts by mass or less per 100 parts by mass of the PB pigment (p1). From the viewpoint of more effectively bringing out the heat and humidity resistance, it is preferably 8 parts by mass or less, 7 parts by mass or less, or 5 parts by mass or less, more preferably 3 parts by mass or less, or 2 parts by mass or less, and may also be 1.5 parts by mass or less. 【0075】On the other hand, from the viewpoint of enhancing jet blackness and UV resistance, it is preferable to combine phthalocyanine pigment with other complementary pigments as the complementary pigment (p2) to ensure the total content of complementary pigments (p2). The other pigment to be combined with phthalocyanine pigment is not limited as long as it is a complementary pigment (p2), and may be any of perylene red pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, diketopyrrolopyrrole pigment, and carbon black pigment. Among these, perylene red pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, and diketopyrrolopyrrole pigment are preferred as the other pigment to be combined with phthalocyanine pigment, dioxazine pigment and diketopyrrolopyrrole pigment are more preferred, and diketopyrrolopyrrole pigment is particularly preferred. The mass ratio of diketopyrrolopyrrole pigment to phthalocyanine pigment ([diketopyrrolopyrrole pigment] / [phthalocyanine pigment]) is preferably 1 to 8, more preferably 2 to 7, and even more preferably 2.5 to 6. The total content of phthalocyanine pigment and other complementary pigments (p2) is preferably 3 to 20 parts by mass per 100 parts by mass of PB pigment (p1) from the viewpoint of jet blackness and UV resistance, and may be 10 parts by mass or more, 12 parts by mass or more, or 15 parts by mass or more from the viewpoint of effectively bringing out the above characteristics. From the viewpoint of reflectance and PID resistance, it is preferable not to combine phthalocyanine pigment with IBR pigment (p3). 【0076】By using a dispersant (W), the dispersibility of the complementary pigment (p2) in the black resin composition can be significantly improved. By improving the dispersibility of the complementary pigment (p2) in the black resin composition, it becomes possible to form a homogeneous black layer without color unevenness, providing a high-quality black layer. A high-quality black layer with excellent homogeneity and dispersibility can be obtained, improving stability over time. Furthermore, when used in solar cell modules, PID resistance can be improved. The content of the dispersant (W) in 100% by mass of the dispersion is, for example, 5 to 95% by mass. The dispersant (W) is preferably polyolefin wax (WO). The content of polyolefin wax (WO) is preferably 5 to 95% by mass relative to 100% by mass of the dispersion. In the black resin composition, the mass ratio of the complementary pigment (p2) to the dispersant (W) ([complementary pigment (p2)] / [dispersant (W)]) is preferably 0.01 to 100, more preferably 0.05 to 30, even more preferably 0.1 to 10, and even more preferably 0.3 to 5, from the viewpoint of dispersibility and migration (PCT) as described in the examples below. 【0077】 This black resin composition may be used with a solvent as appropriate to improve its coatability when forming sheets or the like. Preferably, the solvent is used in an amount of 800 to 4000 parts by mass per 100 parts by mass of the coloring agent (P). The solid content concentration can be set appropriately according to the viscosity. For example, the solid content concentration is 5 to 40% by mass. 【0078】 The content of thermoplastic resin (R) in this black resin composition can be appropriately set depending on the application. When this black resin composition is used as a masterbatch for a colorant (P), for example, 50 to 5,000 parts by mass of thermoplastic resin (R) can be used per 100 parts by mass of colorant (P). When this black resin composition is used as is in molded products, the concentration of colorant (P) can be designed according to the shape, thickness, etc. of the molded product. In this case, for example, 1,000 to 500,000 parts by mass of thermoplastic resin (R) can be used per 100 parts by mass of colorant (P). 【0079】From the viewpoint of obtaining a molded product with excellent flexibility and high durability, the thermoplastic resin (R) is preferably a polyolefin resin. From the viewpoint of obtaining a molded product with excellent flexibility and high durability, the polyolefin resin content is preferably 50% by mass or more, more preferably 60% by mass, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and may also be 85% by mass or more, 90% by mass or more, or 95% by mass or more, based on 100% by mass of the thermoplastic resin (R). It may also be 100% by mass. Among polyolefin resins, POE resin and EVA resin are more preferred. 【0080】 From the viewpoint of obtaining molded products with excellent PCT resistance and high durability, the thermoplastic resin (R) is preferably a resin with a Tg above 0°C. The content of the resin with a Tg above 0°C is preferably 50% by mass or more, more preferably 60% by mass, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and may also be 85% by mass or more, 90% by mass or more, or 95% by mass or more, based on 100% by mass of the thermoplastic resin (R). It may also be 100% by mass. 【0081】 2. Method for Manufacturing the Black Resin Composition The method for manufacturing the black resin composition is not limited and can be manufactured by various methods. An example of a method for manufacturing the black resin composition is described below. The components of the black resin composition are weighed out. It is preferable to pre-mix the complementary pigment (p2) with a dispersant (W) to form a dispersion. The dispersant (W) can be any component that can improve the dispersibility of the complementary pigment (p2). Suitable examples of the dispersant (W) include thermoplastic resins (R) and surfactants. From the viewpoint of improving the uniformity of the complementary pigment (p2), thermoplastic resins (R) are preferred. Among thermoplastic resins (R), polyolefin wax (WO) is suitable as the dispersant (W). The PB pigment (p1) may also be pre-mixed with the dispersant (W). 【0082】The production of this black resin composition is preferably carried out by, for example, mixing a complementary pigment (p2) and a dispersant (W), pre-dispersing them to form a dispersion, and then melt-kneading it with a PB pigment (p1) and a thermoplastic resin (R). By mixing with the dispersant (W) in advance, pigment aggregation and color unevenness caused by poor dispersion of the complementary pigment (p2) can be prevented, and a molded article with a good appearance can be obtained when a sheet is formed. 【0083】 A known method can be used for mixing the complementary pigment (p2) and the dispersant (W). For example, a method can be used to stir and mix the complementary pigment (p2) and the dispersant (W) using a dry grinder such as a fluid energy grinder or an impact grinder, or a high-speed agitator such as a Henschel mixer or a super mixer, or a method can be used to melt and knead the complementary pigment (p2) and the dispersant (W) using a kneader, roll mill, Banbury mixer, etc. 【0084】 Next, the dispersion and other components of the black resin composition are introduced into a mixing device for melt-kneading. The mixing device may be a high-speed shear mixer such as a Henschel mixer or a super mixer. Melt-kneading is performed using, for example, a two-roll, three-roll, pressure kneader, or Banbury mixer. The mixing process is heated to a temperature above the flow initiation temperature of the thermoplastic resin (R). The temperature is, for example, 0 to 80°C above the flow initiation temperature of the thermoplastic resin (R). The heating time is, for example, 30 seconds to 1 hour. The pressure is, for example, atmospheric pressure. 【0085】 After mixing, the mixture is extruded from a manufacturing device such as a die, cooled, and then cut into pellets. In addition to pelletizing, the pellets may also be crushed into a powder. 【0086】3. Molded Articles and Methods for Manufacturing the Same The molded articles of this disclosure (hereinafter also referred to as "the molded articles") are formed from either (i) the black resin composition, or (ii) a moldable black composition obtained by adding at least the black resin composition to a diluted resin. (ii) is a molded article formed from a moldable black composition obtained by adding at least the black resin composition to a diluted resin (binder resin) and mixing, using the black resin composition as a masterbatch. The moldable composition may be obtained directly by method (i), but by method (ii), the uniform dispersibility of the colorant (P) can be significantly improved by obtaining the moldable black composition from a black resin composition in which a high concentration of colorant (P) has been dispersed beforehand. The case of (ii) will be described below, but it may also be formed by method (i). 【0087】 As the diluent, the thermoplastic resin (R) described above is preferred. By using the same type of resin for the black resin composition and the diluent, compatibility can be improved, as well as the homogeneity of the colorant (P). A thermosetting resin may also be used as the diluent. Alternatively, a thermoplastic resin different from that of the black resin composition may be used. To prevent decomposition of the colorant (P) when the diluent resin and the black resin composition are mixed, the melting temperature of the diluent resin is preferably 350°C or lower, more preferably 320°C or lower, and even more preferably 300°C or lower. The diluent resin can be one type alone or a mixture of two or more types. 【0088】 The amount of this black resin composition added to the diluted resin is not particularly limited and can be appropriately designed depending on the application. For example, 1 to 50 parts by mass of this black resin composition can be added to 100 parts by mass of the diluted resin. A solvent can be added to the molding black composition to adjust its viscosity. 【0089】The black resin composition for molding may contain components other than the diluted resin and the black resin composition itself. From the viewpoint of improving durability under high-temperature use, it is preferable to further incorporate a crosslinking agent. The type of crosslinking agent is not limited, but organic peroxides are preferred. Preferred examples include tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexylisopropyl carbonate, tert-butylperoxyacetate, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-butylperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 2,2 Examples include -di(tert-butylperoxy)butane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-diperoxybenzoate, tert-butyl hydroperoxide, p-menthane hydroperoxide, dibenzoyl peroxide, p-chlorobenzoyl peroxide, tert-butylperoxyisobutyrate, n-butyl-4,4-di(tert-butylperoxy)valerate, ethyl-3,3-di(tert-butylperoxy)butyrate, hydroxyheptyl peroxide, dichlorohexanone peroxide, 1,1-di(tert-butylperoxy)3,3,5-trimethylcyclohexane, n-butyl-4,4-di(tert-butylperoxy)valerate, and 2,2-di(tert-butylperoxy)butane. 【0090】 To ensure the crosslinking reaction of the crosslinking agent proceeds efficiently, a crosslinking aid may be used. The crosslinking aid is preferably an unsaturated compound such as a polyallyl compound or a polyacryloxy compound. The amount of the crosslinking agent and the crosslinking aid is preferably 0.05 to 3 parts by mass per 100 parts by mass of the total thermoplastic resin (R) and diluent resin. 【0091】 A silane coupling agent may be added to improve adhesion to the surface protective glass and power generation elements (solar cells). The silane coupling agent is a compound having functional groups such as vinyl groups, acryloxy groups, and methacryloxy groups, as well as hydrolyzable functional groups such as alkoxy groups. The amount of silane coupling agent added is preferably 0.05 to 3 parts by mass per 100 parts by mass of the total of the thermoplastic resin (R) and the diluent resin. 【0092】 To improve weather resistance, ultraviolet absorbers may be added. Preferred ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, triazine compounds, salicylate ester compounds, and the like. The amount of ultraviolet absorber added is preferably 0.01 to 3 parts by mass per 100 parts by mass of thermoplastic resin (R). 【0093】 Light stabilizers may be added to improve weather resistance. Weather resistance is further improved when light stabilizers are used in combination with ultraviolet absorbers. Hindered amine compounds are preferred as light stabilizers. The amount of light stabilizer added is preferably 0.01 to 3 parts by mass per 100 parts by mass of thermoplastic resin (R). 【0094】 Antioxidants may be added to improve stability at high temperatures. Specific examples of antioxidants include monophenol compounds, bisphenol compounds, high molecular weight phenol compounds, sulfur compounds, and phosphoric acid compounds. The amount of antioxidant added is preferably 0.05 to 3 parts by mass per 100 parts by mass of thermoplastic resin (R). 【0095】 Furthermore, various additives can be added to this black molding composition without departing from the spirit of this disclosure. For example, various additives such as dispersants, inorganic fillers, ion scavengers, porous adsorbents, antistatic agents, flame retardants, light diffusers, and wavelength converters can be added. 【0096】 This molded product includes a coating film using a black molding composition as a paint. It also includes sheets formed by coating, injection molding, etc., of the black molding composition, and structures formed by using a mold to form the black molding composition. 【0097】This molded product can be manufactured by various methods. An example of a manufacturing method for this molded product is described below. First, the black resin composition is obtained by the method described above. The black resin composition is more efficient in the subsequent mixing step if it is in the form of pellets or granules, for example. 【0098】 Next, at least the black resin composition is added to the diluting resin and mixed. Other additives may be added to the molding black composition at any time. It is important that the colorant (P) is sufficiently dispersed during the mixing process. From the viewpoint of compatibility and dispersibility of the black resin composition, the mixing process is carried out at a temperature of +0 to 80°C above the flow start temperature of the thermoplastic resin (R) and the diluting resin used as the diluting resin, whichever has the higher flow start temperature. Mixing equipment such as a single-screw extruder, twin-screw extruder, or kneader-ruder can be used. The kneading time is, for example, 30 seconds to 1 hour. 【0099】 Simultaneously with or after the mixing step, a molding step is performed to mold the black composition for molding. The molding step is carried out, for example, by uniscrew or twin-screw extrusion molding, injection molding, or blow molding. The obtained black composition for molding may first be pelletized, and molded products may be obtained from the pellets. The flow start temperature refers to the minimum temperature at which the melt viscosity of the resin becomes 4800 Pa·s or less under a pressure of 9.8 MPa, as evaluated by a flow tester. 【0100】 This molded product is suitable as a solar cell encapsulant because it uses a highly reliable black pigment that has excellent aesthetic appeal, high stability over time, and excellent PID resistance when used as a solar cell encapsulant in solar cell modules. Furthermore, because it uses a PB pigment (p1) that has excellent aesthetic appeal and high infrared transmittance, it is suitable for applications such as laser welding. 【0101】4. Laminate and Method for Manufacturing the Same The laminate of the present disclosure (hereinafter also referred to as "the laminate") has a laminate of a white layer and a black layer. The black layer is formed from either (i) the present black resin composition, or (ii) a molding black composition obtained by adding at least the present black resin composition to a diluted resin. The following will describe (ii), but the black layer may also be obtained from (i). 【0102】 The black layer obtained from (ii) is a layer formed from a molding black composition obtained by adding at least this black resin composition to a diluted resin. The type of diluted resin and suitable amounts are described in "3. Molded articles and their manufacturing methods" above. Suitable examples, suitable combinations, and suitable blending ratios of optional components of the molding black composition (crosslinking agents, crosslinking aids, silane coupling agents, ultraviolet absorbers, light stabilizers, antioxidants, and other additives) are also described in "3. Molded articles and their manufacturing methods" above. When used as a solar cell encapsulant or a back-surface protective sheet for a solar cell module described later, it is possible to enhance the design of the solar cell module while increasing the transmittance of near-infrared rays and suppressing the temperature rise of the black layer. 【0103】 The white layer is a layer formed from a white molding composition containing a diluted resin and a white pigment. The white layer only needs to be a layer that can reflect near-infrared light with a wavelength of 800 to 1200 nm. Known pigments can be used as the white pigment. Examples of white pigments include titanium dioxide, calcium carbonate, barium sulfate, and silicon dioxide. A preferred example is a white layer in which titanium dioxide with an average particle size D50 of 0.2 to 2.0 μm is blended at a concentration of 2 to 10% by mass per 100% by mass of the white layer. It is also preferable to use a white masterbatch for the white layer. That is, when forming the white layer, it is preferable to prepare a mixture by adding at least a white masterbatch to the diluted resin and then form the white layer. 【0104】 The laminate is suitably used as a solar cell encapsulant for sealing power generation elements within a solar cell module. When used in the aforementioned application, the volume resistivity of the laminate is, for example, 1.0 × 10⁻⁶. １５ ~1.0 x 10 １８ It is preferable to use Ω·cm. 【0105】 The method for manufacturing this laminate is not particularly limited, and known methods for manufacturing laminates can be used. Crosslinking agents, crosslinking aids, silane coupling agents, ultraviolet absorbers, light stabilizers, and antioxidants may be added during molding. The thickness of the laminate is, for example, about 0.1 to 2 mm. Preferred examples include co-extrusion multilayer molding methods such as the multilayer T-die method and the multilayer circular die method. For example, the components of the black resin composition and the white molding composition for forming the white layer of the disclosed material are dry-blended and supplied from hoppers of a multilayer T-die extruder, calendering machine, etc., and the laminate can be obtained by extruding it into a sheet at an extrusion temperature of 80 to 130°C. 【0106】 Alternatively, lamination may be performed after separately forming the black and white layers, and the surface of the sealant may be embossed on both sides or one side, depending on the purpose. Furthermore, post-treatments such as heat setting, corona treatment, or plasma treatment may be performed for dimensional stabilization. 【0107】 When the laminate of this disclosure is used as a encapsulant for a solar cell module, by including 0.1 to 10% by mass of PB pigment (p1) in the black layer and including the complementary pigment (p2) in the above-mentioned amount relative to the PB pigment (p1) (0.5 to 50 parts by mass per 100 parts by mass of PB pigment (p1)), UV resistance can be improved and a decrease in the output of the solar cell module can be suppressed. When sunlight is irradiated onto a solar cell module having a laminate of a black layer and a white layer on the back side, if the concentrations of PB pigment (p1) and complementary pigment (p2) in the black layer are low, the ultraviolet transmittance of the black layer increases, and the white layer below it is more easily exposed to ultraviolet light. If titanium dioxide is included in the white layer, in a low-oxygen environment such as a solar cell module, the titanium dioxide is reduced, causing the white layer to blacken and the reflectance of the white layer to decrease. This decrease in reflectance reduces the output of the solar cell module. By including the above-mentioned amounts of PB pigment (p1) and complementary pigment (p2) in the black layer, it is possible to improve UV resistance and suppress the decrease in output. 【0108】Furthermore, in the laminate of this disclosure, by including 0.1 to 10% by mass of PB pigment (p1) in the black layer and including the complementary pigment (p2) in the above-mentioned amount relative to the PB pigment (p1) (0.5 to 50 parts by mass per 100 parts by mass of PB pigment (p1)), excellent moist heat resistance can be achieved. That is, if there is too much pigment such as PB pigment (p1) and complementary pigment (p2) in the black layer, the pigment will adsorb the crosslinking agent and crosslinking aid in the encapsulant, reducing the amount of active ingredients of the crosslinking agent and crosslinking aid, which reduces the degree of hardening of the encapsulant and makes it easier for moist heat resistance to decrease. Since this decrease in moist heat resistance reduces the output of the solar cell module, including the above-mentioned PB pigment (p1) and complementary pigment (p2) in the black layer can improve moist heat resistance and suppress the decrease in output. 【0109】 5. Solar Cell Module The solar cell module of this disclosure can have various known configurations. Figure 1 shows an example of a schematic plan view of the solar cell module of this embodiment. As shown in the figure, the solar cell module 100 has multiple tandem-type power generation elements 1 arranged in the X direction and the Y direction perpendicular to the X direction. The Z direction in the figure is the thickness direction of the solar cell module. The multiple power generation elements (solar cell elements) 1 are electrically connected in series or in parallel by conductive connecting members such as copper, aluminum, and gold (not shown). 【0110】 Figure 2 shows an example of a schematic cross-sectional view of a power generation element along the II-II line in Figure 1. The power generation element 1 has a top cell 3 and a bottom cell 5 in the thickness direction. The solar cell module 100 is a single-sided module that receives sunlight from the top cell 3 side. The power generation element 1 is a double-sided light-receiving cell. 【0111】The power generation element 1 has, in order from the side that receives sunlight, a top electrode 2, a top cell 3, an intermediate electrode 4, a bottom cell 5, and a bottom electrode 6. The top cell 3 has a structure in which a photoactive layer containing a perovskite semiconductor is sandwiched between buffer layers. The photoactive layer containing the perovskite semiconductor mainly receives light in the visible broadband of 400 to 800 nm. The bottom cell 5 has a structure in which a photoactive layer containing silicon is sandwiched between doped layers. The photoactive layer containing silicon receives light in the near-infrared band of 800 to 1200 nm. 【0112】 Figure 3 shows an example of a schematic cross-sectional view of a solar cell module along the III-III cutting line in Figure 1. The solar cell module 100 is arranged in the following order from the side that receives sunlight: surface protective glass 11, top-side solar cell encapsulant 12 composed of a transparent layer, power generation element 1, bottom-side solar cell encapsulant 13, and back surface protective member 16. The bottom-side solar cell encapsulant 13 has a black layer 14 and a white layer 15. The top-side solar cell encapsulant 12 is preferably transparent to increase the transmittance of sunlight. In the solar cell module 100, the power generation element 1 is sandwiched between encapsulants (top-side solar cell encapsulant 12, bottom-side solar cell encapsulant 13), the surface protective glass 11, back surface protective member 16, etc. are arranged outside the encapsulants, and a frame 20 (see Figure 1) is arranged on the outer frame. 【0113】 To form the bottom-side solar cell encapsulant 13, this laminate having a laminate of a white layer and a black layer is used. As shown in Figure 3, sunlight is received from the top cell 3 side of the power generation element 1, and sunlight incident on the gap between the power generation elements 1 is reflected by the white layer, allowing sunlight mainly in the infrared band to be received from the bottom cell 5 side. By combining the black layer formed using this black resin composition with the white layer, it becomes possible to appropriately control the transmittance of the black layer and the reflection characteristics of the laminated structure of the black and white layers, resulting in excellent blackness while efficiently increasing power generation efficiency. 【0114】Preferred examples of the back surface protective member 16 include a sheet in which glass or aluminum is sandwiched between vinyl fluorine films, and a sheet in which aluminum is sandwiched between hydrolysis-resistant polyethylene terephthalate films. For heating and pressurizing, a vacuum laminator can be used, for example. 【0115】 Figure 4 shows a schematic cross-sectional view illustrating an example of the manufacturing process of a solar cell module 100. As shown in Figure 4, for example, the solar cell module 100 is manufactured by arranging the components in the following order from the sun side: surface protective glass 11, top solar cell encapsulant 12, power generation element 1, bottom solar cell encapsulant 13, and back surface protective member 16, and then sealing the power generation element 1 with the top solar cell encapsulant 12 and bottom solar cell encapsulant 13 by heating and pressing. 【0116】 The power generation element 1 is typically black in color, and the gaps between the power generation elements are conventionally made of a transparent material to efficiently receive sunlight. Furthermore, by placing a white layer on the back surface protective member 16, the light reception rate of light incident on the gaps between the power generation elements 1 is increased. However, from a design perspective, there is a market demand to make the gaps between the power generation elements 1 black instead of white, given that the power generation elements 1 are normally black. 【0117】 The thicknesses of the black layer 14 and the white layer 15 can be designed arbitrarily, but in order to reduce the temperature rise due to visible light absorption, it is desirable to make the black layer 14 a thin film within a range that ensures jet blackness. For example, the thickness of the black layer 14 can be 150 to 300 μm, and the thickness of the white layer 15 can be 200 to 400 μm. 【0118】 According to the solar cell module of this embodiment, by using a bottom-side solar cell encapsulant 13 having a black layer 14 and a white layer 15, a solar cell module with excellent jet-black appearance can be provided. Furthermore, by using the black resin composition of this disclosure (black resin composition) in the black layer of the encapsulant, a highly reliable encapsulant with high stability over time and excellent PID resistance can be provided. 【0119】The present disclosure will be further described by examples. The present disclosure is not limited thereto. In the examples, "parts" means "parts by mass" and "%" means "percent by mass". 【0120】 The raw materials used in the examples are listed below. <Thermoplastic Resin (R)> (R-1) POE (Ethylene-1-butene copolymer, MFR: 14 g / 10 min) (R-2) EVA (Vinyl acetate content: 28% by mass, MFR: 20 g / 10 min) (R-3) PC (Polycarbonate, MFR: 15 g / 10 min) (R-4) PMMA (Polymethyl methacrylate, MFR: 2 g / 10 min) [Dispersant (W) (Polyolefin Wax (WO))] (W-1) Sanwax 131P (Manufactured by Sanyo Chemical Industries, Ltd., Polyethylene wax, Mn 3,500, Melting point 105°C, MFR: Over 100 g / 10 min) (W-2) Highwax NP056 (Manufactured by Mitsui Chemicals, Ltd., Polypropylene wax, Mn 7,200, Melting point 130°C, MFR: Over 100 g / 10 min) 【0121】 <Colorants (P)> [PB Pigments (p1)] (p1-1) Paliogen Black L0086 (P.B32) (average primary particle size 200 nm, manufactured by BASF) (p1-2) Spectrasense Black K0087 (average primary particle size 30 nm, manufactured by BASF) (p1-3) Spectrasense Black K0088 (average primary particle size 30 nm, manufactured by BASF) [Complementary Pigments (p2)] In the following compounds, (p2-1) corresponds to dioxazine pigment, (p2-2) to quinacridone pigment, (p2-3) to perylene red pigment, (p2-4) and (p2-6) to phthalocyanine pigment, (p2-7) and (p2-8) to carbon black pigment, (p2-10) to diketopyrrolopyrrole pigment, and (p2-11) to anthraquinone pigment. Furthermore, (p2'-5) corresponds to an isoindolinone pigment, (p2'-9) is classified as a monoazo pigment, and (p2'-12) corresponds to a perylene violet pigment; these are pigments that do not correspond to the complementary pigment (p2). 【0122】 (p2-1) PV First Violet RL (C.I. Pigment Violet 23 (PV23), manufactured by Clariant Japan) (p2-2) Shinkasha Pink K 4410 (C.I. Pigment Red 122 (PR122), manufactured by BASF Japan) (p2-3) Pigment Red 224 (C.I. Pigment Red 224 (PR224), manufactured by Liaoning Honggang Chemicals) (p2-4) LIONOL BLUE FG-7330 (C.I. Pigment Blue 15:3 (PB15), manufactured by Toyo Color Co., Ltd.) (p2'-5) Irgazine Yellow L2060 (C.I. Pigment Yellow 110 (PY110), manufactured by BASF Japan) (p2-6) Heliogen Green K8730 FP (C.I. Pigment Green 7 (PG7), manufactured by BASF Japan) (p2-7) Mitsubishi Carbon Black #40 (CB-1, average particle size 24 nm, pH: 7.5, manufactured by Mitsubishi Chemical Corporation) (p2-8) Mitsubishi Carbon Black #MA100 (CB-2, average particle size 24 nm, pH: 3.5, manufactured by Mitsubishi Chemical Corporation) (p2'-9) Paliotol Yellow K1800 (C.I. Pigment Yellow 183 (PY183), manufactured by BASF) (p2-10) Irgazine Red K3840 (C.I. Pigment Red 254 (PR254), manufactured by BASF Japan) (p2-11) Sinilex Red SR4C (C.I. Pigment Red 177 (PR177), manufactured by BASF Japan) (p2'-12) Pariogen Red Violet K5011 (C.I. Pigment Violet 29 (PV29), manufactured by BASF Japan) [Inorganic black reflective pigment (p3)] (p3-1) chromium iron oxide (Cr ２ O ３ Fe ２ O ３ ), 42-707A (C.I. Pigment Brown 29, average particle size 0.9 μm, manufactured by TOMATEC) 【0123】<Manufacture of Dispersions> [Manufacturing Example 1] 100 parts by mass of a complementary color pigment (p2-1) and 100 parts by mass of a dispersant (W-1), which is a polyolefin wax, were mixed and kneaded at 140 °C using a three-roll mill to obtain Dispersion 1. 【0124】 [Manufacturing Examples 2 to 16] Dispersions 2 to 16 were obtained in the same manner as in Manufacturing Example 1, except that the types and amounts (parts by mass) of the complementary color pigment (p2) and the dispersant (W) (polyolefin wax (WO)) were changed as described in Table 1, respectively. 【0125】 【0126】 [Manufacture of Black Resin Composition (I)] The examples shown below are manufacturing examples of a black resin composition used as a masterbatch for the manufacture of the molding black composition (I) described later. (Example 1 ａ ) 0.500 parts by mass of Dispersion 1, 94.500 parts by mass of a thermoplastic resin (R-1), and 5.000 parts by mass of perylene black pigment (p1-1) were blended, melt-kneaded at 160 °C using a twin-screw extruder (manufactured by Japan Steel Works, Ltd.), and then pelletized to obtain a pellet-shaped black resin composition X-1. 【0127】 (Example 2 ａ to 15 ａ , 31 ａ to 50 ａ , Comparative Example 11 ａ to 13 ａ ) Pellet-shaped black resin compositions X-2 to X-15, X-31 to X-50, and Y-11 to Y-13 were obtained in the same manner as in Example 1, except that the components and blending ratios shown in Tables 2A to 2D were changed. ａ 【0128】 【0129】 【0130】 【0131】 【0132】[Production of a moldable black composition (I) using the black resin composition obtained in production (I) as a masterbatch, and production of a black sheet (I) made from the moldable black composition] (Example 1) ｂ A black composition for molding was obtained by melt-kneading the following materials in a T-die extruder at a temperature of 80°C: 100 parts by mass of thermoplastic resin (R-1) as a diluent, 25 parts by mass of black resin composition X-1 as a masterbatch, 0.600 parts of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a crosslinking agent, 0.600 parts of triallyl isocyanurate as a crosslinking aid, and 0.600 parts of γ-methacryloxypropyltrimethoxysilane as a silane coupling agent. After melt-kneading the black composition for molding, a black sheet with a thickness of 250 μm was obtained by extruding it into a sheet from the T-die extruder. 【0133】 (Example 2) ｂ ~9 ｂ , 11 ｂ ~15 ｂ , 31 ｂ ~50 ｂ Comparative Example 11 ｂ ~13 ｂ Except for changing the type of black resin composition as shown in Table 3, a black composition for molding and a black sheet were obtained in the same manner as in Example 1b. The blending ratios (%) in Table 3 represent the blending ratios of resin (including dispersant (W)) and colorants (PB pigment (p1), complementary pigment (p2), and IBR pigment (p3)), and are calculated excluding crosslinking agents, crosslinking aids, and silane coupling agents. (Example 10) ｂ Except for using 100 parts by mass of thermoplastic resin (R-2) as a diluent resin and 25 parts by mass of black resin composition X-10 as a masterbatch, a black composition for molding was obtained by the same method as in Example 1b. After melt-kneading, a black sheet with a thickness of 250 μm was obtained by extruding it into a sheet shape from a T-die extruder. 【0134】 【0135】[Production of Black Resin Composition (II), and Production of Black Sheet Without Using a Masterbatch (II)] The following example is an example of producing a black sheet directly from a black resin composition. Therefore, this black resin composition is not an example of masterbatch production as described in "Production of Black Resin Composition (I)" above. Furthermore, it is a composition containing a thermoplastic resin and a colorant, and does not contain a crosslinking agent, etc., which is similar to Example 1 described above. ｂ This differs from "black compositions for molding," etc. (Example 16) ｃ A black resin composition consisting of thermoplastic resin (R-1), dispersant (W), perylene black (p1-1), and complementary color pigment (p2) was obtained by blending 0.200 parts by mass of dispersion 1, 97.800 parts by mass of thermoplastic resin (R-1), perylene black (p1), and complementary color pigment (p2) in a T-die extruder and melt-kneading at a temperature of 80°C. The obtained black resin composition was extruded into a sheet from the T-die extruder to obtain a black sheet with a thickness of 250 μm. 【0136】 (Example 17) ｃ , 18 ｃ , 51 ｃ Comparative Example 1 ｃ ~4 ｃ ) Example 16, except that the components and blending ratios shown in Table 4 were changed. ｃ A black sheet with a thickness of 250 μm was obtained using the same method. 【0137】 【0138】 [Production of White Masterbatch Z1] 60 parts by mass of thermoplastic resin (R-1) and 40 parts by mass of titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., average primary particle size 0.2 μm) were blended, and the mixture was melt-kneaded at 160°C in a twin-screw extruder (manufactured by Japan Steel Works, Ltd.), followed by granulation to obtain pellet-shaped white masterbatch Z1. [Production of White Masterbatch Z2] 60 parts by mass of thermoplastic resin (R-2) and 40 parts by mass of titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., average primary particle size 0.2 μm) were blended, and the mixture was melt-kneaded at 160°C in a twin-screw extruder (manufactured by Japan Steel Works, Ltd.), followed by granulation to obtain pellet-shaped white masterbatch Z2. 【0139】 [Manufacturing of laminates for solar cell encapsulants] (Example 1)e A black molding composition was obtained by combining 100 parts by mass of thermoplastic resin (R-1) as a diluent, 25 parts by mass of black resin composition (X-1) as a masterbatch, and 0.600 parts each of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a crosslinking agent, triallyl isocyanurate as a crosslinking aid, and γ-methacryloxypropyltrimethoxysilane as a silane coupling agent. A white molding composition was also obtained by combining 100 parts by mass of thermoplastic resin (R-1) as a diluent, 15 parts by mass of white masterbatch Z1, and 0.600 parts each of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a crosslinking agent, triallyl isocyanurate as a crosslinking aid, and γ-methacryloxypropyltrimethoxysilane as a silane coupling agent. Next, a laminate consisting of two layers, a black layer (thickness 250 μm) and a white layer (thickness 350 μm), was obtained by multilayer extrusion molding of the molding black composition and the molding white composition at a temperature of 80°C using a multilayer T-die method. 【0140】 (Example 2) ｅ ~9 ｅ Example 11 ｅ ~15 ｅ , Example 31 ｅ ~50 ｅ Comparative Example 11 ｅ ~13 ｅ ) Except for using the molding black composition of the corresponding example with the same numerical number shown in Table 3 as the molding black composition, Example 1 ｅ Using a similar method, a laminate consisting of two layers, a black layer (250 μm thick) and a white layer (350 μm thick), corresponding to each example, was obtained. 【0141】 (Example 10) e ) As a diluent, 100 parts by mass of thermoplastic resin (R-2) and 25 parts by mass of black resin composition (X-10), Example 1 ｅ A black molding composition was obtained by blending 0.600 parts each of the same type of crosslinking agent, crosslinking aid, and silane coupling agent. In addition, 100 parts by mass of thermoplastic resin (R-2) and 15 parts by mass of white masterbatch Z2 were used as diluents in Example 1. ｅA white molding composition was obtained by blending 0.600 parts each of the same type of crosslinking agent, crosslinking aid, and silane coupling agent. Then, by multilayer extrusion molding of the black molding composition and the white molding composition at a temperature of 80°C using a multilayer T-die method, a laminate with a two-layer structure having a black layer thickness of 250 μm and a white layer thickness of 350 μm was obtained. 【0142】 (Example 16) ｅ ~18 ｅ , 51 ｅ Comparative Example 1 ｅ ~4 ｅ ) Example 16 ｃ ~18 ｃ A black resin composition for molding was obtained by further adding 0.600 parts each of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a crosslinking agent, triallyl isocyanurate as a crosslinking aid, and γ-methacryloxypropyltrimethoxysilane as a silane coupling agent to the black resin compositions (X-16) to (X-18) and (X-51) to (X-53). Comparative Example 1 ｃ ~4 ｃ Black resin compositions (Y-1) to (Y-4) were obtained for molding in the same manner. A white composition for molding was also obtained by blending 100 parts by mass of thermoplastic resin (R-1) as a diluent, 15 parts by mass of white masterbatch Z1, and 0.600 parts each of the same crosslinking agent, crosslinking aid, and silane coupling agent as described above. Then, by multilayer extrusion molding of the black and white compositions for molding at a temperature of 80°C using a multilayer T-die method, laminates of each example with a two-layer structure, having a black layer thickness of 250 μm and a white layer thickness of 350 μm, were obtained. 【0143】 [Manufacturing of solar cell modules] [Example 1] ｆ ~18 ｆ , 31 ｆ ~51 ｆ Comparative Example 1 ｆ ~4 ｆ , 11 ｆ ~13 ｆA solar cell module was fabricated as shown in Figure 5. Specifically, a 3 mm thick surface protective glass 11, a top-side solar cell encapsulant 12, a power generation element 1, a bottom-side solar cell encapsulant 13, and a back-side protective member 16 were laminated in this order, placed in a vacuum laminator, and then heated and pressurized under vacuum at 145°C for 17 minutes to crosslink the encapsulant and obtain a solar cell module. As the bottom-side solar cell encapsulant 13, Example 1 ｆ ~18 ｆ , 31 ｆ ~51 ｆ Comparative Example 1e ｆ ~4e ｆ , 11 ｆ ~13 ｆ A 250 μm thick black layer obtained by the above method and a 350 μm thick white layer obtained from the above-mentioned white composition (a white composition containing 100 parts by mass of thermoplastic resin (R-1), 15 parts by mass of white masterbatch Z1, and 0.600 parts each of crosslinking agent, crosslinking aid, and silane coupling agent) were used. An LM-50×50-S vacuum laminator (manufactured by NPC Corporation) was used. 【0144】 In the PID resistance test, a solar cell module 100a was fixed to a metal frame 35, and then the power generation element 1 was wired with the negative terminal and the metal frame 35 with the positive terminal, and the positive and negative output terminals were wired to prepare a solar cell module sample for the PID resistance test. 【0145】 [Evaluation] Laminates, solar cell modules, and black sheets molded using the black resin composition of this disclosure were measured and evaluated using the following methods. The evaluation results are shown in Table 5. In Table 5, the results are shown for each numerical number of the example, and those with the same number but different alphabetical letters are listed together in the same row. That is, in each example and comparative example, for example, "Example 1 ｂ " and "Example 1 ｅ These are all shown together in the "Example 1" section. 【0146】 <Jet Blackness> Example 1 ｂ ~15 ｂ , 31 ｂ ~50 ｂ , 16 ｃ ~18 ｃ, 51 ｃ and Comparative Example 1 ｃ ~4 ｃ , 11 ｂ ~13 ｂ Each of the black sheets of ~ was cut to a size of 10 cm × 10 cm, and the blackness was evaluated according to the following criteria. For the measurement, a spectrophotometer "CM-36dG" manufactured by Konica Minolta was used, and the L value was measured according to JIS Z 8722 (2009), Condition C (Condition C: di(de)8°). ++++: The L value is less than 32. The best. +++: The L value is 32 or more and less than 33. Excellent. ++: The L value is 33 or more and less than 34.5. Good. +: The L value is 34.5 or more and less than 35. Acceptable. NG: The L value is 35 or more. The target was not achieved. 【0147】 <Reflectance> Example 1 e ~18 e , 31 e ~51 e , and Comparative Example 1 e ~4 e , 11 e ~13 e For each of the laminates for solar cell encapsulants of ~, ~, and Comparative Example 1, using an ultraviolet-visible-infrared spectrophotometer "UV-3150" with an integrating sphere manufactured by Shimadzu Corporation, the total light reflectance at wavelengths of 800 to 1100 nm was measured. The total light reflectance indicates the ratio of all reflected light reflected on the sample surface such as specularly reflected light and diffusely reflected light, and the incident light from the light source was made to be perpendicularly incident on the sample. Also, the total light reflectance is the relative reflectance when the reflectance of a standard plate (barium sulfate) is set to 100%. Evaluation was made according to the following criteria. ++++: The average reflectance is 82% or more. The best. +++: The average reflectance is less than 8, 2% and 80% or more. Excellent. ++: The average reflectance is less than 80% and 72% or more. Good. +: The average reflectance is less than 72% and 65% or more. Acceptable. NG: The average reflectance is less than 65%. The target was not achieved. 【0148】 <Dispersibility> Example 1 ｂ ~15 ｂ , 31 ｂ ~50 ｂ , 16 ｃ ~18 ｃ , 51 ｃ and Comparative Example 1 ｃ ~4 ｃ, 11 ｂ ~13 ｂ For each of the black sheets, a 10cm x 10cm sheet was cut (using the same method as for evaluating jet blackness) to obtain test sheets. Each test sheet was observed using an optical microscope, "Digital Microscope VHX-100" (manufactured by Keyence Corporation), at a magnification of 50x. Dispersibility was evaluated according to the following criteria based on the size of the black dot aggregates observed in the field of view. The fewer large particles there are, the better the dispersibility and the superior the appearance. [Judgment Criteria] +++: No black dot aggregates larger than 100 μm. Very good. ++: Black dot aggregates larger than 100 μm are present, but none larger than 200 μm. Good. +: Black dot aggregates larger than 200 μm are present, but none larger than 300 μm. Practical level. NG: Black dot aggregates larger than 300 μm are observed in the field of view. Target not met. 【0149】 <PID resistance (evaluation of stability over time)> Example 1 ｆ ~18 ｆ , 31 ｆ ~51 ｆ Comparative Example 1 ｆ ~4 ｆ , 11 ｆ ~13 ｆFor the solar cell modules used for PID resistance evaluation, the initial I-V characteristics (Isc and Pm) and leakage current were measured. The initial leakage current was confirmed to be 0A in all examples and comparative examples. Next, the samples were subjected to PID testing under the following conditions, and the I-V characteristics and leakage current were measured after the test. The Pm retention rate was then calculated using the following formula: Pm retention rate = (initial Pm value / Pm value after test) × 100. PID resistance test conditions: The test was conducted at a temperature of 60°C and a humidity of 85% RH, with an applied voltage of 1000V for 96 hours. In order to promote the PID phenomenon, the surface protective glass was covered with water to increase the potential difference between the power generation element and the surface protective glass during the measurement. The I-V characteristics were measured using a solar cell simulator MS-180AAA (manufactured by Ushio Specs) and a solar cell characteristic tester DKPVT-30 (manufactured by DENKEN). Furthermore, leakage current was measured by setting the output terminal with the power generation element as the negative terminal and the frame as the positive terminal, and applying 1000V to measure the current flowing from the frame through the sealing material to the power generation element. [Judgment Criteria] +++: Pm retention rate of 95% or more. Very good. ++: Pm retention rate of less than 95% or 90% or more. Excellent. +: Pm retention rate of less than 90% or 85% or more. Good. NG: Pm retention rate of less than 85%. Target not met. 【0150】 <Migration (PCT)> Example 1 ｅ ~18 ｅ , 31 ｅ ~51 ｅ , and Comparative Example 1 ｅ ~4 ｅ , 11 ｅ ~13 ｅEach laminate for the solar cell encapsulant was placed in a vacuum laminator and then crosslinked by heating and pressurizing under vacuum at 145°C for 17 minutes. An LM-50×50-S vacuum laminator (manufactured by NPC Corporation) was used. Subsequently, the crosslinked laminates were subjected to a 240-hour pressure cooker (PCT) test under environmental conditions of 121°C, 100% RH relative humidity, and 2 atmospheres. The degree of discoloration of the white sheet (color difference ΔE) was evaluated by visually comparing the white layer after the test with the test piece before the test. The color difference ΔE was measured using the white surface of the fabricated solar cell encapsulant laminate with a Konica Minolta spectrophotometer "CM-36dG" based on JIS Z 8722 (2009) condition C, and evaluated according to the following criteria: ++++: ΔE value is 0.3 or less. +++: ΔE value is greater than 0.3 and 0.45 or less. ++: ΔE value is greater than 0.45 and less than or equal to 0.7. +: ΔE value is greater than 0.7 and less than or equal to 2. NG: ΔE value is greater than or equal to 2. 【0151】 <Plate-out resistance> Example 1 using a T-die molding machine ｂ ~15 ｂ Example 16 ｃ ~18 ｃ , Example 31 ｂ ~50 ｂ , 51 ｃ and Comparative Example 1 ｃ ~4 ｃ , 11 ｃ ~13 ｃ One kilogram of each black sheet was prepared, and the state of plate-out material adhesion inside the die was visually observed and evaluated according to the following criteria: +++: Colored material is observed in less than 10% of the area inside the die. ++: Colored material is observed in 10% or more but less than 30% of the area inside the die. +: Colored material is observed in 30% or more but less than 70% of the area inside the die. NG: Colored material is observed in 70% or more of the area inside the die. 【0152】<Humidity and Heat Resistance (Stability over Time)> The fabricated solar cell modules were subjected to a humidity and heat test under the following conditions, and the I-V characteristics and Pm value were measured after the test. The Pm retention rate was calculated using the following formula: Pm retention rate = (Initial Pm value / Pm value after test) × 100 ・Humidity and heat resistance test conditions: Temperature 121°C, relative humidity 100% RH, 1 atm, and timed for 288 hours. The I-V characteristics were measured using a solar cell simulator MS-180AAA (manufactured by Ushio Specs) and a solar cell characteristic tester DKPVT-30 (manufactured by DENKEN). [Judgment Criteria] ++++: Pm retention rate of 98% or more. Very good. +++: Pm retention rate less than 98% but 95% or more. Excellent. ++: Pm retention rate less than 95% but 90% or more. Good. +: Pm retention rate less than 90% but 85% or more. Within acceptable limits. NG: PM retention rate less than 85%. Target not met. 【0153】 <UV Resistance (Stability over Time)> The fabricated solar cell modules were subjected to UV testing under the following conditions. The I-V characteristics and Pm value were measured after the test, and the Pm retention rate was calculated using the following formula: Pm retention rate = (Initial Pm value / Pm value after test) × 100 ・UV resistance test conditions: Temperature 60°C, relative humidity 50% RH, irradiation intensity 1000 W / m ２ The test duration was 300 hours, and the total irradiation intensity was 300 kWh / m². ２ The following was done. The I-V characteristics were measured using a solar simulator MS-180AAA (manufactured by Ushio Specs) and a solar cell characteristic tester DKPVT-30 (manufactured by DENKEN). [Judgment Criteria] ++++: Pm retention rate of 98% or more. Very good. +++: Pm retention rate of less than 98% but 95% or more. Excellent. ++: Pm retention rate of less than 95% but 90% or more. Good. +: Pm retention rate of less than 90% but 85% or more. Within acceptable limits. NG: Pm retention rate of less than 85%. Target not met. 【0154】 【0155】 [Production of Black Resin Composition (III)] The following example shows how to produce a pelletized black resin composition from a black resin composition. (Example 19) ａA black resin composition (X-19) in pellet form was obtained by blending 0.500 parts by mass of complementary pigment (p2-4), 89.500 parts by mass of thermoplastic resin (R-3), and 10.00 parts by mass of perylene black pigment (p1-2), melt-kneading the mixture at 280°C in a twin-screw extruder (manufactured by Japan Steel Works, Ltd.), and then granulating the mixture. 【0156】 (Example 20) ａ A black resin composition (X-20) in pellet form was obtained by blending 0.500 parts by mass of complementary pigment (p2-4), 89.500 parts by mass of thermoplastic resin (R-4), and 10.000 parts by mass of perylene black pigment (p1-2), melt-kneading the mixture at 260°C in a twin-screw extruder (manufactured by Japan Steel Works, Ltd.), and then granulating it. 【0157】 (Example 21) ａ Comparative Example 5 ａ Comparative Example 6 ａ ) Example 19, except that the components and blending ratios shown in Table 6 were changed. ａ Pellet-shaped black resin compositions (X-21), (Y-5), and (Y-6) were obtained by the same method. (Example 22) ａ ) Example 20, except that the components and blending ratios shown in Table 6 were changed. ａ A pellet-shaped black resin composition (X-22) was obtained by the same method. 【0158】 【0159】 [Manufacturing of plate test specimens] (Example 19) ｂ Two parts of the black resin composition (X-19) and 100 parts of the diluent resin (R-3) were mixed and molded at 280°C using an injection molding machine (manufactured by Toshiba Machine Co., Ltd.) to obtain a plate test piece measuring 150 mm in length, 125 mm in width, and 2.5 mm in thickness. 【0160】 (Example 21) ｂ Comparative Example 5 ｂ , 6 ｂ ) Example 19, except that the black resin composition shown in Table 7 was changed. ｂ Using a similar method, a plate test specimen measuring 150 mm in length, 125 mm in width, and 2.5 mm in thickness was obtained. 【0161】 (Example 20) ｂ Example 22ｂ ) Example 19 is the same except that the black resin composition shown in Table 7 is changed, and the molding temperature of the injection molding machine is changed to 260°C. ｂ Using a similar method, a plate test specimen measuring 150 mm in length, 125 mm in width, and 2.5 mm in thickness was obtained. 【0162】 【0163】 [Evaluation] The black resin composition and test plate of this disclosure were measured and evaluated using the following methods. The evaluation results are shown in Table 8. 【0164】 <Variable Observation Angle Test (Jet Blackness)> Example 19 ｂ ~22 ｂ Comparative Example 5 ｂ , 6 ｂ The jet-black hue was evaluated for plate test specimens obtained from the molding black composition by varying the observation angle. The measurement was performed under a D50 light source, with light irradiated onto the plate test specimen at a 45° angle from the normal n (perpendicular line), the observer positioned at 90°, and the appearance of the test specimen was determined so that it was not in the observer's shadow. The appearance of the test specimen was observed visually at 20°, 45°, 75°, and 110°. The visual evaluation was performed according to the following criteria: +++: The jet-black hue is consistent when observed at 20°, 45°, 75°, and 110° (the hue does not change). ++: The jet-black hue is consistent when observed at 3 out of 4 angles. +: The jet-black hue is consistent when observed at 2 out of 4 angles. NG: The jet-black hue is not consistent when observed at any of the 4 angles. 【0165】 <PCT resistance (evaluation of stability over time)> Example 19 ｂ ~22 ｂ , and Comparative Example 5 ｂ , 6 ｂ A pressure cooker (PCT) test was performed on plate test specimens obtained from the black molding composition using the same method as for laminates used in solar cell encapsulants. The degree of discoloration of the test specimens (color difference ΔE before and after the test) was evaluated by visually comparing the specimens before and after the test. The evaluation criteria were the same as those for the migration (PCT) evaluation described above. 【0166】<Near-infrared transmittance evaluation> Example 19 ｂ ~22 ｂ , and Comparative Example 5 ｂ , 6 ｂ Using plate test pieces (2.5 mm thick) obtained from the black molding composition, the near-infrared transmittance at wavelengths of 800 to 1100 nm was measured using a Shimadzu UV-3150 ultraviolet-visible-infrared spectrophotometer with an integrating sphere. The near-infrared transmittance represents the proportion of all transmitted light that passed through the sample, including straight-linked transmitted light and diffuse-linked transmitted light, and the incident light from the light source was incident perpendicularly to the sample. The near-infrared transmittance is a relative transmittance with the transmittance when the sample is not placed in the holder set to 100%. The following criteria were used for evaluation: +++: Average transmittance of 70% or more. Excellent. ++: Average transmittance of less than 70% but 60% or more. Good. +: Average transmittance of less than 60% but 55% or more. Good. NG: Average transmittance of less than 55%. Target not met. 【0167】 【0168】 The embodiments of this disclosure, which contain specific amounts of PB pigment (p1) and complementary pigment (p2), and further have a ratio of [CB pigment] / [PB pigment (p1)] of less than 0.1, and an IBR pigment (p3) content of 0.9 parts by mass or less per 100 parts by mass of PB pigment (p1), were confirmed to exhibit excellent jet blackness, as well as excellent reflectivity, dispersibility, PID resistance, migration resistance, and plate-out resistance, as shown in Examples 1 to 18 and 31 to 51. Furthermore, as shown in Examples 19 to 22, it was confirmed that the jet blackness was excellent regardless of the observation angle. 【0169】 This application claims priority based on Japanese Patent Application No. 2024-216310, filed on 11 December 2024, and incorporates all of its disclosures herein. 【0170】 1: Power generation element 2: Top electrode 3: Top cell 4: Intermediate electrode 5: Bottom cell 6: Bottom electrode 11: Surface protective glass 12: Top side solar cell encapsulant 13: Bottom side solar cell encapsulant 14: Black layer 15: White layer 16: Back surface protective material 20: Frame 35: Metal frame 100: Solar cell module

Claims

1. A black resin composition comprising a colorant (P) and a thermoplastic resin (R), wherein the colorant (P) comprises a perylene black pigment (p1) and a complementary pigment (p2), and may further contain an inorganic black reflective pigment (p3), the complementary pigment (p2) is one or more selected from the group consisting of perylene red pigment, anthraquinone pigment, quinacridone pigment, phthalocyanine pigment, dioxazine pigment, diketopyrrolopyrrole pigment and carbon black pigment, if the carbon black pigment is included, the mass ratio of the carbon black pigment to the perylene black pigment (p1), [carbon black pigment] / [perylene black pigment (p1)], is less than 0.1, the content of the inorganic black reflective pigment (p3) is 0.9 parts by mass or less per 100 parts by mass of the perylene black pigment (p1), and the glass transition temperature of the thermoplastic resin (R) is 0°C or less.

2. The complementary pigment (p2) is the black resin composition according to claim 1, satisfying the following (I): (I) The complementary pigment (p2) is a complementary pigment that, when a composition is prepared by blending the complementary pigment (p2) in an amount of 0.3 parts by mass per 100 parts by mass of low-density polyethylene resin, and a test piece with a thickness of 250 μm has an average transmittance of 50% or more at wavelengths of 800 to 1100 nm in accordance with ASTM-E424-71-2023.

3. The black resin composition according to claim 1, wherein the complementary color pigment (p2) is a complementary color organic pigment (p2-a), and of 100% by mass of the complementary color organic pigment (p2-a), 55% by mass or more is a complementary color organic pigment (p2-a) that is a nitrogen-containing compound containing nitrogen.

4. The black resin composition according to claim 1, wherein the content of the complementary pigment (p2) is 0.5 to 20 parts by mass per 100 parts by mass of the perylene black pigment (p1).

5. The black resin composition according to claim 1, wherein the thermoplastic resin (R) contains polyolefin wax (WO), and the mass ratio [complementary pigment (p2)] / [polyolefin wax (WO)] is 0.01 to 100.

6. A molded article formed from either (i) a black resin composition according to any one of claims 1 to 5, or (ii) a moldable black composition obtained by adding at least the black resin composition to a diluted resin.

7. A laminate having a white layer and a black layer formed from either (i) a black resin composition according to any one of claims 1 to 5, or (ii) a molding black composition obtained by adding at least the black resin composition to a diluted resin.

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