Laminate, container, resin composition used therein, and method for manufacturing a laminate.

Abstract

To provide a laminate that can achieve both oxygen barrier properties and light shielding properties, and a container that, by using the laminate, also has excellent mechanical strength and design in addition to oxygen barrier properties and light shielding properties. Furthermore, by suppressing the migration and leaching of colorants, the aim is to provide containers that offer excellent storage stability for contents such as beverages. [Solution] The problem is solved by a laminate comprising a resin composition layer containing a colorant and a thermoplastic resin, and a diamond-like carbon layer, characterized in that when observing 10 locations in a 500 μm × 500 μm area at 100x magnification with an optical microscope, the average number of aggregates with a major axis of 20 μm or more is 10 or less.

Description

Technical Field

[0001] The present invention relates to a laminate having a diamond-like carbon layer, a container, and a resin composition used for producing these. The present invention also relates to a method for producing the laminate.

Background Art

[0002] Plastic containers have characteristics such as designability, light weight, and safety, and are therefore used in many fields such as food, healthcare, cosmetics, and medicine, and the usage amount is increasing. However, compared with glass containers, they have high gas permeability, such as oxygen, so oxygen in the atmosphere may enter the container and cause deterioration of the quality of the contents.

[0003] As a method for reducing the gas permeability of plastic containers, a method of laminating a material with low gas permeability by coating is known. Among them, plastic containers coated with a diamond-like carbon layer are known to have very low oxygen permeability and excellent transparency and recyclability. For example, Patent Documents 1 to 3 disclose a manufacturing apparatus and a manufacturing method for a plastic container whose inner wall surface is coated with a diamond-like carbon layer.

Prior Art Documents

Patent Documents

[0004] <9>

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] Besides oxygen, light is a major factor in the degradation of the contents of a container. Visible light and ultraviolet light degrade the contents by promoting the breaking of chemical bonds within molecules and intermolecular reactions. Therefore, plastic containers require not only oxygen barrier properties to suppress oxygen permeability but also light-shielding properties. However, conventional plastic containers coated with a diamond-like carbon layer do not provide sufficient light shielding.

[0006] Furthermore, when manufacturing plastic containers, it has been considered to impart light-shielding properties by mixing colorants into the thermoplastic resin used as the raw material. However, it has been found that simply coating plastic containers colored with common pigments such as carbon black with a diamond-like carbon layer results in a decrease in oxygen barrier properties compared to uncolored plastic containers.

[0007] Therefore, the present invention aims to provide a laminate that can achieve both oxygen barrier properties and light shielding properties, and a container that, by using the laminate, is excellent not only in oxygen barrier properties and light shielding properties but also in mechanical strength and design. Furthermore, by suppressing the migration and leaching of colorants, the challenge is to provide containers that offer superior storage stability for contents such as beverages. [Means for solving the problem]

[0008] After diligent research by the inventors, it was found that the problems of the present invention can be solved in the following embodiment. We discovered this and completed the present invention. [1] A resin composition layer containing a colorant and a thermoplastic resin, It has a diamond-like carbon layer, A laminate characterized in that, when observing 10 areas of 500 μm × 500 μm at a magnification of 100x with an optical microscope, the average number of aggregates with a major axis of 20 μm or more is 10 or less. [2]: The laminate according to [1], characterized in that the haze is 30% or less. [3]: The laminate according to [1] or [2], characterized in that the thermoplastic resin contains a polyester resin. [4]: The laminate according to any one of [1] to [3], characterized in that the resin composition layer contains a fatty acid amide. [5]: A container comprising at least a portion of the laminate described in any of [1] to [4]. [6]: A resin composition used to form the resin composition layer in a laminate having a resin composition layer and a diamond-like carbon layer, The aforementioned resin composition contains a colorant and a thermoplastic resin, A resin composition characterized in that, when a 300 μm thick sheet formed using the aforementioned resin composition is observed with an optical microscope at a magnification of 100x, in 10 locations of a 500 μm × 500 μm area, the average number of aggregates with a major axis of 20 μm or more is 10 or less. [7]: A method for manufacturing a laminate described in any of [1] to [4], A step of forming a resin composition layer from a resin composition containing a colorant and a thermoplastic resin, The process includes a step of depositing diamond-like carbon onto the resin composition layer to form a diamond-like carbon layer. A method for manufacturing laminates. [Effects of the Invention]

[0009] According to the present invention, it is possible to create a laminate that can achieve both oxygen barrier properties and light shielding properties, and by using this laminate, it is possible to provide a container that is excellent in terms of design as well as oxygen barrier properties and light shielding properties. Furthermore, by suppressing the migration and leaching of colorants, the goal is to provide containers that offer superior storage stability for contents such as beverages. [Modes for carrying out the invention]

[0010] Hereinafter, an example of an embodiment to which the present disclosure is applied will be described. However, the present disclosure is not limited to this embodiment, and other embodiments may belong to the scope of the present disclosure as long as they conform to the gist of the present disclosure. Further, the numerical values "A to B" specified in this specification refer to a range that satisfies a value greater than the numerical value A and a value smaller than the numerical value B. Note that the numerical values specified in this specification are values obtained by the methods disclosed in the embodiments or examples. Further, in this specification, sheet, film, and plate-like are synonymous. Unless otherwise noted, the various components appearing in this specification may be used alone or in combination of two or more. Incidentally, "C.I." means Color Index.

[0011] ≪Laminate≫ The laminate of the present disclosure has a resin composition layer containing a colorant and a thermoplastic resin, and a diamond-like carbon layer. Preferably, it is a laminate obtained by coating the resin composition layer with a diamond-like carbon layer. Among them, coating by vapor deposition is preferable.

[0012] The laminate may further have an arbitrary layer such as another resin layer, etc., but it is preferable from the viewpoints of oxygen barrier properties and light shielding properties that the resin composition layer containing a colorant and a thermoplastic resin and the diamond-like carbon layer are directly laminated.

[0013] When the laminate is observed at 100 times magnification with an optical microscope in a region of 500 μm × 500 μm at 10 locations, the average number of aggregates having a major diameter of 20 μm or more is 10 or less. The laminate of the present disclosure has low oxygen permeability and light transmittance, enables both oxygen barrier properties and light shielding properties, and also has little color unevenness and is transparent, so it is excellent in design. Furthermore, since the migration and elution of the colorant are suppressed, it can be suitably used as a container having excellent storage stability even in the case of a container containing contents such as beverages.

[0014] Since the number of aggregates with a major axis of 20 μm or more is 10 or less on average, there are no coarse particles derived from a coloring material or the like in the resin composition layer, and the surface of the resin composition layer is smooth. Therefore, a diamond-like carbon layer with a thickness of several hundred nm or less can coat the resin composition layer with a uniform thickness, thereby resulting in a laminate having high oxygen barrier properties. In addition, since there is little color unevenness and it is transparent, it has excellent glass-like design properties. The average number of aggregates is preferably as small as possible, more preferably 5 or less on average, and even more preferably 1 or less on average. Note that the diamond-like carbon layer is usually very thin, and no aggregates with a major axis of 20 μm or more are observed in the diamond-like carbon layer. Therefore, the smoothness of the resin composition layer or the uniform coating property of the diamond-like carbon layer can be judged by the number of aggregates in the laminate.

[0015] Therefore, setting the average number of aggregates in the laminate to 10 or less represents reducing the average number of aggregates in the resin composition layer. In order to make the average number of aggregates in the laminate 10 or less, it can be controlled by the structure, particle diameter, content of the coloring material used in the resin composition layer, or the compatibility with the resin, the type and content of the dispersant used as necessary, the manufacturing method of the resin composition, and the like. Among them, it is preferable to control by dissolving or finely dispersing the coloring material contained in the resin composition layer in a thermoplastic resin. Specifically, the number of aggregates can be reduced by using a coloring material having excellent solubility or dispersibility in a thermoplastic resin or using a dispersant such as fatty acid amide. Also, when mixing the thermoplastic resin and the coloring material, the number of aggregates can be reduced by controlling the kneading conditions such as the structure, temperature, and time of the kneading device or by manufacturing the laminate using a resin composition via a masterbatch.

[0016] The average number of aggregates can be measured by observing 10 regions of 500 μm × 500 μm at a magnification of 100 times with transmitted light using an optical microscope "Digital Microscope VHX-100" (manufactured by Keyence Corporation) for the laminate and counting the observed aggregates with a major axis of 20 μm or more. The measurement of aggregates yields the same results regardless of which side of the laminate is used. However, since the aggregates represent the number of aggregates in the resin composition layer, it is preferable to measure from the resin composition layer side. Further details can be obtained by the method described in the examples.

[0017] The aggregates observed in the laminate using the method described above preferably have a maximum major axis of 50 μm or less, and more preferably 30 μm or less.

[0018] From the viewpoint of oxygen barrier properties, the haze of the laminate is preferably 30% or less. The haze is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less. Haze can be measured using HazeGuard Plus (manufactured by Gardner) in accordance with JIS K7136:2000. Haze can be measured from any surface of the laminate, but for example, the diamond-like carbon layer can be pointed towards the light source during measurement. Further details can be obtained by the method described in the examples.

[0019] The light transmittance of the laminate in the 350-450 nm range is preferably 30% or less. The light transmittance can be measured using a UV-3150 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation, by measuring the transmittance at 1 nm intervals in the wavelength range of 350 nm to 450 nm and calculating the average value. When the light transmittance is 30% or less, the contents have excellent preservation properties. The light transmittance is preferably 20% or less, and more preferably 10% or less. Furthermore, the light transmittance in the 300-400 nm range is preferably 10% or less, and even more preferably 5% or less. Light transmittance can be measured from any surface of the laminate, but for example, the diamond-like carbon layer can be pointed towards the light source during measurement. Further details can be obtained by the method described in the examples.

[0020] The thickness of the laminate is not particularly limited and may be between 1 and 10,000 μm, and can be appropriately selected depending on the application. The laminate of this disclosure exhibits high oxygen barrier properties and excellent lightweight properties even at thicknesses of 1,000 μm or less. The thickness of the laminate is preferably between 10 and 3,000 μm, more preferably between 100 and 1,000 μm, and even more preferably between 200 and 600 μm. The thickness of the laminate can be measured using calipers.

[0021] The laminate may take any shape, such as a film, sheet, or container, but it is preferably used as a container or its lid, and in particular, as a container. The laminate of the present invention can be used to create a container with excellent light-shielding and barrier properties. This suppresses deterioration of the contents and provides excellent storage stability for the contents, so it is preferable that the container be made of at least a portion of the laminate of the present invention. The container can be suitably used for a variety of applications, including beverages, food, pharmaceuticals, and cosmetics.

[0022] The shape of the container may be selected as appropriate depending on the application, and examples include bottles, tubes, jars, tanks, cups, etc. The container may have a lid component such as a sealing material or a cap. The laminate may form at least a part of the container body or lid component.

[0023] The thickness of the laminate constituting at least a part of the container may be, for example, 10 μm or more at its thinnest point, but 100 μm or more is preferred in terms of the mechanical strength of the container. The thickness of the thickest part may be any thickness, but 10 mm or less is preferred from the viewpoint of lightweightness. The thickness of the laminate constituting at least a part of the container is preferably 100 to 1000 μm, and more preferably 200 to 600 μm.

[0024] The laminate can be obtained, for example, by molding a resin composition layer and then coating the resin composition layer with diamond-like carbon by vapor deposition or the like. When the laminate constitutes part of a container, it is preferable to place the diamond-like carbon layer on the inside to prevent damage to the diamond-like carbon layer from contact with objects outside the container.

[0025] Furthermore, it is preferable to have a step of forming a resin composition layer from a resin composition containing a colorant and a thermoplastic resin, and a step of depositing diamond-like carbon onto the resin composition layer to form a diamond-like carbon layer. By performing the above steps, a uniform diamond-like carbon layer can be provided on a resin composition layer of any shape, so that a laminate with a suitable shape and high oxygen barrier properties can be obtained depending on the application.

[0026] <Resin composition layer> The resin composition layer contains a colorant and a thermoplastic resin, and primarily imparts light-shielding properties and mechanical strength to the laminate. The resin composition layer may further contain components such as dispersants and additives. Coating the resin composition layer with a diamond-like carbon layer to form a laminate is preferable because it provides superior oxygen barrier properties and light-shielding properties. Furthermore, if diamond-like carbon is included, it is considered a diamond-like carbon layer even if it also contains colorants and thermoplastic resins.

[0027] [Colorants] As the colorant, at least one selected from the group consisting of dyes and pigments can be used. The colorant may be used alone or two or more. By including the colorant in the resin composition layer, light-shielding properties can be imparted to the laminate. On the other hand, the colorant may aggregate in the resin composition layer to form coarse particles, which may hinder the uniform film formation of the diamond-like carbon layer. However, we have found that by reducing the content of aggregates in the resin composition layer, the diamond-like carbon layer can uniformly cover the resin composition layer, resulting in a laminate that combines light-shielding and oxygen barrier properties. Therefore, the present invention makes it possible to achieve both oxygen barrier properties and light shielding properties by having an average number of aggregates with a major axis of 20 μm or more in the laminated structure be 10 or less.

[0028] The colorants used in the resin composition are not particularly limited, but it is preferable that the colorants produce few aggregates in the resin composition layer, and it is preferable that the colorants have high compatibility with the thermoplastic resin used, and, if necessary, have excellent dispersibility with the use of a dispersant.

[0029] The colorant content may be 0.01 to 5.0% by mass of 100% by mass of the resin composition layer. From the viewpoint of oxygen barrier properties, 1.0% by mass or less is preferred, and 0.50% by mass or less is more preferred. From the viewpoint of light shielding properties, 0.01% by mass or more is preferred, and 0.10% by mass or more is more preferred.

[0030] As a colorant with high compatibility with thermoplastic resins, it is preferable to use a colorant that has high solubility in bis(2-ethylhexyl) phthalate, which has solubility parameters similar to those of general thermoplastic resins. It is preferable that the solubility in bis(2-ethylhexyl) phthalate is 0.1% by mass or more at 250°C, as this results in a laminate with superior oxygen barrier properties. Solubility is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. There is no particular upper limit, but it may be 50% by mass or less.

[0031] The content of the colorant, which has a solubility in bis(2-ethylhexyl) phthalate of 0.1% by mass or more at 250°C, is preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, from the viewpoint of oxygen barrier properties in the resin composition layer. From the viewpoint of light shielding properties, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more.

[0032] The content of the colorant, which has a solubility in bis(2-ethylhexyl) phthalate of less than 0.1% by mass at 250°C, is preferably 0 to 0.05% by mass, and more preferably 0 to 0.01% by mass, in the resin composition layer.

[0033] Furthermore, it is preferable that the colorant used in the resin composition is one that exhibits minimal migration and elution from the resin composition layer. This suppresses color transfer to articles in contact with the laminate. Additionally, its low solubility in the contents of the container makes it suitable for use in containers as well.

[0034] As such a colorant, it is preferable to use a colorant that has solubility parameters similar to those of general thermoplastic resins, and whose solubility in bis(2-ethylhexyl) phthalate is 0.01% by mass or less at room temperature (25°C). Such colorants are preferred because their movement within the resin composition layer is suppressed and their migration from the laminate is low. The solubility in bis(2-ethylhexyl) phthalate is more preferably 0.005% by mass or less, and more preferably 0.001% by mass or less.

[0035] Furthermore, the amount of colorant with solubility exceeding 0.01% by mass at room temperature is preferably 0.3% by mass or less in the resin composition layer, and more preferably 0 to 0.10% by mass.

[0036] From the viewpoint of the oxygen barrier properties of the laminate, dyes or organic pigments are preferred as colorants. Compared to inorganic pigments, they can provide sufficient light shielding with a small amount and have high affinity with thermoplastic resins, which reduces the number of aggregates in the resin composition layer and allows for a more uniform formation of the diamond-like carbon layer. This improves the oxygen barrier properties of the laminate. Furthermore, from the viewpoint of resistance to migration and elution of colorants, organic pigments are preferred.

[0037] (dye) In this disclosure, dyes include compounds classified as other than pigments in the color index. Examples of dyes include oil-soluble dyes, disperse dyes, acid dyes, basic dyes, direct dyes, salt-making dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, oxidation dyes, and natural dyes. Oil-soluble dyes or disperse dyes are preferred, and oil-soluble dyes are more preferred.

[0038] Examples of dye chemical structures include azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, and por Examples of dye structures derived from dyes selected from rimethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof include, but are not particularly limited to, these. Azomethine dyes, anthraquinone dyes, methine dyes, and perinone dyes are preferred, and azomethine dyes and anthraquinone dyes are more preferred.

[0039] Examples of azomethine-based dyes include CI Solvent Brown 53 and Solvent Yellow 93. Examples of anthraquinone-based dyes include CI Solvent Yellow 163, Solvent Red 52 and 151, Solvent Green 3 and 28, Solvent Violet 13 and 36, and Solvent Blue 97. Examples of methine-based dyes include CI Solvent Yellow 179. Examples of perinone-based dyes include CI Solvent Red 135 and 179.

[0040] From the viewpoint of resistance to migration and elution, the dye content in the resin composition layer is preferably 0.10% by mass or less.

[0041] (Pigment) Pigments include substances classified as pigments in the color index. These pigments can be inorganic or organic. Organic pigments are preferred because they offer both light-shielding and barrier properties in the laminate, as well as excellent resistance to migration and elution.

[0042] Examples of inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin gray, talc, bentonite, black iron oxide, carbon black, cadmium red, red iron oxide, molybdenum red, molybdate orange, chromium vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chromium green, Victoria green, ultramarine, dark blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, or cobalt violet.

[0043] Examples of the inorganic pigments mentioned above include CI Pigment White 6, Pigment Brown 24, Pigment Red 101, Pigment Blue 29, and Pigment Black 7.

[0044] Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo. Lake pigments, which are dyes that have been laked, can also be used. From the viewpoint of reducing aggregates in the resin composition and providing oxygen barrier properties, anthraquinone pigments, azo pigments, quinacridone pigments, and perylene pigments are preferred, with anthraquinone pigments being particularly preferred.

[0045] Examples of anthraquinone pigments include CI Pigment Yellow 147, Pigment Blue 60, and Pigment Red 177. Examples of azo pigments include CI Pigment Yellow 180, 181, Pigment Orange 64, Pigment Red 144, 166, 214, and 221. Examples of quinacridone pigments include CI Pigment Violet 19 and Pigment Red 122. Examples of perylene pigments include CI Pigment Red 149, 178, Pigment Black 31, and 32. Examples of diketopyrrolopyrrole pigments include CI Pigment Red 254. Examples of phthalocyanine pigments include CI Pigment Blue 15:1, 15:3, Pigment Green 7, and 36.

[0046] From the viewpoint of oxygen barrier properties, the content of organic pigment in the resin composition layer is preferably 2% by mass or less. Furthermore, from the viewpoint of light shielding properties, it is preferably 0.05% by mass or more.

[0047] [Thermoplastic resin] Thermoplastic resin is the main component of the resin composition layer and is selected appropriately according to the application of the laminate. One type of thermoplastic resin may be used alone, or two or more types may be used together.

[0048] There are no particular restrictions on the thermoplastic resin, and examples include polyester resin, polycarbonate resin, acrylic resin, polyamide resin, polyvinyl chloride resin, polystyrene resin, and cycloolefin resin. From the viewpoint of oxygen barrier properties, polyester resin, polycarbonate resin, and polyamide resin are preferred, and from the viewpoint of moldability, polyester resin is particularly preferred.

[0049] (Polyester resin) Polyester resins can be obtained by polymerizing a carboxylic acid component (a compound having a carboxyl group) and a hydroxyl group component (a compound having a hydroxyl group).

[0050] Examples of carboxylic acid components that make up polyester resins include benzoic acid, p-tert-butylbenzoic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, tetrehydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid, tetrachlorophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, methylcyclohexentricarboxylic acid anhydride, pyromellitic anhydride, and ε-caprolactone.

[0051] Examples of hydroxyl group components that make up polyester resins include diols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, 3-methylpentanediol, and 1,4-cyclohexanedimethanol, as well as polyfunctional alcohols having three or more hydroxyl groups, such as trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, pentaerythritol, and dipentaerythritol.

[0052] Polyester resins can also be obtained by polymerizing hydroxycarboxylic acids. Examples of hydroxycarboxylic acids include lactic acid, hydroxybutyric acid, and polycaprolactone.

[0053] Specific examples of polyester resins include polyethylene terephthalate resin (PET resin), polyethylene (terephthalate / isophthalate) resin (I-PET resin), glycol-modified polyethylene terephthalate resin (PET-G resin), polybutylene terephthalate resin (PBT resin), polycyclohexylene dimethylene terephthalate resin (PCT resin), polytrimethylene terephthalate resin (PTT resin), polyethylene naphthalate (PEN resin), polybutylene naphthalate resin (PBN resin), polybutylene adipate terephthalate resin (PBAT resin), polybutylene succinate resin (PBS resin), polyethylene adipate resin (PEA resin), polylactic acid resin (PLA resin), polyglycolic acid resin (PGA resin), and polyhydroxyalkanoate resin (PHA resin). Polyethylene terephthalate resin (PET resin) is preferred because it has excellent transparency and low transmittance of ultraviolet rays, which accelerate the degradation of organic compounds.

[0054] (Polycarbonate resin) Polycarbonate resins are produced by reacting aromatic dihydroxy compounds with carbonate precursors such as phosgene or diester carbonates. The reaction can be carried out using known methods, such as the interfacial method when using phosgene, or the transesterification method when using diester carbonates, which involves reacting the compounds in a molten state.

[0055] Examples of the above aromatic dihydroxy compounds include bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, as well as 1,1-bis(4-hydroxy( Examples include bis(hydroxyaryl)cycloalkanes such as cyphenyl)cyclopentane and 1,1-bis(4-hydroxyphenyl)cyclohexane, dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, and dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. These are used individually or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcinol, and 4,4'-dihydroxydiphenyl compounds may be used in combination. Furthermore, branched aromatic polycarbonate resins incorporating polyfunctional compounds such as phloroglucin can also be used.

[0056] Examples of carbonate precursors to be reacted with the aromatic dihydroxy compound include phosgene, diaryl carbonates such as diphenyl carbonate and ditril carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

[0057] (Polyamide resin) Polyamide resins can be obtained, for example, by reacting the carboxylic acid component described above with a compound having two or more amino groups. For example, they can be obtained by a dehydration condensation reaction between a carboxylic acid component and a compound (Am) having two or more amino groups.

[0058] As compounds (Am) having two or more amino groups, known compounds can be used, for example, aliphatic polyamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and triethylenetetramine; aliphatic polyamines including alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; and diamino alcohols such as 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexane-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecane-2-ol, and 3-(2-hydroxypropyl)-o-xylene-α,α'-diamine.

[0059] (Acrylic resin) Acrylic resins can be obtained by polymerizing (meth)acrylic monomers as exemplified below. Examples of monomers include (meth)acrylic monomers having alkyl groups, (meth)acrylic monomers having hydroxyl groups, (meth)acrylic monomers having carboxyl groups, (meth)acrylic monomers having glycidyl groups, vinyl esters such as vinyl acetate and vinyl propionate, maleic anhydride, vinyl ethers, and styrene. In this specification, "(meth)acrylic" means "acrylic and / or methacrylic," and "(meth)acrylate" means "acrylate and / or methacrylate." Specifically, polymethyl methacrylate (PMMA) resin is preferred.

[0060] The thermoplastic resin content is preferably 60 to 99.99% by mass, and more preferably 90% by mass or more, based on 100% by mass of the resin composition layer. If the thermoplastic resin content is 60% by mass or more, it is easier to maintain sufficient strength in the laminate.

[0061] In 100% by mass of the resin composition layer, the total content of colorant and thermoplastic resin is preferably 65 to 100% by mass, and more preferably 80 to 99.99% by mass.

[0062] [Dispersant] The resin composition layer may contain dispersants such as fatty acid amides, metal soaps, fatty acid esters, and fatty acids. Dispersants uniformly disperse the colorant in the thermoplastic resin, thereby suppressing the formation of aggregates in the resin composition layer and laminate, and further suppressing color unevenness. Fatty acid amides are preferred as dispersants in terms of heat resistance and oxygen barrier properties of the laminate. By using fatty acid amides, the pigment is dispersed more finely, and aggregates in the resin composition can be further reduced. In addition, because of their high heat resistance, thermal decomposition during the manufacture of the resin composition is suppressed, and the formation of aggregates due to decomposition products can be reduced.

[0063] From the viewpoint of suppressing color unevenness in the resin composition layer, the dispersant content is preferably 0.1 ppm or more, and more preferably 10 ppm or more, per 100% by mass of the resin composition layer. Furthermore, from the viewpoint of mechanical properties, it is preferably 10% by mass or less, and more preferably 1% by mass or less.

[0064] Furthermore, from the viewpoint of suppressing color unevenness, the amount of dispersant added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more, per 100 parts by mass of colorant. Furthermore, from the viewpoint of mechanical properties, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, per 100 parts by mass of colorant.

[0065] (Fatty acid amide) The resin composition layer preferably contains a fatty acid amide. The fatty acid amide has a structure in which one or more fatty acids are amide-bonded to an amine. The amine may be monovalent or polyvalent. The fatty acid is a monovalent carboxylic acid having a carboxyl group in the hydrocarbon chain, and the number of carbon atoms in the hydrocarbon chain is preferably 10 to 24, more preferably 16 to 20. Examples of fatty acid amides include saturated fatty acid monoamides, unsaturated fatty acid monoamides, saturated fatty acid bisamides, and unsaturated fatty acid bisamides. As fatty acid amides, unsaturated fatty acid monoamides and saturated fatty acid bisamides are preferred, and saturated fatty acid bisamides are more preferred. Examples of saturated fatty acid monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide. Examples of unsaturated fatty acid monoamides include oleic acid amide, erucic acid amide, and ricinoleic acid amide. Examples of saturated fatty acid bisamides include methylenebisstearamide, ethylenebiscaprate, ethylenebislaurate, ethylenebisstearamide, ethylenebisbehenamide, hexamethylenebisstearamide, and hexamethylenebisbehenamide, with ethylenebisstearamide being preferred. Examples of unsaturated fatty acid bisamides include ethylenebisoleamide and hexamethylenebisoleamide. Fatty acid amides may be used individually or in combination of two or more types.

[0066] The fatty acid amide content in the resin composition layer is set to 1 to 1 × 10 in order to balance color uniformity, barrier properties, and mechanical properties. 5 ppm, preferably 10 to 1 × 10 4 ppm, more preferably 100 to 1 × 10 3 The concentration is ppm. When the concentration is 1 ppm or higher, the dispersion of the colorant improves, thus suppressing color unevenness. In addition, the formation of aggregates in the resin composition layer is suppressed, so a diamond-like carbon layer is formed uniformly, and the barrier properties of the laminate are further improved. Also, the concentration is 1 × 10 5 When the value is below ppm, it is preferable because it can suppress the deterioration of the mechanical properties of the laminate and prevent leakage of contents due to breakage in applications such as containers.

[0067] The amount of fatty acid amide in the resin composition layer is preferably 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass, per 100 parts by mass of colorant. From the viewpoint of suppressing color unevenness, it is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of colorant. Furthermore, from the viewpoint of mechanical properties, it is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, per 100 parts by mass of colorant.

[0068] (Metallic soap) Metal soaps are metal salts of fatty acids. The fatty acids constituting metal soaps are monovalent carboxylic acids having a carboxyl group in the hydrocarbon chain, and the metals are divalent or trivalent metals and lithium. Examples of metal soaps include calcium stearate, magnesium stearate, barium stearate, zinc stearate, aluminum stearate, lithium stearate, calcium lauryl latate, magnesium lauryl latate, barium lauryl latate, zinc lauryl latate, aluminum lauryl latate, and lithium lauryl latate. From the viewpoint of suppressing color unevenness, magnesium stearate is preferred.

[0069] [Other ingredients] The resin composition layer may contain optional components other than thermoplastic resin, colorants, and dispersants. Examples include surfactants, antistatic agents, flame retardants, antioxidants, and UV absorbers.

[0070] [Method for manufacturing a resin composition layer] The resin composition layer is formed using a resin composition containing a thermoplastic resin and a colorant. The molding method is not particularly limited, and the molded article can be obtained by extrusion molding, compression molding, injection molding, blow molding, etc.

[0071] The form of the resin composition layer is not particularly limited and may be any shape such as a film, sheet, or container, depending on the application of the laminate. In other words, films, sheets, containers, etc. formed from the resin composition by an injection molding machine or a blow molding machine correspond to the resin composition layer of the present invention.

[0072] The thickness of the resin composition layer is, for example, 1 to 10,000 μm. Preferably, it is 10 to 3,000 μm, more preferably 100 to 1,000 μm, and even more preferably 200 to 600 μm. A thickness of 10 μm or more provides superior moldability and mechanical strength, while a thickness of 3,000 μm or less provides superior lightness.

[0073] The resin composition layer may be formed directly from a resin composition obtained by kneading a colorant with a thermoplastic resin at the melting temperature of the thermoplastic resin, or the resin composition layer may be formed from a resin composition obtained by first using a masterbatch containing a high concentration of colorant and then kneading it with a thermoplastic resin, which is a diluted resin, at a specified ratio during the molding of the molded article. The diluting resin in this case may be the same resin as the thermoplastic resin constituting the masterbatch or a different resin, but it is preferable that it be the same resin. It is preferable that the amount of masterbatch added is 1 to 20 parts by mass per 100 parts by mass of diluting resin, as this further suppresses color unevenness in the resin composition layer. It is also preferable that the oxygen barrier properties are improved because the colorant is uniformly and finely dispersed, suppressing the formation of aggregates.

[0074] The thermoplastic resin content in 100% by mass of the masterbatch is preferably 20% by mass or more, and more preferably 30-60% by mass. A thermoplastic resin content of 20% by mass or more results in better processability during masterbatch production. A thermoplastic resin content of 40% by mass or more is more preferable, and is also preferably 80% by mass or less. Furthermore, the colorant content is preferably 0.1 to 50% by mass, and more preferably 1 to 10% by mass, of 100% by mass of the masterbatch. When the colorant content is 50% by mass or less, color unevenness in the resin composition layer is further suppressed.

[0075] The resin composition used to form the resin composition layer is preferably such that when a 300 μm thick sheet is formed and 10 locations in a 500 μm × 500 μm area are observed with a 100x magnification optical microscope, the average number of aggregates with a major axis of 20 μm or more is 10 or less. More preferably, the average number of aggregates is 5 or less, and even more preferably 1 or less. The maximum major axis of the aggregates is preferably 50 μm or less, and more preferably 30 μm or less. If the number of aggregates in a 300 μm thick sheet is within this range, it is preferable because it allows for both oxygen barrier properties and light shielding properties when the material is laminated.

[0076] Furthermore, the haze of the sheet is preferably 25% or less. When the haze is 25% or less, the oxygen barrier properties and design are excellent. The haze is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less. The measurement procedures and methods for aggregates and haze are the same as those for measuring aggregates in laminates. Further details can be obtained by the method described in the examples.

[0077] <Diamond-like carbon layer> The diamond-like carbon layer is an amorphous (amorphous) hard film made of hydrocarbons and allotropes of carbon, which imparts oxygen barrier properties to the laminate. A diamond-like carbon layer can be obtained by coating a resin composition layer with diamond-like carbon by vapor deposition or the like. When forming the diamond-like carbon layer, methods such as chemical vapor deposition (CVD) and physical vapor deposition (PVD) can be used. Examples of chemical vapor deposition include plasma CVD and thermal CVD. Examples of power sources used in plasma CVD include high frequency and microwave. For forming the diamond-like carbon layer, plasma CVD using high frequency as the power source is preferred.

[0078] When the laminate is a container, the diamond-like carbon layer can be manufactured, for example, according to the method described in Japanese Patent Application Publication No. 8-053116. That is, an external electrode having a cavity slightly larger than the outer shape of the container is prepared, the container is placed in this cavity, an internal electrode is inserted into the inside of the container, a raw material gas is supplied to the inside of the container, and a high frequency is applied to the external electrode to generate plasma, thereby forming a diamond-like carbon layer on the inner wall surface of the container by CVD.

[0079] For example, acetylene (C2H2), toluene, xylene, etc., can be used as raw materials for the diamond-like carbon layer, with acetylene being preferred. The elemental ratio of carbon to hydrogen in the diamond-like carbon layer is preferably 5 / 5 to 9 / 1.

[0080] The thickness of the diamond-like carbon layer is, for example, 1 nm to 200 nm. Preferably, it is 5 nm to 100 nm, and more preferably 10 nm to 50 nm. A thickness of 5 nm or more provides excellent barrier properties. When the thickness is 100 nm or less, degradation of the resin composition layer can be suppressed. [Examples]

[0081] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass," respectively, and "RH" means relative humidity. Furthermore, the amounts listed in the table are in parts by mass, and blank spaces indicate that the ingredient was not included.

[0082] The materials used in the examples and comparative examples are listed below. <Thermoplastic resin> A-1: Polyester MA-2101M (Polyester resin (PET), manufactured by Unitika Corporation)

[0083] <Colorants> B-1: Pigment Yellow 147 (Anthraquinone-based pigment) B-2: Solvent Green 28 (Anthraquinone-based dye) B-3: Solvent Brown 53 (Azomethine-based dye) B-4: Solvent Yellow 93 (Azomethine-based dye) B-5: Pigment Green 7 (Phthalocyanine Pigment) B-6: #45L (Mitsubishi Chemical Corporation, Pigment Black 7, Carbon Black)

[0084] <Dispersant> C-1: Alflow H-50TF (manufactured by NOF Corporation, fatty acid amide, ethylenebisstearic acid amide) C-2: Shinakared SAK-MS-P (manufactured by Sunace Co., Ltd., metal soap, magnesium stearate)

[0085] <Solubility of colorants> The solubility of the colorants was evaluated using the following method. Solubility 1 is an indicator of the affinity of the colorant to the resin; higher solubility indicates higher affinity to the resin. Solubility 2 is an indicator of the dissolution of the colorant into the contents of the container; lower solubility indicates lower dissolution into the contents. "Solubility Evaluation 1" 0.1 parts by mass of colorant was added to 99.9 parts by mass of bis(2-ethylhexyl) phthalate, mixed at 250°C for 10 minutes, and then allowed to stand for 10 minutes. If no particles could be visually observed, it was determined that the mixture had dissolved. [Evaluation Criteria] A: It dissolved. B: It did not dissolve.

[0086] "Solubility Evaluation 2" 0.01 parts by mass of colorant was added to 99.99 parts by mass of bis(2-ethylhexyl) phthalate, mixed at 25°C for 10 minutes, and then allowed to stand for 10 minutes before visual confirmation of dissolution. [Evaluation Criteria] A: It did not dissolve. B: It dissolved.

[0087] [Table 1]

[0088] [Example 1] 97 parts of thermoplastic resin (A-1) "Polyester MA-2101M", 2 parts of colorant (B-1) "Pigment Yellow 147", 0.7 parts of colorant (B-2) "Solvent Green 28", and 0.3 parts of dispersant (C-1) "Alflow H-50TF" were mixed and extruded at 280°C using a twin-screw extruder (manufactured by Japan Steel Works Co., Ltd.) to granulate and obtain a pellet-shaped masterbatch. Next, 10 parts of the obtained masterbatch and 90 parts of the thermoplastic resin (A-1) "Polyester MA-2101M" were melt-kneaded to obtain a resin composition. A resin composition was injected using an injection molding machine to produce preforms with a mass of 30 g each. Next, the preforms were heated to 110°C and biaxial stretch blow molded in a blow molding die to produce cylindrical bottles with a capacity of 500 mL, a body diameter of φ65 mm, and a height of 205 mm. The thickness of the bottle body at the center (near the midpoint between the shoulder and the bottom) was 300 μm. Next, following the method described in Japanese Patent Publication No. 8-053116, a diamond-like carbon (DLC) layer was formed inside the bottle (resin composition layer) by plasma deposition for 10 seconds using acetylene as the raw material gas and a high-frequency power supply of 1000W, thereby obtaining a DLC-coated bottle. The thickness of the diamond-like carbon layer was 30 nm at the center of the DLC-coated bottle body. The thickness of the diamond-like carbon layer was measured using the alpha-step500 stylus step meter (manufactured by Tenchol). A 20mm square section was cut from the center of the body of a DLC-coated bottle, and the resulting laminate 1 was used as a test specimen for the following evaluations.

[0089] [Examples 2-12, Comparative Examples 1-3] DLC coated bottles were manufactured in the same manner as in Example 1, except that the composition of the masterbatch was changed so that the content of thermoplastic resin, colorant, and dispersant in the resin composition layer was as shown in Table 2, and laminates 2-12 and 17-20 were obtained.

[0090] [Example 13] 99.7 parts of polyester MA-2101M (A-1), 0.2 parts of pigment yellow 147 (B-1), 0.07 parts of solvent green 28 (B-2), and 0.03 parts of Alflow H-50TF (C-1) were mixed and extruded at 280°C using a twin-screw extruder to granulate and obtain a pelletized resin composition. Next, the obtained resin composition was melted, and the molten material was injected using an injection molding machine to produce a preform. DLC coated bottles were then manufactured in the same manner as in Example 1, and a laminate 13 was obtained.

[0091] [Example 14] DLC-coated bottles were manufactured in the same manner as in Example 1, except that the mass per preform was changed to 60g, to obtain laminate 15. The thickness at the center of the bottle body (near the midpoint between the shoulder and bottom) was 600 μm.

[0092] [Example 15] A DLC-coated bottle was manufactured in the same manner as in Example 2, except that the plasma deposition time was changed to 20 seconds, to obtain a laminate 16. The thickness of the diamond-like carbon layer was 60 nm at the center of the body of the DLC-coated bottle.

[0093] Measurement and evaluation of the physical properties of laminates. The physical properties of the laminate of the present invention were measured and evaluated using the following method. The results are shown in Tables 2 and 3.

[0094] <Measurement of the number of aggregates in the resin composition layer> Using a resin composition, a 300 μm thick sheet (resin composition layer) was fabricated at a temperature of 280°C using a film molding machine, and the number of aggregates was measured. The number of aggregates was calculated by observing 10 locations in a 500 μm × 500 μm area of ​​the sheet using transmitted light with an optical microscope "Digital Microscope VHX-100" (manufactured by Keyence Corporation) at a magnification of 100x, counting the number of aggregates with a major axis of 20 μm or more, and calculating the average number.

[0095] <Haze measurement of resin composition layer> A 300 μm thick sheet (resin composition layer) was fabricated using a resin composition at a temperature of 280°C in a film molding machine, and the haze was measured. The haze was measured in accordance with JIS K7136:2000 using a haze meter "HazeGuard Plus" (Gardner Corporation), with the diamond-like carbon layer side of the test specimen facing the light source.

[0096] <Measurement of the number of aggregates> The laminate was observed at 100x magnification using an optical microscope, "Digital Microscope VHX-100" (manufactured by Keyence Corporation), at 100x magnification, in a 500 μm x 500 μm area from the resin composition layer side using transmitted light. The number of aggregates with a major axis of 20 μm or larger was counted, and the average number was calculated.

[0097] The reason for measuring the number of aggregates in the laminated section cut from the center of the bottle body is that the resin composition layer and diamond-like carbon layer are relatively thin in the body, and the area it occupies on the container surface is large, thus having a significant impact on the overall barrier properties of the container. Furthermore, since the film thickness is most stable in the center of the body, the overall barrier properties of the container can be judged by evaluating the number of aggregates in the laminated section of the center of the body.

[0098] <Hayes> In accordance with JIS K7136:2000, the haze of the laminate was measured using a haze meter "HazeGuard Plus" (Gardner Corporation). The measurement was performed with the diamond-like carbon layer side of the test specimen facing the light source.

[0099] <Oxygen barrier properties> Using the obtained DLC-coated bottles, oxygen permeability was measured at 22°C and 60% RH using the "Oxtran" oxygen permeability analyzer (manufactured by MOCON), and the oxygen barrier properties were evaluated according to the following criteria. Lower oxygen permeability indicates superior oxygen barrier properties. [Evaluation Criteria] +++ (Excellent): 0.003ml / day / container or less ++ (Good): Exceeds 0.003 ml / day / container and is 0.005 ml / day / container or less. +(Usable): Exceeding 0.005 ml / day / container and less than or equal to 0.01 ml / day / container NG (Defective): Exceeds 0.01 ml / day / container

[0100] <Light blocking property> Using the obtained laminate, the transmittance was measured at 1 nm intervals in the wavelength range of 350 nm to 450 nm using a UV-3150 ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation), and the average value was calculated. The diamond-like carbon layer side of the test specimen was pointed towards the light source for the measurement. A lower transmittance indicates better light shielding performance. [Evaluation Criteria] ++ (Good): Transmittance of 10% or less +(Practical): Transmittance exceeds 10% and is 30% or less. NG (Defective): Transmittance exceeds 30%

[0101] <Dissolution> Ten of the resulting laminates were cut into 10 mm squares and immersed in 30 mL of 99.5% pure ethanol, then left standing in a 50°C water bath for 7 days. The absorption spectrum of the ethanol after removing the test pieces was measured using a UV-3150 ultraviolet-visible-near-infrared spectrophotometer (Shimadzu Corporation), and the absorbance ε in the 380-770 nm range was evaluated according to the following criteria. A smaller absorbance ε indicates suppressed elution into the contents and superior storage stability. [Evaluation Criteria] +++(Excellent):ε≦0.01 ++ (Good): 0.01 < ε ≤ 0.02 +(Practical): 0.02 < ε ≤ 0.03 NG (defective): 0.03<ε

[0102] <Uneven coloring> One test piece was prepared from each of the 10 DLC-coated bottles obtained, and its color was measured using a SpectroColorMeterSE2000 colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd.) in the CIE1976 L*a*b* color system. The standard deviation of L* and visual inspection were evaluated according to the following criteria. A smaller standard deviation of L* and less color unevenness indicate superior design quality. [Evaluation Criteria] ++(Good): The standard deviation of L* is 0.5 or less, and there is no color unevenness between plates. +(Practical): The standard deviation of L* is greater than 0.5 and less than or equal to 0.6, and there is no color unevenness between each plate. NG (Defective): The standard deviation of L* is greater than 0.6 and less than or equal to 0.7, and there is color unevenness in each plate.

[0103] <Strength> The obtained DLC-coated bottles were filled with water, sealed tightly, and dropped from a height of 3 meters onto a concrete floor so that the bottom surface made contact with the surface. The results were then evaluated according to the following criteria. [Evaluation Criteria] ++(Good): No cracks or breaks, and no leakage of contents. +(Usable): No leakage of contents is observed, but cracks or breaks have occurred. NG (Defective): Cracks, breaks, and leakage of contents were observed.

[0104] [Table 2]

[0105] [Table 3]

[0106] As shown in Tables 2 and 3, the laminate of the present invention exhibited low oxygen permeability, light transmittance, and elution resistance, as well as excellent oxygen barrier properties, light shielding properties, and elution resistance, and superior protection of its contents. Furthermore, it showed suppressed color unevenness and excellent mechanical strength and appearance.

[0107] In particular, the oxygen barrier properties were especially excellent when the number of aggregates in the laminate was one or less. Furthermore, the oxygen barrier properties were superior when the haze of the laminate was 10% or less. Furthermore, when the amount of colorant was 0.10 parts by mass or more per 100 parts by mass of the resin composition, the light-shielding properties were superior. Using dispersants such as fatty acid amides or metal soaps resulted in excellent suppression of color unevenness. In particular, the use of fatty acid amides demonstrated superior oxygen barrier properties. Furthermore, the use of a masterbatch resulted in particularly excellent oxygen barrier properties.

Claims

1. A resin composition layer containing a colorant and a thermoplastic resin, It has a diamond-like carbon layer, A laminate characterized in that, when observing 10 locations of a 500 μm × 500 μm area at 100x magnification with an optical microscope, the average number of aggregates with a major axis of 20 μm or more is 10 or less.

2. The laminate according to claim 1, characterized in that the haze is 30% or less.

3. The laminate according to claim 1, characterized in that the thermoplastic resin contains a polyester resin.

4. The laminate according to claim 1, characterized in that the resin composition layer contains a fatty acid amide.

5. A container comprising at least a portion of the laminate described in claim 1.

6. A resin composition used to form the resin composition layer in a laminate having a resin composition layer and a diamond-like carbon layer, The aforementioned resin composition contains a colorant and a thermoplastic resin, A resin composition characterized in that, when a 300 μm thick sheet formed using the above resin composition is observed with an optical microscope at a magnification of 100x in 10 locations of a 500 μm x 500 μm area, the average number of aggregates with a major axis of 20 μm or more is 10 or less.

7. A method for manufacturing a laminate according to any one of claims 1 to 4, A step of forming a resin composition layer from a resin composition containing a colorant and a thermoplastic resin, The process includes a step of depositing diamond-like carbon onto the resin composition layer to form a diamond-like carbon layer. A method for manufacturing laminates.

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