Flame retardant decorative laminates and decorative articles comprising laminates

Abstract

Provided are an environmentally friendly decorative laminate having excellent flame retardancy and a decorative article including the same. A flame retardant decorative laminate includes a substrate, a colored layer, and an adhesive layer. The colored layer contains a biomass-derived extender pigment and contains about 15 mass% or more of at least one selected from the group consisting of a phosphorus-based flame retardant and a boron-based flame retardant.

Description

Technical Field

[0001] This disclosure relates to flame-retardant decorative laminates and decorative articles including such laminates. Background Technology

[0002] Decorative sheets with properties such as flame retardancy have been developed and used in various fields. Such known decorative sheets are used in a wide range of applications, such as interior or exterior products.

[0003] Patent document 1 (JP 2015-182379 A) describes a decorative sheet in which a base sheet, a transparent resin layer and a surface protective layer are laminated in sequence, wherein (1) the base sheet contains a resin component and a flame retardant, (2) the flame retardant content is 10 parts by mass to 100 parts by mass relative to 100 parts by mass of the resin component, (3) the thickness of the base sheet is 15µm to 150µm, (4) the thickness of the transparent resin layer is 15µm to 150µm, and (5) the total thickness of the base sheet, the transparent resin layer and the surface protective layer is 40µm to 200µm.

[0004] Patent document 2 (JP 2017-177527 A) describes a decorative sheet comprising a base film having thermal foaming properties and an adhesive layer disposed on at least one side of the base film, wherein, in the heat release test described below, a laminate comprising a gypsum board and a decorative sheet laminated to the side of the gypsum board to which radiant heat is applied is used as a specimen, and the specimen exhibits a heat release of 7.2 MJ / m² over a test period of 20 minutes. 2 Or a lower total calorific value: Heat release test: Heat release test according to ISO 5660-1:2002 cone calorimetry, where the radiant heat applied to the specimen surface is 50 kW / m². 2 The total calorific value was measured under the following conditions.

[0005] It is known, for example, as described in the background art of Patent Document 3 (JP 2021-044191 A), that inorganic materials such as calcium carbonate can have properties as flame retardants.

[0006] List of cited references

[0007] Patent documents

[0008] Patent document 1: JP 2015-182379 A

[0009] Patent document 2: JP 2017-177527 A

[0010] Patent document 3: JP 2021-044191 A Summary of the Invention

[0011] Technical issues

[0012] In recent years, in the context of environmental issues, materials that take environmental concerns into account have been used to construct decorative laminates. As described in Patent Document 3, since inorganic materials such as calcium carbonate also have properties as flame retardants, it has been anticipated that, considering environmental concerns, flame-retardant decorative laminates could be obtained by using biomass-derived extender pigments as pigments to be blended into the coloring layer of the decorative laminate. However, using biomass-derived extender pigments makes it difficult to achieve the flame retardancy required in decorative laminates in recent years.

[0013] This disclosure provides an environmentally friendly decorative laminate with excellent flame retardancy and a decorative article including the laminate.

[0014] Solution to the problem

[0015] According to embodiments of this disclosure, a flame-retardant decorative laminate is provided, comprising a substrate, a coloring layer, and an adhesive layer, wherein...

[0016] The coloring layer contains biomass-derived endogenous pigments and contains about 15% by mass or more of at least one selected from the group consisting of phosphorus-based flame retardants and boron-based flame retardants.

[0017] According to another embodiment of this disclosure, a decorative article is provided, which includes a support member and a decorative laminate bonded to the support member.

[0018] Beneficial effects of the invention

[0019] According to this disclosure, an environmentally friendly decorative laminate with excellent flame retardancy can be provided, as well as a decorative article including the laminate.

[0020] The above description should not be construed as disclosing all embodiments of the invention or all advantages associated with the invention. Detailed Implementation

[0021] In the following text, this disclosure will be described in more detail for the purpose of illustrating representative embodiments according to this disclosure, but this disclosure is not limited to these embodiments.

[0022] In this disclosure, for example, the term "on" as used in "the coloring layer is disposed on the adhesive layer" means that the coloring layer is disposed directly on the upper side of the adhesive layer, or that the coloring layer is disposed indirectly on the upper side of the adhesive layer via another layer.

[0023] In this disclosure, for example, the term "under" as used in "the coloring layer is disposed under the substrate" means that the coloring layer is disposed directly under the substrate or indirectly under the substrate via another layer.

[0024] In this disclosure, "transparent" means an average transmittance of about 80% or more, as measured according to JIS K 7375, in the visible light region (wavelength from 400 nm to 700 nm), and ideally, this average transmittance may be about 85% or more, or about 90% or more. There is no particular upper limit to the average transmittance, and it may be, for example, about less than 100%, about 99% or less, or about 98% or less.

[0025] In this disclosure, "semi-transparent" means that the average transmittance in the visible light region (wavelength from 400 nm to 700 nm) is less than 80% as measured according to JIS K7375, and the average transmittance is ideally about 75% or less, and "semi-transparent" is intended to mean that the underlying layer is not completely hidden.

[0026] In this disclosure, the term "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and the term "(meth)acrylate" refers to acrylate or methacrylate.

[0027] In this disclosure, the term "film" may cover articles referred to as "sheets".

[0028] In the following sections, details of each component will be described in order to illustrate representative embodiments of the flame-retardant decorative laminate of this disclosure.

[0029] The flame-retardant decorative laminate disclosed herein (which may be simply referred to as a "laminate" or "decorative laminate") comprises a substrate, a coloring layer, and an adhesive layer, wherein the coloring layer contains an extender pigment derived from biomass and contains about 15% by mass or more of at least one selected from the group consisting of phosphorus-based flame retardants and boron-based flame retardants.

[0030] The inventors of this invention have discovered that when a specific flame retardant is blended, i.e., when a flame retardant selected from the group consisting of phosphorus-based and boron-based flame retardants is blended in an amount of about 15% by mass or more relative to the coloring layer, an environmentally friendly decorative laminate with good flame retardancy can be obtained.

[0031] The flame retardancy of laminates can be assessed, for example, by heat release testing according to the cone calorimetry method of ISO 5660-1:2002, where the total calorific value (THR) is 50 kW / m² of radiant heat applied to the surface of the specimen. 2Measurements were taken under the following conditions. Here, as the specimen used in the test, a laminate comprising a gypsum board and a decorative laminate laminated on the side of the gypsum board to which radiant heat was applied was used. In some embodiments, the flame-retardant decorative laminate of this disclosure can provide such a specimen with approximately 8.0 MJ / m² during a 20-minute test time. 2 Or smaller, less than about 8.0 MJ / m 2 Approximately 7.9 MJ / m 2 Or smaller, approximately 7.8 MJ / m 2 Or smaller, approximately 7.7 MJ / m 2 Or smaller, approximately 7.6 MJ / m 2 Or smaller or about 7.5 MJ / m 2 Or a lower total calorific value. The lower limit of the total calorific value is not particularly limited, and it can be, for example, about 4.0 MJ / m³. 2 Or larger, approximately 4.5 MJ / m 2 Or larger, approximately 5.0 MJ / m 2 Or larger, approximately 5.5 MJ / m 2 Or larger or about 6.0 MJ / m 2 Or larger.

[0032] In some embodiments, the flame-retardant decorative laminate of this disclosure can have approximately 240 kW / m³. 2 Or smaller, approximately 220kW / m 2 Or smaller, approximately 200kW / m 2 Or smaller, approximately 190kW / m 2 Or smaller or about 180kW / m 2 Or a smaller maximum heat release rate (sometimes simply referred to as "PHRR"), as determined by the heat release test described later. The lower limit of the maximum heat release rate is not particularly limited, and it can be, for example, about 100 kW / m³. 2 Or larger, approximately 110kW / m 2 Or larger or approximately 120kW / m 2 Or larger.

[0033] In some embodiments, the flame-retardant decorative laminate of this disclosure may have a heat release rate of more than 200 kW / m² relative to a heat release rate of less than about 10.0 seconds, about 9.0 seconds or less, about 7.0 seconds or less, about 5.0 seconds or less, about 3.0 seconds or less, or about 1.0 seconds or less, as determined by the heat release test described later. 2 The time. There is no particular restriction on the lower limit of such time, but it can be, for example, about 0 seconds or longer or more than about 0 seconds.

[0034] From a flame-retardant point of view, the thickness of the flame-retardant decorative laminate of this disclosure is preferably, for example, about 200 micrometers or less, about 190 micrometers or less, about 180 micrometers or less, about 175 micrometers or less, or about 170 micrometers or less. The lower limit of the thickness is not particularly limited, and it can be, for example, about 100 micrometers or more, about 110 micrometers or more, or about 120 micrometers or more. Here, the thickness of the laminate refers to the thickness of the laminate in its state when applied to an adhesive, and, for example, when a release liner is applied to the laminate, the thickness of the laminate does not include the liner.

[0035] The substrate disclosed herein can be used as a component to support coloring layers, adhesive layers, and any layer (e.g., surface layer) constituting a decorative layered assembly.

[0036] The substrate is not particularly limited, and for example, a substrate containing at least one selected from the group consisting of polyester resins (e.g., polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin), vinyl chloride resin, resins having urethane bonds, polyolefin resins, polycarbonate resins, (meth)acrylate resins, cellulose resins, polylactic acid resins, and fluoropolymers can be used. Herein, in this disclosure, the term "resin having urethane bonds" can include, for example, resins prepared using at least one selected from urethane (meth)acrylate and urethane (meth)acrylate oligomers, in addition to urethane resins, and urethane resins can also include (meth)acrylate urethane resins, etc.

[0037] Polyester resin is preferred, and polyethylene terephthalate resin (which may be simply referred to as "PET resin") is more preferred. A substrate containing such a resin can contribute to improvements in properties such as the strength of the decorative laminate (e.g., flexibility and breakage resistance). On the other hand, PET resin (particularly recycled PET resin described below) is a more flammable resin than vinyl chloride resin used as a material constituting the substrate of known decorative laminates. Therefore, it is generally difficult to impart flame retardancy to decorative laminates comprising a substrate containing PET resin. The decorative laminate of this disclosure includes a coloring layer containing an extender pigment derived from biomass and containing about 15% by mass or more of at least one selected from the group consisting of phosphorus-based flame retardants and boron-based flame retardants. Therefore, even when PET resin is used as the substrate material, the decorative laminate can exhibit excellent flame retardancy.

[0038] The substrate disclosed herein may contain PET resin in an amount of about 50% or more, about 70% or more, or about 90% or more of the total amount of resin components relative to the substrate, or all resin components of the substrate may be PET resin.

[0039] It allows the substrate surface to undergo surface treatments such as corona treatment, plasma treatment, or primer treatment.

[0040] The thickness of the substrate is not particularly limited, but is preferably about 10 micrometers or more, about 20 micrometers or more, about 30 micrometers or more, or about 40 micrometers or more, for example, from the viewpoint of strength, workability, etc., of the decorative laminate. The upper limit of the thickness is not particularly limited, but is preferably about 180 micrometers or less, about 150 micrometers or less, about 100 micrometers or less, about 80 micrometers or less, or about 60 micrometers or less, for example, from the viewpoint of flame retardancy. The thickness of a corresponding layer in the flame-retardant decorative laminate of this disclosure can be defined, for example, as the average of the thickness measured at at least any five points on the substrate using a thickness gauge (PC-465N manufactured by TECLOCK Co., Ltd., Japan). In cases where the layers constituting the laminate are thin and it is difficult to measure the thickness with a thickness gauge, a scanning electron microscope can be used to measure the cross-section in the thickness direction of the laminate configuration, and the thickness can be defined as the average of the thickness at at least any five points in the target layer (e.g., surface layer) of the laminate configuration.

[0041] In some embodiments, the substrate of this disclosure includes recycled PET resin as the PET resin. The inclusion of recycled PET resin in the substrate of this disclosure can further contribute to providing environmentally friendly decorative laminates.

[0042] The substrate disclosed herein may contain a quantity of recycled PET resin of about 10% or more, about 30% or more, about 50% or more, about 70% or more, or about 90% or more, relative to the total amount of PET resin components in the substrate, or all PET resin components may be recycled PET resin. The proportion of recycled PET resin components contained in the recycled PET resin relative to the total amount of PET resin components constituting the recycled PET resin may be about 50% or more, about 70% or more, or about 90% or more, and about 100% or less, or less than about 100% by mass. As used herein, the term "recycled PET resin" means a PET resin containing recycled PET resin components and may be mechanically recycled PET resin or chemically recycled PET resin. The term "mechanically recycled PET resin" refers to PET resin obtained by subjecting recycled products from used molded products and waste to fractionation, crushing, washing, molten filtration, extraction with organic solvents, vacuum heat treatment, etc., and the term "chemically recycled PET" refers to PET resin regenerated through further depolymerization, etc.

[0043] The difference between recycled PET resin and virgin PET resin can be assessed using, for example, differential scanning calorimetry (DSC). Recycled PET resin contains impurities compared to virgin PET resin, or, depending on the type of molded article made from the recycled PET resin, contains copolymer components (e.g., isophthalic acid), and therefore typically has a lower melting point compared to virgin PET resin. Recycled PET resin has, for example, a melting point (peak) of about 250°C ± about 5°C calculated by DSC from a second heating profile, which is about 2°C to about 3°C ​​lower than the melting point of virgin PET resin calculated in the same manner.

[0044] As recycled PET resin, recycled raw materials from PET bottles can be used. Such recycled raw materials are polyesters produced and molded through typical polymerization and solid-state polymerization methods, and preferably consist mainly of polyethylene terephthalate, and may contain other polyester components and copolymer components. The recycled raw materials may contain metal compounds (such as antimony, germanium, or titanium) as catalysts, phosphorus compounds as stabilizers, etc. Since germanium is commonly used as a catalyst in polyesters for PET bottles, the substrate prepared using recycled PET bottle materials may contain germanium in amounts of about 1 ppm or more, or about 3 ppm or more, and about 100 ppm or less, or about 50 ppm or less relative to the total amount in the substrate. Therefore, the use of recycled PET resin can be evaluated by examining the amount of germanium in the substrate. Here, the germanium content in the substrate can be measured by the following analytical methods: (Analytical methods for germanium) A 2g sample was ashed in a platinum crucible, 5ml of 10% sodium bicarbonate solution was added and evaporated, followed by the addition of hydrochloric acid and evaporation to dryness. The temperature was increased from 400°C to 950°C in an electric furnace, and the material was left to melt for 30 minutes. The obtained material was dissolved in 10ml of water by heating and transferred to a germanium distillation apparatus (washed with 7.5ml x 2). 35ml of hydrochloric acid was added and distillation was performed, collecting 25ml of distillate. A suitable amount was taken from the distillate and hydrochloric acid was added to bring the final concentration to 1mol / L to 1.5mol / L. 2.5ml of 0.25% polyvinyl alcohol solution, 2.5ml of 1% hexadecyltrimethylammonium chloride solution, and 5ml of 0.04% phenylfluorescein (2,3,7-trihydroxy-9-phenyl-6-fluorescein) solution were added, and water was brought to a final volume of 25ml. It forms a yellow complex with germanium, and the absorption at 505 nm is measured using a spectrophotometer (UV-150-02 manufactured by Shimadzu Corporation) for colorimetric analysis.

[0045] Typically, during the production stage of recycled raw materials, the recycled raw materials for PET bottles can be subjected to alkaline washing using sodium hydroxide and / or potassium hydroxide solutions. As a result, the recycled raw materials may contain amounts of sodium and / or potassium greater than 0 ppm, about 3 ppm or more, or about 5 ppm or more, about 150 ppm or less, about 120 ppm or less, or about 80 ppm or less. Therefore, the intended use of the recycled PET resin can also be evaluated by examining the amount of sodium and / or potassium in the substrate. The amount of sodium and / or potassium in the substrate can be measured using the following analytical methods: (Analytical methods for sodium and potassium) The substrate was molded into a disk shape with a thickness of approximately 5 mm on a smooth metal plate, and the smooth surface was measured using a fluorescence X-ray analyzer. Calibration curves were prepared using standard samples whose concentrations had been previously confirmed by emission plasma analysis.

[0046] The substrate disclosed herein may contain fillers, reinforcing materials, antioxidants, UV absorbers, flame retardants, light stabilizers, heat stabilizers, dispersants, plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, catalysts, pigments, and dyes as optional components, the range of which does not negatively affect the effectiveness of this disclosure. These optional components may be used alone or in combination of two or more types. The individual and total amounts of the optional components can be determined without impairing the desired characteristics of the substrate.

[0047] In some embodiments, the amount of flame retardant in the substrate of this disclosure is about 10% by mass or less, about 5% by mass or less, about 3% by mass or less, about 1% by mass or less, or about 0.5% by mass or less, or the substrate of this disclosure contains no flame retardant. Because substrates containing or not containing flame retardant at such ratios exhibit excellent transparency, it is possible to mitigate or suppress the deterioration of decorative properties caused by coloring layers disposed on or under the substrate. Since the decorative laminate of this disclosure comprises an extender pigment derived from biomass and a coloring layer containing about 15% by mass or more of at least one selected from the group consisting of phosphorus-based and boron-based flame retardants, the decorative laminate can exhibit excellent flame retardancy even when the amount of flame retardant in the substrate is low or the substrate contains no flame retardant.

[0048] The coloring layer disclosed herein contains biomass-derived extender pigments and contains about 15% by mass or more of at least one selected from the group consisting of phosphorus-based flame retardants and boron-based flame retardants. The coloring layer can be a colored layer, and can be transparent or translucent, or opaque, i.e., it can have concealing properties. The coloring layer can be, for example, a light-colored (such as white or yellow) or dark-colored (such as red, brown, green, blue, gray, or black) layer. The coloring layer can be applied locally to the decorative laminate, but from a flame-retardant point of view, it is preferable to apply it to the entire surface of the decorative laminate. The decorative layer can have a monolayer structure or a layered structure. The coloring layer can be applied directly or indirectly to one or both surfaces of the substrate described above.

[0049] The coloring layer can be applied directly or indirectly to one or both surfaces of the substrate described above. The method of application to the substrate is not particularly limited, and known methods such as blade coating, bar coating, scalpel coating, powder knife coating, roller coating, and casting coating can be used.

[0050] In this disclosure, the term "biomass-derived body pigment" refers to a body pigment produced using biomass intended as a renewable resource from animals and plants as a raw material. Such a biomass-derived body pigment can be a body pigment prepared using biomass-derived raw materials as all of its raw materials, or it can be a body pigment prepared using biomass-derived raw materials as at least a portion of its raw materials. That is, when biomass-derived raw materials are used as at least a portion of the raw materials for the body pigment, the body pigment may contain about 50% or more, about 70% or more, or about 90% or more and less than about 100% or about 95% or less of biomass components relative to the total amount of components constituting the body pigment. Biomass-derived body pigments can be used alone or in combination of two or more types.

[0051] Biomass as a raw material is not particularly limited, and for example, scallop and oyster shells, eggshells, wood materials, etc., can be used. From the viewpoint of flame retardancy, biomass-derived extender pigments preferably contain biomass-derived inorganic extender pigments (e.g., calcium carbonate, silica, and calcium oxide), and more preferably contain biomass-derived calcium carbonate. Such extender pigments, for example, products such as scallop powder, oyster shell nanopowder, and pearl powder, are commercially available. In some embodiments, from a processability viewpoint, biomass-derived inorganic extender pigments are preferably unbaked inorganic extender pigments, and more preferably unbaked calcium carbonate. Here, the term "unbaked" means that the biomass pigment was not baked at the time of obtaining the biomass pigment. Since unbaked extender pigments do not undergo a baking step, they can contribute to cost and environmental impact reduction.

[0052] The content of inorganic body pigments derived from biomass (e.g., calcium carbonate) may be about 50% or more by mass, about 70% or more by mass, or about 90% or more by mass, and about 100% or less by mass or less than about 100% by mass, relative to the total amount of biomass-derived body pigments.

[0053] In some embodiments, from a decorative point of view, the average particle size D50 of the biomass-derived extender pigment can be about 100 micrometers or less, preferably about 60 micrometers or less, and more preferably about 40 micrometers or less. The particle size (D50) of the extender pigment can be measured using a Microtrac MT 3300 EX II series laser diffraction scattering particle size distribution analyzer, available from MicrotracBel, under measurement conditions according to JIS Z 8825:2013.

[0054] Because biomass-derived endogenous pigments contain a greater amount of impurities than virgin endogenous pigments, the differences can be assessed, for example, using thermogravimetric analysis (TG measurement) with a thermal analyzer (TG8120, manufactured by Rigaku Corporation, Akishima City, Tokyo, Japan). TG measurements were performed by placing approximately 10 mg of sample into an aluminum dish at a heating rate of 20 °C / min and a maximum temperature of 500 °C. The mass reduction of virgin endogenous pigments was very small, but the mass reduction of biomass-derived endogenous pigments was only a few percent. Furthermore, because biomass-derived endogenous pigments contain a greater amount of impurities than virgin endogenous pigments, a greater amount of trace elements were detected. Therefore, the differences between biomass-derived and virgin endogenous pigments can also be assessed by comparing the types and amounts of trace elements detected using ICP-MS (ionizing radiation mass spectrometry). In addition, in body pigments derived from seashells, compared with the original body pigments of industrial products (e.g., calcium carbonate produced by carbon dioxide processes), it can be observed that the amount of at least one element selected from the group consisting of magnesium, manganese, phosphorus and sodium is larger.

[0055] From the viewpoints of flame retardancy, colorability, etc., the amount of biomass-derived endogenous pigments mixed relative to the total amount of the coloring layer is preferably, for example, about 5.0% by mass or more, about 10% by mass or more, about 15% by mass or more, about 17% by mass or more, or about 20% by mass or more, about 40% by mass or less, about 35% by mass or less, about 30% by mass or less, or about 28% by mass or less.

[0056] The coloring layer of this disclosure may include an amount of at least one selected from the group consisting of phosphorus-based flame retardants and boron-based flame retardants, ranging from about 15% by mass or more, about 17% by mass or more, or about 20% by mass or more. The upper limit of this amount may be, for example, about 50% by mass or less, about 45% by mass or less, about 40% by mass or less, or about 35% by mass or less. When phosphorus-based or boron-based flame retardants are used alone, the blending amount is intended to refer to a single amount, and when phosphorus-based and boron-based flame retardants are used in combination, the blending amount is intended to refer to their total amount. When phosphorus-based and boron-based flame retardants are used in combination, their blending ratio may be set within the range of, for example, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, and 10:90 by mass.

[0057] Examples of phosphorus-based flame retardants include monomeric phosphate flame retardants such as triaryl phosphates, condensed phosphate flame retardants such as diphenyl resorcinol phosphate and diphenyl bisphenol A phosphate, phosphonate flame retardants, phosphonate metal salt flame retardants, hypophosphonate flame retardants, hypophosphonate metal salt flame retardants, red phosphorus, and ammonium polyphosphate. Surface-coated ammonium polyphosphate (e.g., melamine-coated ammonium polyphosphate) can also be used as ammonium polyphosphate. Additionally, phosphorus-nitrogen flame retardants that can be used to replace melamine polyphosphate, phosphazene compounds, etc., can be listed. From the viewpoint of flame retardancy, phosphonate metal salts, melamine polyphosphate, ammonium polyphosphate, and melamine-coated ammonium polyphosphate are preferred, with phosphonate metal salts and melamine polyphosphate being more preferred, and from the viewpoint of water resistance, melamine polyphosphate is particularly preferred. Phosphorus-based flame retardants can be used alone or in combination of two or more types.

[0058] Boron-based flame retardants are flame retardants containing boron-containing components. Examples of boron-based flame retardants include boric acid, borates, boron-based nonmetallic compounds, borate minerals, and organoboron-based compounds. Examples of boric acid include boric acid, orthoboric acid, and metaboric acid. Examples of borates include salts of boric acid described above with metal ions or ammonium ions. Examples of metals constituting the metal ions include sodium, potassium, calcium, magnesium, barium, aluminum, and zinc. Examples of boron-based nonmetallic compounds may include boron oxide and boron nitride. Examples of borate minerals include borax, cholemanite, and urexite. Examples of organoboron-based compounds include borate esters, borates, and borooxanes. From a flame retardant viewpoint, borates are preferred, metal salts of boric acid are more preferred, and zinc borate and alkaline earth metal salts of boric acid are particularly preferred. Boron-based flame retardants can be used alone or in combination of two or more types.

[0059] The coloring layer of this disclosure may include one or more of a variety of resins. Examples of such resins include thermoplastic resins, thermosetting resins, and radiation-curable resins. Specific examples include fluoropolymers, polyester resins (such as PET and PEN), (meth)acrylic resins, polyolefin resins (such as polyethylene and polypropylene), thermoplastic elastomers, polycarbonate resins, polyamide resins, ABS resins, acrylonitrile-styrene resins, polystyrene resins, vinyl chloride resins, and resins having urethane bonds. Among these, vinyl chloride resins are preferred from a flame retardant viewpoint. Here, in this disclosure, in addition to homopolymers of vinyl chloride, "vinyl chloride resin" may also include copolymers of vinyl chloride monomer and another monomer that can be copolymerized with the vinyl chloride monomer. As other monomers that can be copolymerized with the vinyl chloride monomer, commonly used known monomers can be used without any particular limitation. Examples include one or more of vinyl esters (such as vinyl acetate), alkyl vinyl ethers (such as ethyl vinyl ether and octyl vinyl ether), α-olefins (such as ethylene and propylene), monovalent unsaturated acids (such as acrylic acid and methacrylic acid) and alkyl esters (such as methyl esters of these monovalent unsaturated acids), divalent unsaturated acids (such as maleic acid and itaconic acid), alkyl esters (such as methyl esters of these divalent unsaturated acids), vinylidene compounds (such as vinylidene chloride), and unsaturated nitrile compounds (such as acrylonitrile). The proportions of these monomers used are not particularly limited, and for example, they may be used at a proportion of about 30% by mass or less, or about 20% by mass or less, relative to vinyl chloride monomer.

[0060] The coloring layer of this disclosure may contain fillers, reinforcing materials, antioxidants, UV absorbers, flame retardants other than those described above, light stabilizers, heat stabilizers, dispersants, plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, catalysts, pigments and dyes other than those described above as optional components, the range of which does not negatively affect the effects of this disclosure. These optional components may be used alone or in combination of two or more types. The individual and total mixing amounts of the optional components can be determined without impairing the required characteristics of the coloring layer.

[0061] The flame-retardant decorative laminate disclosed herein includes a coloring layer containing a biomass-derived extender pigment and containing about 15% by mass or more of at least one selected from the group consisting of phosphorus-based and boron-based flame retardants, and thus can exhibit excellent flame retardancy. Therefore, the coloring layer need not be blended with another flame retardant, or when blended with another flame retardant, the amount of the flame retardant relative to the total amount of the coloring layer can be less than about 15% by mass, about 10% by mass or less, about 5% by mass or less, about 3% by mass or less, about 1% by mass or less, or about 0.5% by mass or less.

[0062] The thickness of the coloring layer can be, for example, about 15 micrometers or more, about 20 micrometers or more, about 23 micrometers or more, or about 25 micrometers or more, and can be about 90 micrometers or less, about 85 micrometers or less, about 80 micrometers or less, about 75 micrometers or less, about 70 micrometers or less, about 65 micrometers or less, or about 60 micrometers or less. From a flame retardant point of view, the thickness of the coloring layer is preferably about 20 micrometers or more and about 85 micrometers or less.

[0063] In some embodiments, the coloring layer of this disclosure satisfies a ratio of the thickness of the coloring layer to the thickness of the decorative laminate in the range of about 0.20 to about 0.80. When the coloring layer of this disclosure, which exhibits flame retardancy, satisfies such a ratio, the flame retardancy of the decorative laminate can be further improved. Such a ratio can be about 0.20 or greater, about 0.21 or greater, or about 0.22 or greater, and about 0.80 or less, about 0.70 or less, about 0.60 or less, or about 0.50 or less.

[0064] The flame-retardant decorative laminate disclosed herein includes an adhesive layer. The adhesive layer is typically a layer applied to an adhesive substrate (such as a support member of an article described below). The adhesive layer may be transparent or translucent, or it may be opaque, i.e., have concealing properties. The adhesive layer may be applied partially or over the entire surface of the decorative laminate. The adhesive layer may have a single-layer structure or a layered structure.

[0065] The adhesive layer can be applied directly or indirectly to one surface of the substrate described above, i.e., to one side of the adhesive (the side opposite to the visible side). The method of applying the adhesive layer is not particularly limited, and known methods such as blade coating, bar coating, knife coating, powder coating, roller coating, and casting coating can be used.

[0066] The material of the adhesive layer is not particularly limited, and for example, solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting, or UV-curable adhesives can be used. These adhesives utilize commonly used (meth)acrylic polymers, polyolefin polymers, resins with urethane bonds (polyurethane polymers), polyester polymers, polyether polymers, rubber materials (e.g., natural and synthetic rubber), silicone polymers, etc. Among these materials, pressure-sensitive adhesives and heat-sensitive adhesives are preferred from the viewpoint of easy adhesion to the adhesive body, etc., and pressure-sensitive adhesives and heat-sensitive adhesives prepared using (meth)acrylic polymers are more preferred. In this disclosure, the term "pressure-sensitive adhesive" refers to an adhesive that adheres to various surfaces under light pressure and does not exhibit a phase change (from liquid to solid) and has permanent adhesion at room temperature (e.g., about 20°C). Additionally, the term "heat-sensitive adhesive" refers to an adhesive that exhibits adhesion (tackiness) upon heating.

[0067] In the adhesive layer of this disclosure, optional components may include, for example, fillers (such as tackifying resins, crosslinking agents, conductive fillers, and thermally conductive fillers), silane coupling agents, plasticizers, thickeners, pigments, dyes, flame retardants, antioxidants, UV absorbers, stabilizers, etc., provided that the effects of this disclosure are not adversely affected. These optional components may be used alone or in combination of two or more types. The individual and total proportions of the optional components can be determined without impairing the desired characteristics of the adhesive layer.

[0068] In some embodiments, the adhesive layer of this disclosure contains about 10% by mass or less, about 5% by mass or less, about 3% by mass or less, about 1% by mass or less, or about 0.5% by mass or less of a flame retardant, or the adhesive layer of this disclosure does not contain a flame retardant. Because the decorative laminate of this disclosure comprises an extender pigment derived from biomass and a coloring layer containing about 15% by mass or more of at least one selected from the group consisting of phosphorus-based and boron-based flame retardants, it exhibits excellent flame retardancy even when the amount of flame retardant in the adhesive layer is low or the substrate does not contain a flame retardant.

[0069] The thickness of the adhesive layer disclosed herein is not particularly limited, and examples include about 5 micrometers or more, about 10 micrometers or more, or about 20 micrometers or more, and about 100 micrometers or less, about 80 micrometers or less, or about 50 micrometers or less.

[0070] In some embodiments, the flame-retardant decorative laminate of this disclosure optionally includes additional layers in addition to those described above, to the extent that it does not adversely affect the effectiveness of the invention. Examples of additional layers include at least one selected from the group consisting of surface layers, decorative layers (e.g., patterned or embossed layers), gloss layers, adhesive layers, and release liner. The additional layers may be applied to the entire surface or a portion of the laminate. The additional layers may have a three-dimensional shape, such as an embossed pattern on their surface.

[0071] The flame-retardant decorative laminate of this disclosure includes a coloring layer containing a biomass-derived extender pigment and about 15% by mass or more of at least one selected from the group consisting of phosphorus-based and boron-based flame retardants, and thus can exhibit excellent flame retardancy. Therefore, the additional layers need not be blended with another flame retardant, or when another flame retardant is blended, the amount of flame retardant mixed relative to the total amount of each additional layer can be less than about 15% by mass, about 10% by mass or less, about 5% by mass or less, about 3% by mass or less, about 1% by weight or less, or about 0.5% by mass or less. In particular, when the surface layer contains a high concentration of flame retardant, properties such as scratch resistance may deteriorate. In the surface layer of this disclosure, it is possible to reduce the amount of flame retardant mixed or not to blend it at all. Therefore, it is possible to reduce or suppress the deterioration of properties such as scratch resistance during the use of decorative articles to which the decorative laminate is applied.

[0072] The raw materials for the surface layer are not particularly limited, and for example, blends of one or more of the following types may be used: (meth)acrylic resins, such as polymethyl methacrylate (PMMA) and (meth)acrylic acid copolymers; resins having urethane bonds (e.g., polyurethane); fluoropolymers, such as ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), and methyl methacrylate-vinylidene fluoride copolymer (PMMA / PVDF); silicone resins; vinyl chloride resins (such as polyvinyl chloride (PVC); polycarbonate (PC); polyolefins, such as polyethylene (PE) and polypropylene (PP); polyesters, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyamides, such as nylon; and copolymers, such as ethylene / acrylic acid copolymer (EAA) and its ionomers, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol copolymers (EVOH).

[0073] The surface layer can have a multilayer structure. For example, the surface layer can be a laminate of a film formed from the resin described above, or it can be a multilayer coating of the resin described above. The surface layer can have a three-dimensional uneven shape, such as an embossed pattern on the entire or part of the surface of the surface layer.

[0074] A surface layer can be formed, for example, by coating a colored layer or substrate directly with a resin composition or via an adhesive layer. The coating of the surface layer can be performed before or after applying the decorative laminate to the adhesive (e.g., the support member described below). Alternatively, a surface film can be formed by coating a release liner with a resin composition, and this film can be laminated onto the colored layer or substrate via an adhesive layer. For example, in the case where the colored layer is bonded to the surface film, the surface film can be laminated directly onto the colored layer without the need for any adhesive layer. For example, a surface film can be formed by coating a release liner with a resin raw material (such as a curable (meth)acrylic resin composition or a reactive polyurethane composition) via blade coating, rod coating, knife coating, roller coating, or cast coating, and subsequently performing photocuring or thermocuring as needed.

[0075] A surface layer that has been pre-formed into a film through extrusion, stretching, etc., can be used. Such a film can be laminated onto a coloring layer or a substrate, with an adhesive layer inserted between them. Alternatively, in the case where the coloring layer is bonded to such a film, the film can be directly laminated onto the coloring layer without any adhesive layer inserted between them. By using a film with high flatness as such a film, a higher surface flatness appearance can be given to the article (structure). The surface layer can also be formed with another layer through multilayer extrusion. For example, a (meth)acrylic film can be used as this other layer. For example, resins containing polymethyl methacrylate (PMMA), polybutyl acrylate, (meth)acrylic copolymers, ethylene / acrylic copolymers, and ethylene vinyl acetate / acrylic copolymers can be formed into films and used as (meth)acrylic films. (Meth)acrylic films exhibit excellent transparency and / or scratch resistance, heat resistance and / or light resistance, and are unlikely to cause discoloration and / or changes in gloss. Furthermore, excellent molding processability can be obtained even without the use of plasticizers, and excellent stain resistance can be achieved since no plasticizers are required. Among these, a (meth)acrylic film having PMMA as the main component is preferred. For example, when using a (meth)acrylic resin with excellent scratch resistance as another layer and a fluoropolymer (such as ETFE, PVDF, or PMMA / PVDF) with excellent chemical resistance as the surface layer, the resulting surface layer can be a surface layer with the properties of both of these layers.

[0076] The surface layer of this disclosure may contain, as optional components, such as fillers, matting agents, antioxidants, UV absorbers, flame retardants, light stabilizers, heat stabilizers, rheology modifiers, surface conditioning agents, hard coating materials, gloss imparters, dispersants, plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, catalysts, pigments, and dyes, provided that the effects of this disclosure are not adversely affected. For example, the use of UV absorbers (such as benzotriazole, Tinuvin 1130 (purchased from BASF)) and hindered amine light stabilizers (HALS) (such as Tinuvin 292 (purchased from BASF)) can effectively prevent discoloration, fading, and degradation of the underlying coloring layer. Rheology modifiers (such as ACRYSOL RM-8W) and surfactants (such as Dynol 604) can also be used to improve coatability. Hard coating materials can be contained in the surface layer or applied as a hard coating by being applied separately to the surface layer.

[0077] The surface layer may be partially opaque, but from the viewpoint of visibility of the coloring layer or any decorative layer, it is preferably translucent or semi-transparent.

[0078] The thickness of the surface layer is not particularly limited and can be, for example, about 1 micrometer or more, about 5 micrometers or more, or about 10 micrometers or more, and can be about 150 micrometers or less, about 100 micrometers or less, about 80 micrometers or less, about 50 micrometers or less, about 30 micrometers or less, or about 20 micrometers or less. From a flame retardant point of view, a thin surface layer is advantageous, and is preferably, for example, about 50 micrometers or less, about 30 micrometers or less, or about 20 micrometers or less.

[0079] In some embodiments, the protective layer includes a matting agent. By blending the matting agent, the surface layer can exhibit matting properties. Here, in this disclosure, "matting properties" is intended to refer to a lower surface gloss compared to a surface layer without a matting agent.

[0080] Matting properties can be evaluated, for example, using a 60-degree surface gloss (i.e., surface gloss at 60 degrees). In some embodiments, the surface layer of the decorative laminate of this disclosure exhibits a 60-degree surface gloss of about 10.0 GU or less, about 8.0 GU or less, about 5.0 GU or less, about 4.5 GU or less, or about 4.0 GU or less. The lower limit of the surface gloss is not particularly limited and can be, for example, about 0.1 GU or more, about 0.5 GU or more, or about 1.0 GU or more. The surface gloss is a value measured using a portable gloss meter GMX-203 (Murakami Color Research Laboratory, Chuo-ku, Tokyo, Japan).

[0081] As a matting agent, resin beads and inorganic particles can be used, for example. Matting agents can be used alone or in combination of two or more types.

[0082] Resin beads are not particularly limited, and examples include resin beads prepared from resins having urethane bonds, styrene resins, nylon resins, polyester resins, melamine resins, silicone resins, and (meth)acrylic resins. Such resin beads may be solid or porous, and may be used alone or in combination of two or more types. Resin beads containing resins having urethane bonds (sometimes referred to as "urethane resin beads") are preferred from the viewpoints of matting properties, scratch resistance, and conformability when stretching the surface layer. The surface of the resin beads can be modified with known surface modifiers.

[0083] As urethane resin beads, cross-linked urethane resin beads obtained through suspension polymerization, seed polymerization, emulsion polymerization, etc., can be used. These urethane resin beads have excellent flexibility, toughness, scratch resistance, etc., and these characteristics can be imparted to the surface layer.

[0084] When the resin beads and the adhesive are of the same type of resin components—for example, when the resin beads and the adhesive contain urethane components or (meth)acrylic components—these resin beads exhibit excellent affinity for the adhesive and thus improve adhesion to the adhesive. Therefore, even if the laminate is scratched or deformed, separation of the resin beads from the adhesive can be reduced or suppressed. Here, "same type of resin component" is not limited to the case where the constituent components of the resin are completely identical, but includes the case where one or more common resin components are present in the components constituting the resin. For example, resin beads prepared from urethane acrylates have two types of urethane components and acrylic components, and therefore such resin beads are of the same type of resin component as urethane resin adhesives and also of the same type of resin component as acrylic resin adhesives.

[0085] In addition to the light scattering effect based on the unevenness of the surface layer, the refractive index of the resin beads is preferably different from that of the binder, in cases where light scattering or refraction effects are expected due to the resin beads inside the surface layer.

[0086] Inorganic particles are not particularly limited, and examples include inorganic oxide particles, mixed oxide particles containing two or more types of metallic elements, and mixtures thereof. Examples of inorganic oxide particles include at least one selected from the group consisting of alumina particles, tin oxide particles, antimony oxide particles, silicon dioxide particles, zirconium oxide particles, titanium dioxide particles, and ferrite particles. Examples of mixed oxide particles containing two or more metallic elements include mixed oxide particles containing at least two metallic elements selected from the group consisting of aluminum, tin, antimony, silicon, zirconium, titanium, and iron. Inorganic particles can be used alone or in combination of two or more types. Alumina particles are preferred from the viewpoint of matting properties and scratch resistance.

[0087] The average particle size of the matting agent can be approximately 3 micrometers or larger, approximately 5 micrometers or larger, approximately 7 micrometers or larger, approximately 10 micrometers or larger, approximately 15 micrometers or larger, approximately 16 micrometers or larger, approximately 18 micrometers or larger, approximately 20 micrometers or larger, approximately 23 micrometers or larger, or approximately 25 micrometers or larger, and can also be approximately 50 micrometers or smaller, approximately 45 micrometers or smaller, approximately 40 micrometers or smaller, approximately 35 micrometers or smaller, approximately 30 micrometers or smaller, approximately 25 micrometers or smaller, approximately 20 micrometers or smaller, approximately 18 micrometers or smaller, approximately 17 micrometers or smaller, approximately 16 micrometers or smaller, approximately 15 micrometers or smaller, approximately 14 micrometers or smaller, approximately 13 micrometers or smaller, approximately 12 micrometers or smaller, approximately 11 micrometers or smaller, or approximately 10 micrometers or smaller. The average particle size of the matting agent is the particle size with 50% cumulative volume, measured using a laser diffraction particle size distribution measurement device.

[0088] The amount of matting agent mixed relative to the total amount of the surface layer can be about 10% by mass or more, about 20% by mass or more, about 30% by mass or more, about 40% by mass or more, about 45% by mass or more, or about 50% by mass or more, and can be about 70% by mass or less, about 65% by mass or less, about 60% by mass or less, about 55% by mass or less, or about 50% by mass or less.

[0089] A decorative layer as an additional layer refers to a layer that can impart decoration in addition to the coloring layers described above. Examples of such decorative layers include, but are not limited to, patterned layers used to impart patterns (such as wood grain, stone grain, geometric or leather patterns, logos or designs) to articles, embossed (embossed pattern) layers with uneven shapes on their surfaces, and combinations thereof.

[0090] Decorative layers can be applied directly or through adhesive layers to the entire surface or a portion of layers (such as surface layers, coloring layers, base layers, or adhesive layers) that make up the decorative layer assembly.

[0091] The patterned layer is not limited to the following, but for example, it can be a patterned layer obtained by applying a pattern (such as a design, logo, or graphic pattern) directly to a surface layer, metal layer, or adhesive layer using a printing method (such as direct gravure printing, gravure offset printing, inkjet printing, laser printing, or screen printing). Alternatively, for example, a film or sheet with a design, logo, or graphic pattern can also be used by coating (such as gravure coating, roller coating, die coating, bar coating, or doctor blade coating), punching, or etching.

[0092] The raw materials used for the patterned layer are not limited to the following, but for example, raw materials obtained by dispersing pigments in a binder resin (such as (meth)acrylic resins or resins having urethane bonds) can be used. Examples of pigments include: inorganic pigments such as carbon black, chrome yellow, yellow iron oxide, red iron oxide, or red iron oxide; or organic pigments such as phthalocyanine pigments (such as phthalocyanine blue or phthalocyanine green), azo lake pigments, indigo pigments, pyrenone pigments, dinaphthalene-based pigments, quinacridone pigments, diazine pigments, and quinacridone pigments (such as quinacridone red).

[0093] For the embossed layer, a thermoplastic resin film with an uneven shape on its surface can be used, which is obtained by methods well known in the art, such as embossing, scratching, laser processing, dry etching, or hot pressing. The embossed layer can also be formed by applying a thermosetting or radiation-curable resin (such as a curable (meth)acrylate resin) to a release liner with an uneven shape, curing the resin by heat or radiation, and removing the release liner.

[0094] The thermoplastic resins, thermosetting resins, and radiation-curable resins used in the embossed layer are not particularly limited, but for example, fluoropolymers, polyester resins (such as PET or PEN), (meth)acrylic resins, polyolefin resins (such as polyethylene or polypropylene), thermoplastic elastomers, polycarbonate resins, polyamide resins, ABS resins, acrylonitrile-styrene resins, polystyrene resins, vinyl chloride resins, or resins having urethane bonds can be used. The embossed layer may contain at least one of the pigments used in the pattern layer.

[0095] The decorative layer of this disclosure may contain, as optional components, such as fillers, reinforcing agents, antioxidants, UV absorbers, flame retardants, light stabilizers, heat stabilizers, dispersants, plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, and catalysts, the range of which does not negatively affect the effectiveness of this disclosure.

[0096] The thickness of the decorative layer only needs to be adjusted appropriately according to the desired decorative effect, and is not particularly limited, but can be, for example, about 1.0 micrometer or larger, about 3.0 micrometer or larger, or about 5.0 micrometer or larger, and can be about 50 micrometer or smaller, about 40 micrometer or smaller, or about 30 micrometer or smaller.

[0097] Examples of brightening layers may include, but are not limited to, layers constituting a decorative composite, such as layers containing metals selected from aluminum, nickel, gold, silver, copper, platinum, chromium, iron, tin, indium, titanium, lead, zinc, or germanium, or alloys or compounds thereof, formed on the entire surface or a portion of the substrate or coloring layer by vacuum deposition, sputtering, ion plating, electroplating, etc. The thickness of the brightening layer may be appropriately selected according to the desired decorative effect, brightness, etc.

[0098] In the flame-retardant decorative laminates disclosed herein, an adhesive layer (e.g., sometimes referred to as a "primer layer") may be used as an additional layer in the adhesive laminate. As the adhesive layer, solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting, or UV-curable adhesives may be used, such as commonly used (meth)acrylic polymers, polyolefin polymers, resins with urethane bonds (polyurethane polymers), polyester polymers, or rubber-based materials. The adhesive layer may be applied by well-known coating methods, etc.

[0099] In the flame-retardant decorative laminates of this disclosure, a release liner is typically applied to the adhesive layer. Examples of release liners include: paper; plastic materials such as polyethylene, polypropylene, polyester (e.g., PET), and cellulose acetate; and paper coated with such plastic materials. These liners may have a surface that has been treated with a release agent (such as silicone). The thickness of the release liner can typically be about 5 micrometers or more, about 15 micrometers or more, or about 25 micrometers or more, and can be about 500 micrometers or less, about 300 micrometers or less, or about 250 micrometers or less.

[0100] The flame-retardant decorative laminate disclosed herein can be, for example, a sheet-like article, a roll-shaped body, or an article having a three-dimensional shape.

[0101] The following production methods are described as examples, but the methods for producing flame-retardant decorative laminates are not limited to these.

[0102] For example, in the case of a laminate having a configuration in which a release liner, an adhesive layer, a substrate, a coloring layer, and a surface layer are provided in sequence, the adhesive is applied to the substrate, drying and curing steps are applied as needed, and then the release liner is bonded to the adhesive layer to form laminate A. The substrate surface of laminate A is coated with a composition for the coloring layer, which contains biomass-derived extender pigments and a specific flame retardant, and drying and curing steps are applied as needed to form the coloring layer. Then, a composition for the surface layer is applied to the coloring layer, and drying and curing steps are applied as needed to form the surface layer, thereby forming a decorative laminate. Alternatively, the coloring layer can be applied to the substrate, then the adhesive can be applied to the coloring layer, and then the surface layer can be applied to one side of the substrate opposite the adhesive layer.

[0103] In some embodiments, a decorative article is provided, comprising a support member and a flame-retardant decorative laminate of the present disclosure adhered to the support member. Such a decorative article is capable of exhibiting flame retardancy. The materials used for the support member are not particularly limited, and examples include: resin raw materials (e.g., polyolefin resins, polyester resins, (meth)acrylic resins, polycarbonate resins, and acrylonitrile-butadiene-styrene copolymers), inorganic raw materials (e.g., glass, ceramics, concrete, gypsum, calcium silicate, natural stone, and bitumen), rubber raw materials, fabrics (e.g., woven fabrics, knitted fabrics, and nonwoven fabrics), and wood raw materials.

[0104] The shape or configuration of the supporting components is not particularly limited: they can be, for example, membrane-like, plate-like, curved, deformable, or three-dimensional, and they can also be single-layered, laminated, or composite configurations, such as multiple components of different shaped materials combined therein.

[0105] Articles using the decorative laminates of this disclosure can be used for a variety of purposes. Examples of such purposes include billboards (e.g., billboards with internal lighting and billboards with external lighting); signs (e.g., signs with internal lighting and signs with external lighting); various interior or exterior articles, such as interior or exterior articles for vehicles (e.g., automobiles, railways, airplanes, and ships) (e.g., ceiling components, column components, door panel components, dashboard components, front components (e.g., hoods), bumper components, fender components, side beam components, and interior panel components); and interior or exterior articles for buildings (e.g., window glass, doors, window frames, roof components (e.g., tiles), exterior wall components, and wallpaper); electrical appliances, such as personal computers, smartphones, mobile phones, refrigerators, and air conditioners; stationery; furniture; tables; and various containers, such as cans. Among these, due to the excellent flame retardancy of the decorative laminates of this disclosure, articles using the decorative laminates of this disclosure are suitable for use as interior or exterior articles for buildings.

[0106] The method for applying the flame-retardant decorative laminate of this disclosure to the support member (adhesive) constituting the decorative article is not particularly limited, and known methods may be used appropriately. Examples of methods include manual application, injection molding methods (such as insert injection molding, in-mold molding, on-mold molding, two-color injection molding, core-back injection molding, and sandwich injection molding), lamination methods, and three-dimensional thermo-stretch blow molding (TOM) methods.

[0107] Example

[0108] The following embodiments illustrate specific implementations of this disclosure, but the invention is not limited to these embodiments. Unless otherwise specified, all “parts” and “percentages” are by mass. Numerical values ​​substantially include errors arising from the measurement principle and measuring device. Numerical values ​​are generally indicated by rounded significant figures.

[0109] The products used in this embodiment are shown in Table 1 below.

[0110]

[0111] Examples 1 to 15 and Comparative Examples 1 to 5

[0112] Production of PET film substrates with colored layers

[0113] The formulation containing the components constituting the coloring layer shown in Table 2, along with methyl ethyl ketone (MEK), was mixed with THINKY (trade name) AR-250 (manufactured by THINKY CORPORATION (Chiyoda-ku, Tokyo, Japan)) for approximately 3 minutes to obtain a coating solution for the coloring layer. This coating solution was applied to a transparent PET film substrate containing recycled PET (RESHINE (trade name) TA-065) using a doctor blade. The substrate was dried at approximately 65°C for approximately 1.5 minutes and then at approximately 155°C for approximately 2 minutes to obtain a PET film substrate with the coloring layer. The thicknesses of the coloring layers used in the various examples and comparative examples are shown in Table 2.

[0114] Example 1

[0115] A formulation containing 20 parts by weight of ETERNACOLL (trade name) UW-1005E, 15 parts by weight of Art Pearl (trade name) C-800T, 18 parts by weight of Takenate (trade name) WB-3936, 34 parts by weight of purified water, 7 parts by weight of isopropanol (IPA), 3 parts by weight of rheology modifier, and 3 parts by weight of surfactant was mixed in THINKY (trade name) AR-250 (manufactured by Shinki Co., Ltd., Chiyoda City, Tokyo, Japan) for approximately 2 minutes to obtain a surface coating solution. The coating solution was applied to the colored layer of a PET film substrate with a colored layer using a doctor blade. Drying was performed at approximately 65°C for approximately 2 minutes and at approximately 150°C for approximately 5 minutes to form a surface layer approximately 12 micrometers thick.

[0116] A mixture of butyl acrylate and acrylate monomers was copolymerized in ethyl acetate to prepare an acrylic pressure-sensitive adhesive composition containing approximately 38% by mass of an acrylic copolymer. The obtained composition was applied by doctor blade coating to the surface of a PET film substrate opposite to the surface to which the colored layer was applied, resulting in a dried thickness of approximately 38 micrometers, thereby producing a decorative laminate. In Table 2, the layer configurations of the laminates are classified into the following three groups, and the layer configuration of Example 1 corresponds to layer configuration A: Layer configuration A: Surface layer / Coloring layer / PET substrate / Adhesive layer Layer configuration B: Surface layer / PET substrate / Coloring layer / Adhesive layer Layer configuration C: Coloring layer / PET substrate / adhesive layer Examples 2 to 7 and Comparative Examples 1 to 3 Except for changing the composition and thickness of the coloring layer to the materials shown in Table 2, the decorative laminate is produced in the same manner as in Example 1.

[0117] Example 8

[0118] The surface coating liquid obtained in Example 1 was applied to the surface of a PET film substrate with a colored layer, opposite to the surface to which the colored layer was applied, using a doctor blade coating method. Drying was performed at approximately 65°C for approximately 2 minutes and at approximately 150°C for approximately 5 minutes to form a surface layer approximately 14 micrometers thick. Next, the acrylic pressure-sensitive adhesive composition obtained in Example 1 was applied to the colored layer using a doctor blade coating method, resulting in a dried thickness of approximately 38 micrometers, to prepare a decorative laminate.

[0119] Examples 9, 10, and 12 to 15

[0120] Except for changing the composition and thickness of the coloring layer as shown in Table 2, the decorative laminate was produced in the same manner as in Example 8.

[0121] Example 11

[0122] A PET film substrate with a colored layer was prepared to have the composition and thickness shown in Table 2. Next, the acrylic pressure-sensitive adhesive composition obtained in Example 1 was applied to the surface of the PET film substrate opposite to the surface to which the colored layer was applied by a doctor blade coating, such that the dried thickness was about 38 micrometers, thereby preparing a decorative laminate.

[0123] Comparative Example 4

[0124] Except for changing the composition of the coloring layer as shown in Table 2, the decorative laminate is produced in the same manner as in Example 11.

[0125] Comparative Example 5

[0126] Except for changing the thickness of the surface layer and the composition and thickness of the coloring layer as shown in Table 2, the decorative laminate was produced in the same manner as in Example 1.

[0127] Physical property evaluation test

[0128] The properties of each decorative laminate were evaluated using the following tests. The results are shown in Table 2.

[0129] (Heat release test: flame retardancy)

[0130] Each decorative laminate, cut into 99mm±1mm squares, was stacked on a 12.5mm thick gypsum board, also cut into 99mm±1mm squares, to prepare a test specimen. The gypsum board was a non-combustible material as specified in the Ministry of Construction's Notice No. 1400 of 2000.

[0131] The specimens were placed in an environment of 23°C and 50% RH for one week or longer, and then heat release tests were performed using a cone calorimeter (manufactured by Toyo Seiki Seisaku-sho, Ltd., Kita-ku, Tokyo, Japan) according to the cone calorimetry method of ISO 5660-1:2002, where the radiant heat applied to the surface of the specimen on the decorative laminate side was 50 kW / m². 2 The total calorific value was measured under the following conditions. From this test, the total calorific value (THR), maximum heat release rate (PHRR), and the heat release rate exceeding 200 kW / m² during the 20-minute test period were determined. 2 The time frame is shown in Table 2.

[0132] (60-degree gloss test: matting properties)

[0133] The 60-degree gloss of the surface or coloring layer of the decorative laminate was measured according to JIS Z8741 using a portable gloss meter GMX-203 manufactured by Murakami Color Research Lab. Gloss measurements were taken at three points, and the average value was used as a representative value. The results are shown in Table 2.

[0134] Table 2

[0135] Various modifications and variations of the above-described embodiments and examples will be readily apparent to those skilled in the art without departing from the fundamental principles of the invention. Furthermore, it will be apparent to those skilled in the art that various modifications and variations of the invention can be made without departing from its spirit and scope.

Claims

1. A flame-retardant decorative laminate comprising a substrate, a colored layer, and an adhesive layer, the colored layer contains a biomass-derived extender pigment, and contains 15 mass% or more of at least one selected from the group consisting of phosphorus-based flame retardants and boron-based flame retardants.

2. The flame-retardant decorative laminate according to claim 1, wherein the colored layer has a thickness of 20 micrometers or more and 85 micrometers or less, the flame-retardant decorative laminate has a thickness of 200 micrometers or less, and a ratio of the thickness of the colored layer to the thickness of the flame-retardant decorative laminate is 0.20 to 0.

80.

3. The flame-retardant decorative laminate according to claim 1 or 2, wherein a compounding amount of a flame retardant in the substrate is 10 mass% or less.

4. The flame-retardant decorative laminate according to claim 1 or 2, wherein the colored layer contains a vinyl chloride resin.

5. The flame-retardant decorative laminate according to claim 1 or 2, wherein the substrate contains a polyethylene terephthalate resin.

6. The flame-retardant decorative laminate according to claim 5, wherein the polyethylene terephthalate resin contains a recycled polyethylene terephthalate resin.

7. The flame-retardant decorative laminate according to claim 1 or 2, wherein the biomass-derived extender pigment contains a biomass-derived calcium carbonate.

8. The laminate of claim 1 or 2, wherein in a heat release test using a laminate panel comprising a gypsum board and the laminate as a test specimen, the laminate being stacked on one side of the gypsum board, which side is subjected to radiant heat, the total heat release of the test specimen is 8.0 MJ / m2 2 or less in 20 minutes of test time.

9. The laminate of claim 1 or 2, wherein in a heat release test using a laminate panel comprising a gypsum board and the laminate as a test specimen, the laminate being stacked on one side of the gypsum board, which side is subjected to radiant heat, the peak heat release rate of the test specimen is 200 kW / m2 2 or less.

10. The laminate of claim 1 or 2, wherein in a heat release test using a laminate panel comprising a gypsum board and the laminate as a test specimen, the laminate being stacked on one side of Heat release test: Heat release test according to ISO 5660-1 :2002 Cone Calorimetry, wherein the gross heat release is measured under the condition that the radiant heat applied to the surface of the test piece is 50 kW / m2 2 .

9. A decorative article comprising: a support member, and the flame-retardant decorative laminate according to claim 1 or 2 bonded to the support member.

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