Decorative sheet and decorative plate

文档序号：277304 发布日期：2021-11-19 浏览：7次中文

阅读说明：本技术 装饰片和装饰板 (Decorative sheet and decorative plate ) 是由根津义昭风间圭佑阪口结香小林义弘于 2020-03-19 设计创作，主要内容包括：本发明提供一种阻燃性优异并且花纹鲜明可见、变色被抑制、清晰性优异的装饰片。本发明提供一种装饰片,其特征在于：具有选自透明性树脂层、基材片和合成树脂制衬垫层中的至少1层的热塑性树脂层,(1)上述热塑性树脂层中的至少1层含有磷腈系阻燃剂,(2)上述透明性树脂层和上述基材片含有选自聚烯烃系树脂和聚酯系树脂中的至少1种。(The invention provides a decorative sheet which has excellent flame retardancy, clear and visible patterns, inhibited color change and excellent clearness. The invention provides a decorative sheet, which is characterized in that: the thermoplastic resin layer comprises at least 1 layer selected from the group consisting of a transparent resin layer, a substrate sheet and a synthetic resin backing layer, (1) at least 1 layer of the thermoplastic resin layer contains a phosphazene flame retardant, and (2) the transparent resin layer and the substrate sheet contain at least 1 selected from the group consisting of polyolefin resins and polyester resins.)

1. A decorative sheet characterized by:

a thermoplastic resin layer having at least 1 layer selected from the group consisting of a transparent resin layer, a substrate sheet and a synthetic resin-made cushion layer,

(1) at least 1 of the thermoplastic resin layers contains a phosphazene flame retardant,

(2) the transparent resin layer and the substrate sheet contain at least 1 selected from the group consisting of polyolefin resins and polyester resins.

2. The decorative sheet of claim 1, wherein:

only the uppermost thermoplastic resin layer of the thermoplastic resin layers contains the phosphazene flame retardant, and the content of the phosphazene flame retardant is 3 mass% or more when the total mass of the thermoplastic resin layers is 100 mass%.

3. The decorative sheet of claim 1, wherein:

only the lowermost thermoplastic resin layer of the thermoplastic resin layers contains the phosphazene flame retardant, and the content of the phosphazene flame retardant is 14 mass% or more when the total mass of the thermoplastic resin layers is 100 mass%.

4. The decorative sheet of claim 1, wherein:

at least 1 of the thermoplastic resin layers contains a NOR type hindered amine compound.

5. The decorative sheet of claim 1, wherein:

at least 1 of the thermoplastic resin layers contains the phosphazene flame retardant and a filler.

6. The decorative sheet of claim 5, wherein:

the filler is an inorganic filler with polar groups on the surface.

7. The decorative sheet according to any one of claims 1 to 6, wherein:

the base sheet has at least a pattern layer and the transparent resin layer in this order.

8. The decorative sheet according to any one of claims 1 to 6, wherein:

the outermost surface has a surface protection layer.

9. The decorative sheet according to any one of claims 1 to 6, wherein:

the base sheet is provided with at least the pattern layer, the transparent resin layer and a surface protective layer in this order.

10. The decorative sheet according to claim 8 or 9, wherein:

the surface protection layer is an ionizing ray curing resin layer.

11. The decorative sheet according to claim 7 or 9, wherein:

the transparent resin layer side has an embossed shape.

12. A decorative panel, characterized in that:

the decorative sheet according to any one of claims 1 to 11 provided on a substrate.

Technical Field

The present invention relates to a decorative sheet and a decorative plate.

Background

Conventionally, a decorative sheet is laminated to impart design properties to the surface of various articles. For example, a decorative sheet used as a floor surface of a building can be used by laminating a decorative sheet on a base material.

Such decorative sheets are laminated on the surface of a building, and therefore, it is sometimes required to satisfy the condition that they are not flammable in case of fire and can provide a non-combustible property. The conditions for obtaining the non-combustible property are conditions specified in the exothermic property test according to ISO 5660-1 specified in Japanese construction Standard Law 2, clause 9, for the total heat release amount, the maximum heat release rate, and the occurrence of cracks and voids.

As a decorative sheet used for a decorative sheet satisfying the above-described conditions, a decorative sheet in which a substrate sheet, a transparent resin layer, and a surface protective layer are laminated in this order, and each layer has a thickness within a specific range and contains a flame retardant has been proposed (for example, see patent document 1).

Although the above-mentioned decorative sheet is also a decorative sheet excellent in flame retardancy, the difficulty of fire propagation in a fire in a decorative sheet on a base material to be applied on a horizontal surface is an important property for securing a safe-keeping time, but the difficulty of fire propagation has not been sufficiently studied. Therefore, important for flame retardancy is the property of reducing the amount of heat release and the rate of heat release in the heat release test according to ISO 5660-1, or the property of increasing the area of the decorative sheet that suppresses ignition during a fire and making the fire less likely to spread.

Flame retardants are useful for imparting flame retardancy to the decorative sheet, and examples of such flame retardants include halogen flame retardants, antimony flame retardants, metal hydroxide flame retardants, and phosphate flame retardants. However, halogen-based flame retardants and antimony-based flame retardants have a problem that they are not preferable from the viewpoint of environment.

When a metal hydroxide-based flame retardant is used as the flame retardant, a large amount of the flame retardant is required. In addition, the phosphate-based flame retardant forms combustion coke during combustion to suppress combustion. When such a phosphate-based flame retardant is used, a large amount of the phosphate-based flame retardant is also required to be added in order to obtain a flame-retardant effect by forming a burned product. Therefore, when these flame retardants are used, the transparency of the layer containing the flame retardants is impaired, and the layer may be colored, which may cause a problem of lowering the clarity of the decorative sheet pattern.

Therefore, it is desired to develop a decorative sheet having excellent flame retardancy, a clear and visible pattern, suppressed discoloration, and excellent clarity.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2015-182379

Disclosure of Invention

Technical problem to be solved by the invention

The invention aims to provide a decorative sheet which has excellent flame retardance, clear and visible patterns, inhibited color change and excellent clearness.

Technical solution for solving technical problem

The present inventors have conducted extensive studies and as a result, have found that the above object can be achieved by a decorative sheet having a thermoplastic resin layer comprising at least 1 layer selected from a transparent resin layer, a substrate sheet and a synthetic resin cushion layer, wherein at least 1 layer of the thermoplastic resin layer contains a phosphazene-based flame retardant, and the transparent resin layer and the substrate sheet contain at least 1 selected from a polyolefin-based resin and a polyester-based resin, and have completed the present invention.

That is, the present invention relates to the following decorative sheet and decorative plate.

1. A decorative sheet characterized by: a thermoplastic resin layer having at least 1 layer selected from the group consisting of a transparent resin layer, a substrate sheet and a synthetic resin-made cushion layer,

(1) at least 1 of the thermoplastic resin layers contains a phosphazene flame retardant,

(2) the transparent resin layer and the substrate sheet contain at least 1 selected from the group consisting of polyolefin resins and polyester resins.

2. The decorative sheet according to item 1, wherein only the uppermost thermoplastic resin layer of the thermoplastic resin layers contains the phosphazene flame retardant, and the content of the phosphazene flame retardant is 3% by mass or more when the total mass of the thermoplastic resin layers is 100% by mass.

3. The decorative sheet according to item 1, wherein only the thermoplastic resin layer in the lowermost layer of the thermoplastic resin layers contains the phosphazene flame retardant, and the content of the phosphazene flame retardant is 14 mass% or more when the total mass of the thermoplastic resin layers is 100 mass%.

4. The decorative sheet according to item 1, wherein at least 1 of the thermoplastic resin layers contains a NOR-type hindered amine compound.

5. The decorative sheet according to item 1, wherein at least 1 of the thermoplastic resin layers contains the phosphazene flame retardant and a filler.

6. The decorative sheet according to item 5, wherein the filler is an inorganic filler having a polar group on the surface.

7. The decorative sheet according to any one of claims 1 to 6, which comprises at least a pattern layer and the transparent resin layer in this order on the substrate sheet.

8. The decorative sheet as claimed in any one of items 1 to 6, which has a surface protective layer on the outermost surface.

9. The decorative sheet according to any one of claims 1 to 6, which comprises the pattern layer, the transparent resin layer and the surface protective layer on the substrate sheet in this order.

10. The decorative sheet according to item 8 or 9, wherein the surface protective layer is an ionizing radiation curable resin layer.

11. The decorative sheet according to item 7 or 9, which has an embossed shape on the transparent resin layer side.

12. A decorative sheet comprising the decorative sheet according to any one of items 1 to 11 on a base material.

Effects of the invention

The decorative sheet of the present invention is less likely to spread a fire, has excellent flame retardancy, has a clear and visible pattern, is inhibited from discoloring, and can exhibit high clarity. In addition, the decorative sheet of the present invention has excellent flame retardancy and can exhibit high clarity because the decorative sheet is provided on a substrate.

Drawings

Fig. 1 is a schematic view showing an example of the layer structure of the decorative sheet of the present invention.

Fig. 2 is a schematic view showing an example of the layer structure of the decorative sheet of the present invention.

Fig. 3 is a schematic view showing an example of the layer structure of the decorative sheet of the present invention.

Fig. 4 is a schematic view showing an example of the layer structure of the decorative sheet of the present invention.

Fig. 5 is a schematic view showing an example of the layer structure of the base material constituting the decorative sheet of the present invention.

Fig. 6 is a schematic view showing an example of the layer structure of the decorative sheet of the present invention.

Fig. 7 is a schematic view showing an example of the layer structure of the decorative sheet of the present invention.

Fig. 8 is a schematic view showing an example of the layer structure of the decorative sheet of the present invention.

Fig. 9 is a schematic view showing an example of the layer structure of the decorative sheet of the present invention.

Fig. 10 is a schematic view showing a test method of the degree of difficulty in spreading fire.

Fig. 11 is a schematic view showing a test method of the degree of difficulty in spreading fire.

Fig. 12 is a graph showing the evaluation result of the fire spread rate.

Detailed Description

The decorative sheet and the decorative plate of the present invention will be described in detail below. In the decorative sheet of the present invention, the surface of the decorative sheet opposite to the laminated substrate side is a so-called "front surface" and is a surface that can be seen when the decorative sheet is applied to a floor or the like. Therefore, in the present specification, the direction of the surface of the decorative sheet opposite to the laminated substrate side is referred to as "upper", and the direction of the surface opposite thereto, i.e., the laminated substrate side is referred to as "back surface" or "lower". Similarly, in the present specification, the direction of the surface of the decorative sheet side of the decorative sheet is referred to as "up", and the direction of the surface of the opposite side, i.e., the base material side, is referred to as "back" or "down".

1. Decorative sheet

The decorative sheet of the present invention is a decorative sheet having at least 1 thermoplastic resin layer selected from the group consisting of a transparent resin layer, a substrate sheet and a synthetic resin cushion layer, wherein (1) at least 1 of the thermoplastic resin layers contains a phosphazene flame retardant, and (2) the transparent resin layer and the substrate sheet contain at least 1 selected from the group consisting of a polyolefin resin and a polyester resin. With respect to the decorative sheet of the present invention having the above-described characteristics, the two conditions that (1) at least 1 layer of the thermoplastic resin layer contains the phosphazene-based flame retardant and (2) the transparent resin layer and the substrate sheet contains at least 1 selected from the polyolefin-based resin and the polyester-based resin cooperate with each other, and even if the flame retardant is not added in a large amount, the decorative sheet can exhibit a characteristic of reducing the heat release amount and the heat release rate in the heat release test according to ISO 5660-1, or a characteristic of suppressing the spread of the area of the decorative sheet upon fire and the spread of the fire, that is, the flame retardancy, and the decorative sheet can exhibit a clear pattern, and is suppressed in discoloration and can exhibit high clarity.

Further, when the flame retardant is contained in the transparent resin layer, the decrease in transparency is suppressed due to the small content, and when the flame retardant is contained in the base sheet, the occurrence of skip printing is suppressed due to the small content, so that the decorative sheet having excellent design properties such as a pattern displayed on the decorative sheet is obtained. Further, by laminating the decorative sheet on a substrate, a decorative sheet having good results of heat release test and horizontal burning test according to ISO 5660-1 and excellent flame retardancy can be obtained.

The decorative sheet of the present invention is a decorative sheet having at least 1 thermoplastic resin layer selected from a transparent resin layer, a substrate sheet and a synthetic resin cushion layer, and the layer configuration is not limited as long as the conditions (1) and (2) are satisfied. As an example of the layer structure of the decorative sheet of the present invention, there is a layer structure in which at least a pattern layer and a transparent resin layer are provided in this order on a base sheet. As shown in fig. 1, there is a layer structure (decorative sheet having a double layer standard of a synthetic resin backing layer) comprising a synthetic resin backing layer 11, a base sheet 12, a pattern layer 13 (a full coat ink layer and/or a pattern ink layer), an adhesive layer (not shown), a transparent resin layer 14, a primer layer (not shown), and a surface protective layer 15 in this order. As shown in fig. 2, the decorative sheet of the present invention may have a layer structure (multilayer decorative sheet) having no liner layer made of a synthetic resin and having a base sheet 12, a pattern layer 13 (a full coat ink layer and/or a pattern ink layer), an adhesive layer (not shown), a transparent resin layer 14, and a surface protective layer 15 in this order. As shown in fig. 3, the decorative sheet of the present invention may have a layer structure (single-layer decorative sheet) including a base sheet 12, a design pattern layer 13 (a full-coat ink layer and/or a pattern ink layer), a primer layer (not shown), and a surface protective layer 15 in this order. As shown in fig. 4, the decorative sheet of the present invention may be a decorative sheet (a back-printing-standard decorative sheet) having a pattern layer 13 (a full-coat ink layer and/or a pattern ink layer), an adhesive layer (not shown), a transparent resin layer 14, a primer layer (not shown), and a surface protective layer 15 in this order. Hereinafter, a decorative sheet having such a layer structure will be specifically described as a representative example.

(phosphazene flame retardant)

The phosphazene flame retardant is not particularly limited as long as a phosphazene compound is used. Examples of the phosphazene compound include a phosphazene compound having a cyclic structure represented by the following general formula (1) and a phosphazene compound having a linear structure represented by the following general formula (3).

In the general formula (1), n represents an integer of 1 or more, and A represents an alkoxy group having 1 to 4 carbon atoms or a phenoxy group represented by the following general formula (2).

In the general formula (2), R¹Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.

In the general formula (3), m represents an integer of 0 or1 or more, and B represents an alkoxy group having 1 to 4 carbon atoms or a phenoxy group represented by the following general formula (4).

In the general formula (4), R²Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.

The phosphazene flame retardant is preferably a phosphazene flame retardant using a phosphazene compound having a cyclic structure, from the viewpoint of further improving the flame retardancy of the decorative sheet.

As the phosphazene flame retardant, rabile FP-100 and rabile FP-110 manufactured by Kogyo Kagaku K.K.; SPB-100, SPS-100, SP-100, SPR-100, SA-100 and the like available from Otsuka chemical Co.

The phosphazene flame retardant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

In the decorative sheet having a thermoplastic resin layer having at least 1 layer selected from the group consisting of a transparent resin layer, a substrate sheet and a synthetic resin cushion layer, it is sufficient that at least 1 layer of the thermoplastic resin layer contains a phosphazene flame retardant, and when the decorative sheet has a transparent resin layer and a substrate sheet, for example, there are a configuration in which the transparent resin layer and the substrate sheet contain a phosphazene flame retardant, a configuration in which the transparent resin layer contains a phosphazene flame retardant and the substrate sheet does not contain a phosphazene flame retardant, a configuration in which the substrate sheet contains a phosphazene flame retardant and the transparent resin layer does not contain a phosphazene flame retardant, and the like.

When only the uppermost thermoplastic resin layer of the thermoplastic resin layers contains the phosphazene flame retardant, the content of the phosphazene flame retardant is preferably 3 mass% or more, and more preferably 4.4 mass% or more, assuming that the total mass of the thermoplastic resin layers is 100 mass%. In the case of the above configuration, the content of the phosphazene flame retardant is preferably 20% by mass or less, and more preferably 15% by mass or less, when the total mass of the thermoplastic resin layers is 100% by mass. When the lower limit of the content of the phosphazene flame retardant is within the above range, the flame retardancy of the decorative sheet is further improved. In addition, when the upper limit of the content of the phosphazene flame retardant is within the above range, the clarity of the decorative sheet is further improved.

When only the lowermost thermoplastic resin layer of the thermoplastic resin layers contains the phosphazene flame retardant, the content of the phosphazene flame retardant is preferably 14.0 mass% or more, and more preferably 14.4 mass% or more, where the total mass of the thermoplastic resin layers is 100 mass%. In the case of the above configuration, the content of the phosphazene flame retardant is preferably 30% by mass or less, and more preferably 20% by mass or less, when the total mass of the thermoplastic resin layers is 100% by mass. When the lower limit of the content of the phosphazene flame retardant is within the above range, the flame retardancy of the decorative sheet is further improved. When the upper limit of the content of the phosphazene flame retardant is within the above range, the lowermost layer exhibits more excellent strength.

(NOR type hindered amine Compound)

The decorative sheet of the present invention has at least 1 thermoplastic resin layer selected from the group consisting of a transparent resin layer, a substrate sheet and a synthetic resin-made backing layer, and preferably at least 1 of the thermoplastic resin layers contains a NOR-type hindered amine compound. Since the NOR type hindered amine compound can trap radicals generated from organic substances during combustion and make it difficult to continue combustion, the heat release amount can be further reduced in the heat release test according to ISO 5660-1 by containing the hindered amine compound in at least 1 of the thermoplastic resin layers. From the viewpoint of further improving the above-described effects, the decorative sheet of the present invention is more preferably configured such that at least 1 layer of the thermoplastic resin layer contains the phosphazene flame retardant and NOR-type hindered amine compound, that is, such that the phosphazene flame retardant and NOR-type hindered amine compound are contained in the same layer.

As the NOR-type hindered amine compound, for example, a compound represented by the following general formula (5) can be used.

In the general formula (5), R⁵～R⁸Each represents a hydrogen atom or an organic group represented by the following general formula (6). R⁵～R⁸At least 1 of them is an organic group of the following general formula (6).

In the general formula (6), R⁹Represents an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group or a phenylalkyl group having 7 to 15 carbon atoms, R¹⁰、R¹¹、R¹²And R¹³Each represents an alkyl group having 1 to 4 carbon atoms. R¹⁴Represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.

As R⁹The alkyl group having 1 to 17 carbon atoms is preferably a methyl group or an octyl group. The cycloalkyl group having 5 to 10 carbon atoms is preferably a cyclohexyl group. The phenyl group or phenylalkyl group having 7 to 15 carbon atoms is preferably a phenyl group. As R¹⁰～R¹³The alkyl group having 1 to 4 carbon atoms is preferably a methyl group. As R¹⁴The C1-12 linear or branched alkyl group is preferably n-butyl.

In the general formula (5), R is preferred⁵、R⁶And R⁷Is an organic radical of the formula (6), or R⁵、R⁶And R⁸Is an organic group of the general formula (6).

Specific examples of NOR-type hindered amine compounds include N, N '-tris {2, 4-bis [ (1-hydrocarbyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) alkylamino ] -s-triazin-6-yl } -3, 3' -ethylidenediiminediisopropyldipropylamine, N '-tris {2, 4-bis [ (1-hydrocarbyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) alkylamino ] -s-triazin-6-yl } -3, 3' -ethylidenediiminediisopropyldipropylamine and a crosslinked derivative thereof, bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) adipate, bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) adipate, and the like, Bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate, 1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl-octadecanoate, and the like.

The NOR-type hindered amine compound may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The content of the NOR-type hindered amine compound in each layer of the thermoplastic resin layer containing the NOR-type hindered amine compound is preferably 0.2 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of at least 1 selected from the polyolefin-based resin and the polyester-based resin in each layer.

(substrate sheet)

In the decorative sheet of the present invention, as described above, the base sheet is one of the thermoplastic resin layers which may contain the phosphazene-based flame retardant.

When the base sheet contains the phosphazene flame retardant, the content of the phosphazene flame retardant in the base sheet is preferably 5 parts by mass or more, and more preferably 7.5 parts by mass or more, when 100 parts by mass of at least 1 selected from the polyolefin resin and the polyester resin in the base sheet is used. The content of the phosphazene flame retardant in the base sheet is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. When the lower limit of the content of the phosphazene flame retardant in the base sheet is within the above range, the flame retardancy of the decorative sheet is further improved. When the upper limit of the content of the phosphazene flame retardant in the base sheet is within the above range, the base sheet exhibits further excellent strength.

The substrate sheet contains at least 1 resin selected from the group consisting of polyolefin resins and polyester resins.

Examples of the polyolefin-based resin include a polyolefin-based thermoplastic resin, such as polyethylene, an ethylene- α -olefin copolymer, polypropylene, polymethylpentene, polybutene, an ethylene-propylene copolymer, a propylene-butene copolymer, an ethylene-vinyl acetate copolymer, a saponified ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid ester copolymer. Of these, polypropylene is preferred.

As the polyester-based resin, a polyester-based thermoplastic resin can be used, and examples thereof include polyethylene terephthalate, polyalkylene terephthalate having high heat resistance [ for example, so-called trade name PET-G (manufactured by Eastman Chemical Company) which is polyethylene terephthalate obtained by substituting a part of ethylene glycol with 1, 4-cyclohexanedimethanol, diethylene glycol, or the like ], polybutylene terephthalate, polyethylene naphthalate, and a polyethylene naphthalate-isophthalate copolymer. Among these, polyalkylene terephthalates having high heat resistance are preferable.

The thickness of the substrate sheet is preferably 20 to 300. mu.m, more preferably 40 to 200. mu.m. The substrate sheet may be colored as desired. The surface may be subjected to surface treatment such as corona discharge treatment, plasma treatment, or ozone treatment, or may be coated with a primer as a base coating material for improving adhesion to an adjacent layer.

(Pattern layer)

The pattern layer is composed of a pattern ink layer and/or a full ink coating layer. The pattern layer can be formed by a known printing method such as gravure printing, offset printing, screen printing, and inkjet printing. Examples of the pattern ink layer include wood grain, stone grain, cloth grain, leather grain, geometric grain, characters, symbols, lines, various abstract grains, flowers, plants, landscape, and letters. The full-coating ink layer can be obtained by full-coating printing of a pigmented ink. The pattern layer is composed of one or two of a pattern ink layer and a full ink coating layer.

As the ink used for the pattern layer, 1 kind of chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane made of isocyanate and polyol, polyacrylic acid, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, cellulose resin, polyamide resin, or the like may be used as a vehicle, or 2 or more kinds thereof may be mixed and used, and a pigment, a solvent, various kinds of auxiliary agents, or the like may be added thereto to prepare an ink. Among them, from the viewpoint of environmental problems, adhesion to a surface to be printed, and the like, a mixture of 1 or 2 or more of polyester, polyurethane formed from isocyanate and polyol, polyacrylic acid, polyamide resin, and the like is preferable.

(transparent adhesive layer)

If necessary, a transparent adhesive layer is provided between the pattern layer and the transparent resin layer. The transparent adhesive layer can be obtained by applying a known adhesive for dry lamination such as a two-pack curable urethane resin and drying the adhesive.

The thickness of the transparent adhesive layer after drying is preferably about 0.1 to 30 μm, more preferably about 1 to 5 μm.

(transparent resin layer)

In the decorative sheet of the present invention, as described above, the transparent resin layer is one of the thermoplastic resin layers which may contain the phosphazene flame retardant.

When the phosphazene flame retardant is contained in the transparent resin layer, the content of the phosphazene flame retardant in the transparent resin layer is preferably 5 parts by mass or more, and more preferably 7.5 parts by mass or more, when at least 1 selected from the polyolefin resin and the polyester resin in the transparent resin layer is 100 parts by mass. The content of the phosphazene flame retardant in the transparent resin layer is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. When the lower limit of the content of the phosphazene flame retardant in the transparent resin layer is within the above range, the flame retardancy of the decorative sheet is further improved. In addition, when the upper limit of the content of the phosphazene flame retardant in the transparent resin layer is within the above range, the clarity of the decorative sheet is further improved.

The transparent resin layer contains at least 1 resin selected from the group consisting of polyolefin resins and polyester resins.

The transparent resin layer may be colored as long as it has transparency. In this case, a colorant may be added to the thermoplastic resin. As the coloring agent, a pigment or a dye used for the pattern layer may be used.

The transparent resin layer may contain various additives such as a filler, a matting agent, a foaming agent, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, and a soft component (for example, rubber).

The filler is not particularly limited as long as the transparency of the transparent resin layer is not impaired, but a filler exhibiting an average particle diameter of a wavelength of visible light or less is preferable from the viewpoint of further improving the clarity of the decorative sheet. Examples of the filler include inorganic fillers such as silica, calcium carbonate, talc, and clay.

The filler is not limited to the transparent resin layer, and is preferably contained in at least 1 layer of the thermoplastic resin layer, and is preferably contained in the same layer as the layer containing the phosphazene flame retardant. That is, at least 1 of the thermoplastic resin layers preferably contains a phosphazene flame retardant and a filler.

When at least 1 of the thermoplastic resin layers, particularly the transparent resin layer contains a phosphazene flame retardant, the transparent resin layer preferably further contains an inorganic filler having a polar group on the surface. The transparency resin layer containing the phosphazene flame retardant contains the inorganic filler having a polar group on the surface, and thus the clarity and flame retardancy of the decorative sheet are further improved. This is presumably because the polar portion of the phosphazene flame retardant is attracted to the polar group on the surface of the inorganic filler having a polar group, and the phosphazene flame retardant is present on the surface, thereby improving dispersibility. As the inorganic filler having a polar group on the surface, a hydrophilic inorganic filler can be used, and for example, an inorganic filler having a hydroxyl group such as a silanol group on the surface, more specifically, hydrophilic silica can be used.

The silica used as the filler may be natural or synthetic, or may be crystalline or amorphous. The synthetic amorphous silica may be prepared by any of a wet method and a dry method. The method for producing synthetic wet process silica produced by a wet process is not particularly limited, and examples thereof include a precipitation method and a gel method. The method for producing synthetic dry-process silica produced by the dry process is not particularly limited, and examples thereof include a combustion method and an arc method. In order to further improve the clarity of the decorative sheet, the silica is preferably a silica having a small average particle size, and more preferably a fumed silica obtained by a combustion method or a hydrophilic fumed silica.

The BET specific surface area of the filler such as hydrophilic fumed silica is preferably 50m²More preferably 130 m/g or more²(ii) at least g, more preferably 200m²More than g. When the BET specific surface area of the filler is within the above range, the average particle diameter is small, and the amount of silanol is increased in the case of hydrophilic fumed silica, so that the decrease in transparency of the transparent resin layer due to the addition of the filler is further suppressed, the dispersibility of the phosphazene flame retardant is further improved, and the clarity and flame retardancy of the decorative sheet are further improved. When the lower limit of the BET specific surface area of the filler is within the above range, the flame retardancy of the decorative sheet is improved, and the content of the phosphazene flame retardant can be reduced.

In the present specification, the BET specific surface area is a BET specific surface area obtained by measurement by a nitrogen adsorption method using a measurement method based on DIN 66131.

As the hydrophilic fumed silica used as the filler, commercially available ones can be used. Examples of such commercially available products include Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, and Aerosil 380 manufactured by Nippon Aerosil co.

When the phosphazene flame retardant and the filler are contained in the transparent resin layer, the content of the filler in the transparent resin layer is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and further preferably 200 parts by mass or more, when the content of the phosphazene flame retardant in the transparent resin layer is 100 parts by mass. When the lower limit of the content of the filler in the transparent resin layer is within the above range, the clarity of the decorative sheet is further improved. The content of the filler in the transparent resin layer is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less, based on 100 parts by mass of the resin component in the transparent resin layer.

The thickness of the transparent resin layer is preferably 60 μm or more, and more preferably 80 μm or more. The thickness of the transparent resin layer is preferably 300 μm or less, and more preferably 200 μm or less. When the lower limit of the thickness of the transparent resin layer is within the above range, the scratch resistance and abrasion resistance of the decorative sheet are further improved. When the upper limit of the thickness of the transparent resin layer is within the above range, the degree of difficulty in spreading the fire of the decorative sheet is further increased.

The surface of the transparent resin layer may be subjected to a surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, or dichromic acid treatment, as necessary. The surface treatment may be carried out according to a conventional method for each treatment.

A primer layer (a primer layer for facilitating the formation of the surface protective layer) may be formed on the surface of the transparent resin layer.

The undercoat layer can be formed by applying a known undercoat agent to the transparent resin layer. Examples of the primer include a urethane resin-based primer containing an acrylic-modified urethane resin or the like, and a resin-based primer formed of a block copolymer of acrylic and urethane.

The thickness of the undercoat layer is not particularly limited, but is usually about 0.1 to 10 μm, preferably about 1 to 5 μm.

(surface protective layer)

A surface protective layer (transparent surface protective layer) may be provided to impart surface properties such as abrasion resistance, water resistance, and stain resistance required for the decorative sheet.

The decorative sheet of the present invention preferably has a surface protective layer on the outermost surface. By providing the surface protective layer on the outermost surface, as will be described later, the surface protective layer can cooperate with at least 1 of the curable resins contained in the surface protective layer, and the surface protective layer can retard the generation of combustion gas due to the decomposition of the resin in the lower layer than the surface protective layer in the case of a fire or the like, thereby suppressing the spread of the fire and further improving the flame retardancy.

The resin for forming the surface protective layer preferably contains at least 1 kind of curable resin such as a thermosetting resin or an ionizing radiation curable resin. The ionizing radiation curable resin is particularly preferred from the viewpoint of high surface hardness, productivity, and the like. In addition, an electron beam curable resin is most preferable from the viewpoint of further improving the weather resistance. In addition, among the curable resins, an ionizing radiation curable resin, which is a curable resin having a high crosslinking density, is preferable, and an electron radiation curable resin is more preferable, from the viewpoint of delaying the generation of combustion gas due to the decomposition of the resin in the layer below the surface protective layer in the case of a fire or the like as described above.

Examples of the thermosetting resin include unsaturated polyester resins, polyurethane resins (including two-pack curable polyurethane), epoxy resins, aminoalkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea co-condensation resins, silicone resins, and polysiloxane resins.

The resin may be added with a curing agent such as a crosslinking agent and a polymerization initiator, and a polymerization accelerator. As the curing agent, for example, isocyanate, organic sulfonate or the like may be added to an unsaturated polyester resin, a polyurethane resin or the like, organic amine or the like may be added to an epoxy resin, and a peroxide such as methyl ethyl ketone peroxide or a radical initiator such as azobisisobutyronitrile or the like may be added to an unsaturated polyester resin.

As a method for forming the surface protective layer from the thermosetting resin, for example, a method of applying a solution of the thermosetting resin by a coating method such as a roll coating method or a gravure coating method and drying and curing the solution is exemplified. The amount of the solution to be applied is about 5 to 50 μm, preferably about 5 to 40 μm, in terms of solid content.

The ionizing radiation curable resin is not limited as long as it is a resin that is converted into a three-dimensional polymer structure by a crosslinking polymerization reaction upon irradiation with an ionizing radiation. For example, 1 or more of a prepolymer, an oligomer, and a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule that can be crosslinked by irradiation with an ionizing ray can be used. Examples thereof include: acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicone resins such as siloxane; a polyester resin; epoxy resins, and the like.

The ionizing radiation includes visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc., and among them, ultraviolet light and electron beams are preferable, and electron beams are more preferable.

As the ultraviolet source, a light source of an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. The wavelength of the ultraviolet ray is about 190 to 380 nm.

As the electron beam source, various electron beam accelerators such as a kockcroft-walton type, a van der bragg type, a resonance transformer type, an insulated core transformer type, a linear type, a denami type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000keV, more preferably about 100 to 300 keV. The irradiation dose of the electron beam is preferably about 2 to 15 Mrad.

The ionizing radiation-curable resin can be sufficiently cured by irradiation with electron beams, but when it is cured by irradiation with ultraviolet rays, a photopolymerization initiator (sensitizer) is preferably added.

In the case of a resin system having a radical polymerizable unsaturated group, at least 1 kind of photopolymerization initiator selected from acetophenone, benzophenone, thioxanthone, benzoin methyl ether, Michler's benzoyl benzoate, Michler's sketone, diphenyl sulfide, dibenzyldisulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate, and the like can be used, for example. In the case of a resin system having a cation-polymerizable functional group, at least 1 kind of aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonates, furyloxy sulfoxonium diallyl iodoxy salts (furanoxy sulfonium diallyl salts), and the like can be used.

The amount of the photopolymerization initiator added is not particularly limited, and is generally about 0.1 to 10 parts by mass per 100 parts by mass of the ionizing radiation-curable resin.

As a method for forming the protective layer from the ionizing radiation-curable resin, for example, a solution of the ionizing radiation-curable resin may be applied by a coating method such as a gravure coating method or a roll coating method. The amount of the solution to be applied is about 10 to 50 μm, preferably about 15 to 40 μm, in terms of solid content.

The thickness of the surface protective layer is preferably 4 μm or more, more preferably 8 μm or more, still more preferably 10 μm or more, and particularly preferably 12 μm or more. The thickness of the surface protective layer is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, particularly preferably 20 μm or less, and most preferably 15 μm or less. When the lower limit of the thickness of the surface protective layer is within the above range, the scratch resistance and abrasion resistance of the decorative sheet are further improved. In addition, when the upper limit of the thickness of the surface protective layer is within the above range, the flame retardancy of the decorative sheet is further improved.

In the present specification, when the fine particles 16 are exposed from the surface of the surface protective layer as indicated as ts in fig. 1 to 4, the thickness of the surface protective layer is measured using the portion other than the exposed fine particles 16 as the surface of the surface protective layer. As shown in fig. 1 to 4, when the decorative sheet is embossed, the thickness of the surface protective layer is measured at a portion other than the uneven pattern.

When the surface protective layer is further provided with scratch resistance and abrasion resistance, or when the gloss is reduced, fine particles 16 may be blended as shown in fig. 1 to 4. As the fine particles, inorganic filler can be cited. Examples of the inorganic filler include acrylic beads, mica, powdery alumina, silicon carbide, silica, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, silicon carbide, and glass fiber.

The average particle diameter of the fine particles is not particularly limited, and when the surface protective layer is further provided with scratch resistance and abrasion resistance, the average particle diameter is preferably larger than the thickness of the surface protective layer. The average particle diameter of the fine particles is larger than the thickness of the surface protective layer, whereby the scratch resistance and abrasion resistance of the decorative sheet are further improved. The average particle diameter of the fine particles for imparting further abrasion resistance and wear resistance to the surface protective layer is preferably more than 15 μm and 50 μm or less, more preferably 16 to 35 μm, and most preferably 16 to 20 μm.

The fine particles used as a matting agent for reducing the gloss of the surface protective layer preferably have an average particle diameter of 3 to 15 μm, more preferably 4 to 15 μm, and most preferably 8 to 15 μm. When the average particle diameter of the fine particles used as the matting agent is in the above range, the gloss of the surface protective layer can be further reduced.

In addition, when the scratch resistance is imparted to the surface protective layer, fine particles having a small average particle size may be used. The average particle diameter of the fine particles for imparting scratch resistance to the surface protective layer is preferably 1 to 5 μm, more preferably 3 to 5 μm, and still more preferably 3 to 4 μm. When the average particle diameter of the fine particles for imparting scratch resistance to the surface protective layer is in the above range, the scratch resistance of the surface protective layer is further improved.

In the present specification, the average particle diameter of the fine particles is a mode diameter. The mode diameter is a particle diameter indicating the maximum value of the particle diameter distribution, and is a particle diameter having the largest appearance ratio.

The amount of the inorganic filler is about 1 to 80 parts by mass per 100 parts by mass of the ionizing radiation curable resin.

The surface protective layer preferably contains the phosphazene flame retardant. When the surface protective layer contains the phosphazene flame retardant, the flame retardancy of the decorative sheet of the present invention can be further improved by coke formation and combustion gas capture with respect to heat applied from the surface of the decorative sheet.

The content of the phosphazene flame retardant in the surface protective layer is preferably 1 to 20 parts by mass, and more preferably 3 to 10 parts by mass, based on 100 parts by mass of the ionizing radiation curable resin.

(cushion layer made of synthetic resin)

In the decorative sheet of the present invention, the synthetic resin cushion layer is one of the thermoplastic resin layers which may contain a phosphazene flame retardant, as described above. By providing the synthetic resin cushion layer, the impact resistance of the decorative sheet is further improved.

When the synthetic resin backing layer contains the phosphazene flame retardant, the content of the phosphazene flame retardant in the synthetic resin backing layer is preferably 5 parts by mass or more, and more preferably 7.5 parts by mass or more, with respect to 100 parts by mass of the resin in the synthetic resin backing layer. The content of the phosphazene flame retardant in the cushion layer made of a synthetic resin is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. When the lower limit of the content of the phosphazene flame retardant in the synthetic resin backing layer is within the above range, the flame retardancy of the decorative sheet is further improved. Further, when the upper limit of the content of the phosphazene flame retardant in the cushion layer made of a synthetic resin is in the above range, the cushion layer made of a synthetic resin exhibits more excellent strength.

Examples of the resin constituting the backing layer made of a synthetic resin include polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, polyalkylene terephthalate having high heat resistance [ for example, so-called trade name PET-G (manufactured by Eastman Chemical Company) of polyethylene terephthalate obtained by substituting a part of ethylene glycol with 1, 4-cyclohexanedimethanol, diethylene glycol, or the like ], polybutylene terephthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, and the like. These resins may be used alone, or 2 or more kinds may be used.

The synthetic resin backing layer preferably has a thickness of 0.1 to 0.6mm, more preferably 0.15 to 0.45mm, and still more preferably 0.20 to 0.40 mm. When the lower limit of the thickness of the synthetic resin cushion layer is within the above range, the impact resistance of the decorative sheet is further improved. In addition, when the upper limit of the thickness of the synthetic resin cushion layer is in the above range, the warpage of the decorative sheet is further suppressed.

The lamination of the layers described above can be performed, for example, by the following method: after a pattern layer (a full coat ink layer or a pattern ink layer) is formed on one surface of a base sheet by printing, a transparent resin layer is laminated on the pattern layer by a known adhesive for dry lamination such as a two-liquid curable urethane resin by a dry lamination method, a T-die extrusion lamination method or the like, a surface protective layer is further formed, an intermediate is produced, and a synthetic resin layer backing layer produced by a T-die extrusion film-forming method or the like and a base sheet side of the intermediate are laminated by thermal lamination.

The total thickness of the decorative sheet is preferably 110 μm or more, and more preferably 120 μm or more. The total thickness of the decorative sheet is preferably 600 μm or less, and more preferably 400 μm or less. When the lower limit of the total thickness of the decorative sheet is within the above range, the scratch resistance and abrasion resistance of the decorative sheet are further improved. In addition, when the upper limit of the total thickness of the decorative sheet is within the above range, the degree of difficulty in spreading the fire of the decorative sheet is further increased.

In the present specification, when the fine particles 16 are exposed from the surface of the surface protective layer as denoted by td in fig. 1 to 4, the portions other than the exposed fine particles 16 are regarded as the surface of the decorative sheet, and the total thickness of the decorative sheet is measured. As shown in fig. 1 to 4, when the emboss pattern is formed on the decorative sheet by the embossing, the total thickness of the decorative sheet is measured at a portion other than the emboss pattern.

The decorative sheet is embossed from the transparent resin layer side or the surface protective layer side (upper side of the decorative sheet), whereby an uneven pattern can be formed. The embossing pattern may be formed by hot pressing, hair line processing, or the like. Examples of the uneven pattern include a duct groove, an uneven stone plate surface, a cloth surface texture, a pearskin texture, a sand texture, a hair texture, and a ruled line groove.

In the present specification, the layer thickness such as the total thickness of the decorative sheet is measured at a portion where the uneven pattern is not formed.

In the decorative sheet of the present invention, it is preferable that the various additives (fine particles contained in the surface protective layer, phosphazene flame retardant contained in the thermoplastic resin layer, and the like) added to each layer be encapsulated. The method for making the various additives into a capsule is not particularly limited, and the capsule can be made by a known method, and among them, a supercritical reverse evaporation method is preferable.

The supercritical reverse phase evaporation method is explained in detail below. The supercritical reverse phase evaporation method is as follows: the outer membrane forming material of the vesicle is uniformly dissolved in carbon dioxide under the conditions of temperature or pressure in the supercritical state or at the supercritical point or higher, an aqueous phase containing various additives as water-soluble or hydrophilic encapsulating materials is added to the resulting mixture, and a capsule-like vesicle containing various additives as encapsulating materials is formed by one layer of the membrane. The supercritical carbon dioxide is carbon dioxide in a supercritical state at a critical temperature (30.98 ℃) and a critical pressure (7.3773. + -. 0.0030MPa) or higher, and the carbon dioxide at a temperature or pressure condition at a critical point or higher is carbon dioxide under a condition where only the critical temperature or only the critical pressure exceeds the critical condition. By using the method, the unilamellar vesicles with the diameter of 50-800 nm can be obtained. In general, vesicles are a general term for a state in which a liquid phase is contained inside a vesicle having a membrane structure enclosed in a spherical shell, and in particular, vesicles whose outer membrane is composed of a biological lipid such as phospholipid are called "liposome".

Examples of the phospholipid include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingomyelins such as sphingomyelin, ceramide phosphoethanolamine, and ceramide phosphoglyceride.

As the material constituting the outer film, a dispersant such as a nonionic surfactant or a mixture thereof with cholesterol or triacylglycerol can be used.

As the nonionic surfactant, 1 or 2 or more of polyglycerin ether, dialkylglycerol, polyoxyethylene hardened castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly 2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylene copolymer, polyoxyethylene-polycaprolactam copolymer, and the like can be used.

The cholesterol may be 1 or more than 2 of cholesterol, alpha-cholestanol, beta-cholestanol, cholestane, desmosterol (5, 24-cholestan-3 beta-ol), sodium cholate, cholecalciferol, etc.

The outer membrane of the liposome may be formed of a mixture of phospholipid and a dispersing agent. In the decorative sheet of the present invention, the compatibility between the resin composition as a main component of each layer and various additives can be improved by forming the liposome in which the outer film is formed of the phospholipid.

Since the decorative sheet of the present invention has the above-described structure, even when it is laminated on a base material having a low thermal conductivity, the fire is not easily spread. Therefore, the flame retardant sheet can be used as a decorative sheet to be laminated on a substrate having a thermal conductivity of less than 0.1W/(m.K), and the flame is less likely to spread even when the flame retardant sheet is laminated on the substrate. Therefore, the decorative sheet of the present invention is suitable for use as a decorative sheet for interior materials, particularly a decorative sheet for floors.

2. Decorative board

The decorative sheet of the present invention is a decorative sheet having the above decorative sheet on a base material.

(decorative sheet)

As the decorative sheet constituting the decorative sheet of the present invention, the decorative sheet of the present invention described above can be used.

(substrate)

The material of the substrate is not particularly limited, and an inorganic substrate such as a metal plate of an aluminum plate or the like may be used, or a resin substrate in which a synthetic resin contains a filler such as an inorganic substance may be used. For example, as shown in fig. 5, a wood base material in which a surface material 22 made of a material exhibiting a thermal conductivity in the above range is laminated on a wood board 21 which is generally used for a decorative board such as a decorative board for a floor can be used. Fig. 6 to 9 show an example of the layer structure of the decorative sheet of the present invention using the base material of fig. 5. In fig. 6, a surface material 22 of a base material 2 is bonded to a synthetic resin cushion layer 11 of a decorative sheet 1, and the decorative sheet 1 is laminated on the base material 2 to form a decorative sheet. In fig. 7 and 8, the decorative sheet 1 is laminated on the base material 2 by attaching the surface material 22 of the base material 2 to the base material sheet 12 of the decorative sheet 1, thereby forming a decorative sheet. In fig. 9, the decorative sheet 1 is laminated on the base material 2 by bonding the surface material 22 of the base material 2 to the pattern layer 13 (full coat ink layer and/or pattern ink layer) side of the decorative sheet 1, thereby forming a decorative sheet.

The surface material is not particularly limited, and examples thereof include cork, wood, Medium Density Fiberboard (MDF), High Density Fiberboard (HDF), and the like, and these may be used in combination. Among these, cork is preferably used in view of imparting heat insulating properties and cushioning properties to the decorative sheet. That is, the base material preferably has a cork layer on the decorative sheet side.

The thickness of the surface material is not particularly limited, but is preferably 1.0 to 5.0mm, more preferably 1.0 to 2.5 mm.

The wood board is not particularly limited, and examples thereof include Medium Density Fiberboard (MDF), High Density Fiberboard (HDF), plywood, and the like. Among these, plywood is suitably used.

The thickness of the wooden plate is not particularly limited, but is preferably 4.0 to 15.0mm, more preferably 5.0 to 10.0 mm.

The method for laminating the surface material and the wood board is not particularly limited, and lamination can be performed by a conventionally known method such as lamination using an adhesive. The adhesive is not particularly limited, and a known adhesive for woodwork can be widely used. Examples of the adhesive include adhesives containing polyvinyl acetate, polyvinyl chloride, polyurethane, acrylic polyurethane, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, chloroprene rubber, natural rubber, and the like as an active ingredient. Examples of the thermosetting adhesive include melamine-based, phenol-based, and urea-based (e.g., vinyl acetate-urea-based) adhesives.

The thermal conductivity of the base material constituting the decorative sheet of the present invention on the side to which the decorative sheet is bonded may be less than 0.1W/(m · K). In the present specification, the thermal conductivity of the base material is measured by the following measurement method.

(method of measuring thermal conductivity of base Material)

The material forming the layer on the side of the substrate to which the decorative sheet was attached was cut into a circular shape having a diameter of 40mm to prepare a sample for measurement. The measurement samples were stacked in the thickness direction in an even number so as to have a thickness exceeding 15 mm. Next, sensors were inserted into half the number of positions of the stacked measurement samples, and the measurement samples were measured according to ISO 22007-2: 2008, heat conductivity was measured by hot plate method. When the measurement samples are stacked, the air layer included between the adjacent measurement samples is negligible.

An example of a method for measuring the thermal conductivity is shown. As a sample for measurement, cork having a diameter of 40mm and a thickness of 1.5mm was prepared and used as a sample for measurement. When the measurement samples were stacked, 30 measurement samples were stacked so that the total thickness exceeded 15 mm. Thus, a 45mm laminate was formed. Next, a sensor was interposed between the 15 th and 16 th measurement samples (positions of 22.5 mm), which were half the thickness of the laminate, and the thickness was measured according to ISO 22007-2: 2008, heat conductivity was measured by hot plate method.

In the case of using cork wood having a thickness of 2.0mm as the measurement sample, since the thickness of the laminate is 40mm when 20 pieces are stacked, the sensor is preferably interposed between the 10 th and 20 th measurement samples.

In the case of using cork with a thickness of 1.0mm as the measurement sample, the thickness of the laminate is 40mm when 40 pieces are stacked, and therefore the sensor is preferably sandwiched between the 20 th and 21 st measurement samples.

The method of laminating the decorative sheet on the front surface of the base material is not particularly limited, and lamination can be performed by a conventionally known method such as forming an adhesive layer on the front surface of the base material and then laminating the decorative sheet.

The thickness of the adhesive layer is not particularly limited, and the thickness after drying is preferably 0.1 to 100 μm, more preferably 0.1 to 30 μm, and still more preferably 1 to 20 μm.

Examples of the adhesive used for the adhesive layer include a water-soluble emulsion adhesive, a polyester adhesive, an acrylic adhesive, and a polyurethane adhesive. The adhesive may be used in 1 kind, or 2 or more kinds may be used in combination.

The decorative sheet of the present invention has the above-described structure, and therefore, is excellent in flame retardancy and can exhibit high clarity. Therefore, the decorative sheet of the present invention is suitably used as a decorative sheet for interior materials, particularly a decorative sheet for floors.

Examples

The present invention will be described in more detail below by way of examples and comparative examples. However, the present invention is not limited to the examples.

Example 1

(production of decorative sheet)

As a substrate sheet, an opaque colored polypropylene film having a thickness of 60 μm was prepared. Next, both surfaces of the base sheet were subjected to corona discharge treatment, and then an undercoat layer (thickness: 2 μm) of a two-liquid curable polyurethane resin was formed on the back surface of the base sheet, and a pattern layer was formed on the front surface of the base sheet from a curable printing ink containing an acrylic polyurethane resin by a gravure printing method. An adhesive agent of a two-liquid curable polyurethane resin is applied to the pattern layer to form a transparent adhesive layer. Further, on the adhesive layer, a transparent polypropylene resin containing a phosphazene flame retardant shown below was heated, melted and extruded by a T-die extruder to form a thermoplastic transparent resin layer (thickness 100. mu.m).

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass.

Next, after the surface of the transparent resin layer was subjected to corona discharge treatment, an undercoat layer (thickness 2 μm) of a two-liquid curable polyurethane resin was formed on the transparent resin layer. Then, an electron beam-curable resin composition containing a urethane (meth) acrylate oligomer was coated on the undercoat layer by a gravure coating method and dried, and then, an electron beam was irradiated under conditions of an accelerating voltage of 165keV and 30kGy, thereby forming a surface protective layer so that the thickness became 15 μm.

Next, the surface-protecting layer side is heated by an infrared non-contact heater to soften the substrate sheet and the transparent resin layer, and then embossing by hot pressing is immediately performed from the surface-protecting layer side to impart an uneven pattern. The decorative sheet of example 1 was produced by the above production method.

The total thickness of the transparent resin layer and the substrate sheet of the decorative sheet of example 1 was 160 μm, and the content of the phosphazene flame retardant was 5.7 mass% when the total mass of the transparent resin layer and the substrate sheet was 100 mass%.

(production of decorative Panel)

A veneer having a thickness of 1.5mm was bonded to a plywood having a thickness of 7.5mm with an adhesive to prepare a wood base.

Next, the surface of the decorative sheet on the base sheet side was bonded to the surface of the wood base on the cork sheet side with a two-component curable water-soluble emulsion adhesive. The coating amount of the two-component curable aqueous emulsion adhesive was 130g/m²。

The following were used as the water-soluble emulsion adhesive.

Water-soluble emulsion adhesive

Main agent: "BA-10L" Japan Coating Resin Co., Ltd., manufactured and modified ethylene vinyl acetate;

curing agent: "BA-11B" Japan Coating Resin Co., manufactured by Ltd., isocyanate group, mixing ratio: the main agent and the curing agent are 100:2.5 (mass ratio).

Then, 10kg/m of a solution was applied at 25 DEG C²Curing for 3 days under the pressure of the pressure, and manufacturing the decorative plate.

Example 2

A decorative sheet and a decorative plate were produced in the same manner as in example 1, except that the content of the phosphazene flame retardant in the transparent resin layer was changed to 12.5 parts by mass. The content of the phosphazene flame retardant was 8.4 mass% when the total mass of the transparent resin layer and the substrate sheet was 100 mass%.

Examples3

The substrate sheet was a 100 μm thick opaque colored polypropylene film and contained a phosphazene flame retardant. The substrate sheet was compounded as follows.

Polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 30 parts by mass.

The thickness of the transparent resin layer was set to 60 μm and the phosphazene flame retardant was not contained.

Except for this, a decorative sheet and a decorative plate were produced in the same manner as in example 1. The content of the phosphazene flame retardant was 14.4 mass% when the total mass of the transparent resin layer and the substrate sheet was 100 mass%.

Example 4

A decorative sheet or a decorative plate was produced in the same manner as in example 1 except that SPB-100 (available from Otsuka chemical Co., Ltd., phosphazene) was used as the phosphazene flame retardant contained in the transparent resin layer. The content of the phosphazene flame retardant was 5.7% by mass, assuming that the total mass of the transparent resin layer and the substrate sheet was 100% by mass.

Example 5

A decorative sheet and a decorative plate were produced in the same manner as in example 1, except that a transparent polypropylene resin containing a phosphazene flame retardant and a filler shown below was heated, melted and extruded on the adhesive layer by a T-die extruder to form a thermoplastic transparent resin layer (thickness: 100 μm). The content of the phosphazene flame retardant was 5.8 mass% when the total mass of the transparent resin layer and the substrate sheet was 100 mass%.

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 12 parts by mass;

filler (product name: AEROSIL 300 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area300m²(iv)/g): 24 parts by mass.

Example 6

A decorative sheet and a decorative plate were produced in the same manner as in example 1, except that a transparent polypropylene resin containing a phosphazene flame retardant and a filler shown below was heated, melted and extruded on the adhesive layer by a T-die extruder to form a thermoplastic transparent resin layer (thickness: 100 μm). The content of the phosphazene flame retardant was 5.0 mass% when the total mass of the transparent resin layer and the substrate sheet was 100 mass%.

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 300 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 300m²(iv)/g): 20 parts by mass.

Example 7

A decorative sheet and a decorative plate were produced in the same manner as in example 1, except that a transparent polypropylene resin containing a phosphazene flame retardant and a filler shown below was heated, melted and extruded on the adhesive layer by a T-die extruder to form a thermoplastic transparent resin layer (thickness: 100 μm). The content of the phosphazene flame retardant was 4.0 mass% when the total mass of the transparent resin layer and the substrate sheet was 100 mass%.

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 7.5 parts by mass;

filler (product name: AEROSIL 300 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 300m²(iv)/g): 15 parts by mass.

Example 8

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 50 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 50m²(iv)/g): 20 parts by mass.

Example 9

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 130 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 130m²(iv)/g): 20 parts by mass.

Example 10

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 200m²(iv)/g): 20 parts by mass.

Example 11

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 380 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 380m²(iv)/g): 20 parts by mass.

Example 12

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 200m²(iv)/g): and 5 parts by mass.

Example 13

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 200m²(iv)/g): 10 parts by mass.

Example 14

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 200m²(iv)/g): 15 parts by mass.

Example 15

Transparent polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET ratioSurface area 200m²(iv)/g): 25 parts by mass.

Comparative example 1

A decorative sheet and a decorative plate were produced in the same manner as in example 1, except that PX200 (phosphoric acid condensation ester flame retardant, manufactured by gakazaki chemical corporation) was used as the flame retardant contained in the transparent resin layer and the content of the flame retardant in the transparent resin layer was set to 15 parts by mass. The content of the flame retardant was 8.2% by mass, assuming that the total mass of the transparent resin layer and the substrate sheet was 100% by mass.

Comparative example 2

A decorative sheet and a decorative plate were produced in the same manner as in example 1, except that FCP790 (ammonium polyphosphate, manufactured by suzuki chemical corporation) was used as the flame retardant contained in the transparent resin layer and the content of the flame retardant in the transparent resin layer was 30 parts by mass. The content of the flame retardant was 14.4% by mass, assuming that the total mass of the transparent resin layer and the substrate sheet was 100% by mass.

Reference example 1

A decorative sheet and a decorative sheet were produced in the same manner as in example 1, except that the transparent resin layer was made to contain no phosphazene flame retardant and filler.

(evaluation)

The decorative sheets and decorative plates of examples and comparative examples produced as described above were evaluated by the following methods.

(1) Horizontal combustibility (fire retardancy: degree of difficulty in spreading fire)

The decorative plate was cut into pieces of 9cm × 30cm to prepare test pieces. As shown in fig. 10 and 11, a metal rectangular stage 103 was placed on a stage 102 of a commercial household heater 101(Zaigle Handsome SJ-100 (trade name)), a test piece 105 was placed in a metal frame 104 provided on the stage, and a test was conducted on the degree of difficulty in the spread of fire under conditions of a heater angle of 45 ° and a heater output scale of 4. Specifically, the test piece was preheated for 2 minutes using the above-mentioned household heater. Next, as shown in fig. 10, the end 106 of the test piece on the heater side in the longitudinal direction was heated by the igniter 107 for 1 minute to ignite, and as shown in fig. 11, the flame was spread in the longitudinal direction of the test piece 105. Next, the flame propagation state was visually observed, and the combustion distance (L1) and the combustion duration were evaluated as follows.

[ distance of combustion (L1) ]

After the test piece was ignited, the flame of the igniter was extinguished, and the distance of flame propagation from the initial ignition was measured and evaluated as the distance of flame propagation (L1) according to the following evaluation criteria. Among them, when the value is + evaluation or more, evaluation is practically no problem.

++: l1 is less than 5 cm;

+: l1 is more than 5cm and less than 10 cm;

-: l1 is 10cm or more.

[ duration of Combustion ]

After the test piece was ignited, the ignition of the igniter was extinguished, and the duration of combustion from the initial ignition to self-extinguishing was measured and evaluated according to the following evaluation criteria. Among them, when the value is + evaluation or more, evaluation is practically no problem.

+++: a duration of combustion of less than 100 seconds, or no ignition;

++: the combustion duration is 100 seconds or more and less than 300 seconds;

+: the combustion duration is 300 seconds or more and less than 600 seconds;

-: the combustion duration is 600 seconds or longer (600 seconds without self-extinguishing).

(2) Clarity of presentation

[ haze ]

Only the transparent resin layer of each decorative sheet was put into the apparatus using a direct-reading haze meter manufactured by toyoyo seiki, ltd, and the haze value was measured. Among them, when the haze value is 90.0 or less, it is evaluated that there is no problem in practical use.

[ appearance ]

The appearance of the decorative sheet was visually observed from the transparent resin layer side (surface protective layer side) of the decorative sheet, and evaluated according to the following evaluation criteria. Among them, when the value is + evaluation or more, evaluation is practically no problem.

++: the pattern design of the pattern layer is vivid and visible;

+: the design of the pattern layer looks slightly blurred;

-: the design of the pattern layer appears to be discolored or to appear blurred.

The results are shown in tables 1 to 4.

[ Table 1]

[ Table 2]

[ Table 3]

In table 3, the influence of BET specific surface area of the filler (hydrophilic fumed silica) on the clearness is shown. It is found that when the BET specific surface area of the filler is increased, the haze value of the transparent resin layer is decreased, and the clarity is further improved.

[ Table 4]

In table 4, the influence of the amount of the filler (hydrophilic fumed silica) on the clearness is shown. It is generally considered that when the amount of the filler in the transparent resin layer is increased, the haze value becomes high and the clarity becomes poor. However, from the results in table 4, it is understood that when the amount of the filler (hydrophilic fumed silica) contained in the transparent resin layer containing the phosphazene flame retardant is increased, the haze value is lowered and the clarity is further improved.

Example 16

The transparent resin layer (thickness: 80 μm) is composed of a phosphazene flame retardant, a NOR type hindered amine compound, and a filler. Further, the substrate sheet (thickness: 60 μm) was constituted to contain a NOR type hindered amine compound. The transparent resin layer and the substrate sheet are blended as follows.

(transparent resin layer)

Polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

NOR type hindered amine (product name: Flamestab NOR116FF (manufactured by BASF corporation)): 3 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 200m²(iv)/g): 20 parts by mass.

(substrate sheet)

Polypropylene resin: 100 parts by mass;

NOR type hindered amine (product name: Flamestab NOR116FF (manufactured by BASF corporation)): 2.3 parts by mass.

Except for this, a decorative sheet was produced in the same manner as in example 1.

(production of decorative Panel)

The surface of the decorative sheet on the base sheet side was bonded to the surface of an aluminum plate having a thickness of 0.8mm by a two-component curable polyurethane adhesive. The coating amount of the two-component curable polyurethane adhesive was 2g/m²。

Among them, the following products were used as the two-component curable polyurethane adhesive.

Two-liquid curing polyurethane adhesive

Adhesive agent: ARON MELT PES-320 SK: 100 parts by mass;

curing agent: coronate: and 5 parts by mass.

Except for this, a decorative sheet was produced in the same manner as in example 1.

Example 17

The transparent resin layer (thickness: 80 μm) and the substrate sheet (thickness: 60 μm) were constituted by containing the phosphazene flame retardant, the NOR-type hindered amine compound, and the filler. The transparent resin layer and the substrate sheet are blended as follows.

(transparent resin layer)

Polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

NOR type hindered amine (product name: Flamestab NOR116FF (manufactured by BASF corporation)): 3 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 200m²(iv)/g): 20 parts by mass.

(substrate sheet)

Polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

NOR type hindered amine (product name: Flamestab NOR116FF (manufactured by BASF corporation)): 2.3 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 200m²(iv)/g): 20 parts by mass.

Except for this, a decorative sheet and a decorative plate were produced in the same manner as in example 16.

Example 18

(transparent resin layer)

Polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 20 parts by mass;

NOR type hindered amine (product name: Flamestab NOR116FF (manufactured by BASF corporation)): 3 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 200m²(iv)/g): 20 parts by mass.

(substrate sheet)

Polypropylene resin: 100 parts by mass;

NOR type hindered amine (product name: Flamestab NOR116FF (manufactured by BASF corporation)): 2.3 parts by mass;

except for this, a decorative sheet and a decorative plate were produced in the same manner as in example 16.

Example 19

The transparent resin layer (thickness: 80 μm) contains a phosphazene flame retardant and a filler. Further, the substrate sheet (thickness: 60 μm) was constituted to contain a NOR type hindered amine compound. The transparent resin layer and the substrate sheet are blended as follows.

(transparent resin layer)

Polypropylene resin: 100 parts by mass;

phosphazene flame retardant (product name: Rabile FP-100 (manufactured by Kyowa Kagaku Co., Ltd.), phosphazene): 10 parts by mass;

filler (product name: AEROSIL 200 (manufactured by Nippon AEROSIL Co., Ltd.), hydrophilic fumed silica, BET specific surface area 200m²(iv)/g): 20 parts by mass.

(substrate sheet)

Polypropylene resin: 100 parts by mass;

NOR type hindered amine (product name: Flamestab NOR116FF (manufactured by BASF corporation)): 2.3 parts by mass.

Except for this, a decorative sheet and a decorative plate were produced in the same manner as in example 16.

Comparative example 3

The transparent resin layer (thickness: 60 μm) and the substrate sheet (thickness: 60 μm) were formed without containing a flame retardant, a NOR-type hindered amine compound, and a filler. Except for this, a decorative sheet and a decorative plate were produced in the same manner as in example 16.

Comparative example 4

The transparent resin layer (thickness: 80 μm) and the substrate sheet (thickness: 60 μm) were formed without containing a flame retardant, a NOR-type hindered amine compound, and a filler. Except for this, a decorative sheet and a decorative plate were produced in the same manner as in example 16.

Reference example 2

A transparent polypropylene resin containing a NOR-type hindered amine compound shown below was heated, melted and extruded by a T-die extruder to form a thermoplastic single-layer transparent resin layer (thickness: 80 μm).

Polypropylene resin: 100 parts by mass;

NOR type hindered amine (product name: Flamestab NOR116FF (manufactured by BASF corporation)): 3 parts by mass.

A decorative sheet was produced in the same manner as in example 16 using a single transparent resin layer.

Reference example 3

The transparent polypropylene resin containing the flame retardant shown below was heated, melted and extruded by a T-die extruder to form a thermoplastic single-layer transparent resin layer (thickness: 80 μm).

Polypropylene resin: 100 parts by mass;

40 parts by mass of a polyphosphoric acid-based flame retardant (product name: FCP790 (manufactured by Suzuki chemical Co., Ltd., ammonium polyphosphate)).

A decorative sheet was produced in the same manner as in example 16 using a single transparent resin layer.

(evaluation)

The decorative sheets of examples 16 to 19, comparative examples 3 and 4, and reference examples 2 and 3 produced as described above were evaluated by the following methods.

(3) Test for exothermic Property

The total heat release amount and the maximum heat release rate of the decorative sheet were measured by a combustion test using a cone calorimeter under a condition of a combustion time of 3 minutes by a measuring method based on ISO 5660-1. Evaluation was carried out according to the following evaluation criteria. When the total heat release amount or the maximum heat release amount is evaluated to be + + or more, it is evaluated that there is no problem in practical use.

[ Total heat release amount ]

+++: less than 5.20MJ/m²；

++：5.20MJ/m²Above and below 5.38MJ/m²；

+：5.38MJ/m²Above and below 5.55MJ/m²；

－：5.55MJ/m²The above.

[ maximum Heat Release Rate ]

+++: less than 133.93KW/m²；

++：133.93KW/m²Above and less than 153.92KW/m²；

+：153.92KW/m²Above and less than 173.93KW/m²；

－：173.93KW/m²The above.

The results are shown in Table 5.

Reference example 4

In example 1, no flame retardant was added to the thermoplastic resin. In addition, no surface protection layer was formed. Except for this, a decorative sheet and a decorative plate were produced in the same manner as in example 1.

Reference example 5

In example 1, no flame retardant was added to the thermoplastic resin. Except for this, a decorative sheet and a decorative plate were produced in the same manner as in example 1.

(evaluation)

For the decorative panels of reference examples 4 and 5, the rate of fire spread was evaluated and compared by the following method.

[ burning distance (L1) ] was determined by the method described in the above (1) horizontal combustibility (flame retardancy: degree of difficulty in fire spread) ". In fig. 10 and 11, the conditions were changed to a heater angle of 20 ° so as to obtain a strong heating condition in which the spread of the fire was easily progressed, and the measurements were performed. After the test piece was ignited, the igniter was extinguished, and the combustion time from the initial ignition was used as the test time, and the combustion distance in the test time was measured, plotted and compared. The results are shown in FIG. 12.

Description of the symbols

1. A decorative sheet; 11. a synthetic resin cushion layer; 12. a substrate sheet; 13. a pattern layer; 14. a transparent resin layer; 15. a surface protection layer; 16. microparticles; 2. a substrate; 21. a wooden board; 22. a surface material; 101. a household heater; 102. a table of a household heater; 103. a metal rectangular table; 104. a metal frame; 105. a test piece; 106. a heater-side end portion in the longitudinal direction of the test piece; 107. an igniter; l1 combustion distance.

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