JP2005022385A - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in design just like as a conventional vinyl chloride resin sheet, which has an excellent fire-retardancy and anti-fire spreading owing to high form-holding ability upon burning, a high mechanical strength, a high stability and a high surface strength. <P>SOLUTION: The sheet comprises a multi-layered formed sheet material and an adhesive layer laminated on the sheet material, in which the formed sheet material comprises a polyester resin layer and a thermoplastic resin composition layer and the polyester resin layer is placed on the surface opposite to the laminated adhesive layer and the thermoplastic resin composition comprises 100 pts.wt. of a thermoplastic resin, 0.1-100 pts.wt. of lamellar silicate and 0.1-70 pts.wt. of a metal hydroxide. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention is excellent in flame retardancy and fire spread prevention, exhibits excellent flame retardancy and fire spread prevention effects due to the shape retention effect during combustion, and has high mechanical strength, stability, surface strength, The present invention relates to a decorative sheet excellent in design as well as a sheet made of vinyl resin.

In general, the decorative sheet is required to have flame retardancy for the purpose of preventing the spread of fire through the decorative sheet in a fire in addition to the concealability and workability of the base material. For this reason, conventionally, a decorative sheet made of a soft polyvinyl chloride resin has been used.

In recent years, polymer materials used for industrial applications have been desired to be converted to so-called environmentally-friendly materials due to the treatment of waste plastics and environmental hormone problems. Specifically, for example, due to problems such as the generation of dioxins during combustion and the toxicity of added plasticizers, conversion from soft polyvinyl chloride resins to materials containing no halogen atoms, such as polyolefin resins, has been studied. Yes.
In the field of decorative sheets as well, for example, Patent Document 1 and Patent Document 2 disclose decorative sheets made of polyolefin resin in order to switch to an environment-adaptive material with a low environmental load during combustion. However, the polyolefin resin is one of the most flammable resins, and it has been difficult to achieve high flame retardancy.

As a method for making a polyolefin resin flame-retardant, a method of kneading a large amount of a flame retardant into the resin is known.
Among flame retardants, if a flame retardant composed of a halogen-containing compound is used, the flame retardant effect is high,
A decrease in moldability and a decrease in mechanical strength of the obtained sheet-like molded body are also relatively small. However, if a flame retardant composed of halogen-containing compounds is used, a large amount of halogen-based gas may be generated during molding or combustion, and the generated halogen-based gas may corrode equipment or have an undesirable effect on the human body. There is. Therefore, so-called non-halogen flame retardant technology that does not use a halogen-containing compound is strongly desired from the viewpoint of safety.

Examples of non-halogen flame retardant technology for polyolefin resins include, for example, Patent Document 3 and Patent Document 4 that use metal compounds such as aluminum hydroxide, magnesium hydroxide, and basic magnesium carbonate that do not generate toxic gas during combustion. A method of adding is disclosed.
However, in order to impart sufficient flame retardancy to the flammable polyolefin resin, it is necessary to add a large amount of a metal compound. As a result, the mechanical strength (particularly stretchability, tearing) of the obtained molded body is required. There is a problem that it is difficult to put it into practical use, for example, it is difficult to form into a film or sheet. In addition, even if metal hydroxide is added to the polyolefin-based resin, the coating layer is not formed during combustion, brittle ash is exposed, and the residue falls off. The fire spread due to deformation of the material cannot be stopped.

Other non-halogen flame retardant technologies for polyolefin resins include, for example, adding phosphorus flame retardants to polyolefin resins, forming a coating on the surface during combustion, and utilizing the oxygen barrier effect of this combustion coating A method for developing flame retardancy has been proposed. However, in order to impart sufficient flame retardancy to the flammable polyolefin resin, it is necessary to add a large amount of a phosphorus flame retardant, and as a result, the mechanical strength of the resulting molded product is significantly reduced. There was a problem that it was difficult to put to practical use. In addition, when a phosphorus-based flame retardant is added to a polyolefin-based resin, it is difficult to form a strong coating layer as a continuous layer although it forms a coating locally, and the mechanical strength of the local coating is Because it is very weak, brittle ash is exposed during combustion, and the residue falls off, so the function as a heat insulation layer is lost early,
There was a problem that the spread of fire due to deformation of the material could not be stopped.

Further, for example, Patent Document 5 discloses a resin composition in which red phosphorus or a phosphorus compound and expandable graphite are added to a polyolefin resin. However, although this resin composition has sufficient flame retardancy when viewed from the oxygen index, it can actually form a film only locally, and a strong film layer can be formed as a continuous layer. Can not. The mechanical strength of the local coating is very weak, and brittle ash is exposed during combustion. Residues fall off, so that the function as a heat insulating layer is lost early, and the spread of fire due to deformation of the material is stopped. I can't. In addition, when red-brown red phosphorus is used, the resulting decorative sheet is colored orange, so that the color developability particularly required in the decorative sheet is limited, and the desired color cannot be expressed, resulting in insufficient design. was there. Furthermore, in order to give sufficient flame retardancy to polyolefin resin, it is necessary to add a large amount of red phosphorus or phosphorus compound and expandable graphite, and ensure the flexibility and elongation necessary for a decorative sheet. There was a problem that became difficult.

As a flame retardant method using non-halogen or non-phosphorus, for example, Patent Document 6 discloses a method of blending flat talc. However, this method also provides 80 to 1 to 100 parts by weight of the polyolefin resin in order to impart sufficient flame retardancy to the polyolefin resin.
It is necessary to add a large amount of flat talc of 30 parts by weight, and there is a problem that it is difficult to ensure flexibility and elongation, which are important physical properties as a decorative sheet.

In addition, the decorative sheet needs to be provided with a transparent layer on the printed layer for the purpose of protecting the printed layer or improving the glossiness of the entire decorative sheet. It is required to have flammability.
However, when a transparent layer is formed by using a conventional flame retardant method, the transparency of the transparent layer is impaired, causing problems such as the printed layer pattern appearing blurred, and the decorative sheet. Since the overall designability deteriorated, it could not be put to practical use.

JP-A-8-3380 JP-A-8-1897 JP-A-57-165437 JP 61-36343 A JP-A-6-25476 JP-A-6-41371

In view of the above situation, the present invention is excellent in flame retardancy and fire spread prevention, exhibits excellent flame retardancy and fire spread prevention effects due to the shape retention effect during combustion, and has mechanical strength and stability, particularly necking and sink marks. Another object of the present invention is to provide a decorative sheet that is less in design and excellent in design as in the case of a conventional vinyl chloride resin sheet.

The present invention is a decorative sheet comprising a sheet-like molded article having a multilayer structure and an adhesive layer laminated on the sheet-like molded article, wherein the sheet-like molded article comprises at least a layer made of a polyester-based resin. A layer composed of a thermoplastic resin composition, the layer composed of the polyester-based resin is on a surface opposite to the side on which the pressure-sensitive adhesive layer is laminated, and the thermoplastic resin composition is thermoplastic. It is a decorative sheet containing 0.1 to 100 parts by weight of layered silicate and 0.1 to 70 parts by weight of metal hydroxide with respect to 100 parts by weight of resin.
The present invention is described in detail below.

The decorative sheet of the present invention comprises a sheet-like molded article and an adhesive layer laminated on the sheet-like molded article.
The sheet-like molded body has at least a layer made of a polyester resin and a layer made of a thermoplastic resin composition, and the layer made of the polyester resin is opposite to the side on which the pressure-sensitive adhesive layer is laminated. On the side surface.

The layer made of the polyester-based resin has a role as a transparent layer for protecting the printed layer or improving the glossiness of the entire decorative sheet of the present invention.
The polyester-based resin is not particularly limited as long as it has excellent transparency when used as a transparent layer of a decorative sheet and has relatively high flame retardancy. For example, crystalline aromatic polyester, polyester-based resin A thermoplastic elastomer, liquid crystal polyester, etc. are mentioned.

The crystalline aromatic polyester can be obtained by reacting an aromatic dicarboxylic acid or an ester-forming derivative thereof with a low molecular weight aliphatic diol or a high molecular weight diol.
Examples of the aromatic dicarboxylic acid or its ester-forming derivative include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, paraphenylene dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, dimethyl orthophthalate, and dimethyl naphthalene dicarboxylate. And dimethyl paraphenylene dicarboxylate. These may be used alone or in combination of two or more.

Examples of the low molecular weight aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5- Pentanediol, 1,6-hexanediol,
Examples include 1,4-cyclohexanedimethanol. These may be used alone or in combination of two or more.

Examples of the high molecular weight diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, and the like. These may be used alone or in combination of two or more.

Examples of the crystalline aromatic polyester composed of the above components include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, butanediol terephthalate polytetramethylene glycol copolymer, and the like. It is done. These may be used alone or in combination of two or more.

It does not specifically limit as said polyester-type thermoplastic elastomer, A conventionally well-known thing can be used. Specific examples include polyester-based thermoplastic elastomers in which the hard segment is the crystalline aromatic polyester and the soft segment is an aliphatic polyether and / or an aliphatic polyester.

It does not specifically limit as said liquid crystalline polyester, A conventionally well-known thing can be used. Specifically, for example, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and polyethylene terephthalate; p-hydroxybenzoic acid and 2-
A thermotropic liquid crystalline polyester comprising hydroxy-6-naphthoic acid as the main constituent unit; p
-Thermotropic liquid crystal polyester mainly composed of hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and terephthalic acid.

The preferable lower limit of the thickness of the layer made of the polyester-based resin is 15 μm, and the preferable upper limit is 7
0 μm. When the thickness is less than 15 μm, the original function of protecting the printed layer may be insufficient, and when it exceeds 70 μm, the curved surface workability may be insufficient.

Further, the layer made of the polyester resin has a preferable lower limit of the stress at 2% elongation of 20N.
/ 10 mm, and a preferable upper limit is 60 N / 10 mm. When it is less than 20 N / 10 mm,
Problems such as air-engagement due to lowering of the film's waist may occur, resulting in insufficient curved surface workability. If it exceeds 60 N / 10 mm, the physical properties of the decorative sheet will be reduced, and the texture as a decorative sheet May be damaged.

It should be noted that the layer made of the polyester-based resin has, as necessary, a nucleating agent that can serve as a crystal nucleus for refining crystals as an auxiliary means for homogenizing physical properties within a range that does not hinder achievement of the problems of the present invention. , One or more of various additives such as antioxidants (anti-aging agents), heat stabilizers, light stabilizers, UV absorbers, lubricants, flame retardants, antistatic agents, antifogging agents, etc. Also good.

The thermoplastic resin is not particularly limited. For example, polyolefin resin, polystyrene resin, polyester resin, polyamide resin, polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl acetate resin, poly (meth) acrylic. Examples include acid ester resins, norbornene resins, polyphenylene ether resins, polyoxymethylene resins, and the like. Among these, polyolefin resins are preferably used. This is because by using the polyolefin resin, the mechanical strength, oil resistance, etc. of the decorative sheet of the present invention are improved, and the burden on the environment can be reduced. These thermoplastic resins
It may be used independently and two or more types may be used together.
In the present specification, (meth) acryl means acryl and methacryl.

The polyolefin resin is obtained by homopolymerizing or copolymerizing an olefin monomer having a polymerizable double bond in the molecule.
The olefin monomer is not particularly limited, and examples thereof include ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-
Examples include α-olefins such as pentene and vinyl acetate; conjugated dienes such as butadiene and isoprene. These olefinic monomers may be used alone or in combination of two or more.

The polyolefin resin is not particularly limited. For example, a homopolymer of ethylene; a copolymer of ethylene and an α-olefin other than ethylene copolymerizable with ethylene; ethylene- (meth) acrylic acid and / or For example, (meth) acrylic ester copolymer such as ethyl (meth) acrylate; ethylene-vinyl acetate copolymer; polyethylene resin such as ethylene-styrene copolymer; homopolymer of propylene; propylene and the propylene Copolymers with copolymerizable α-olefins other than propylene; propylene-ethylene random copolymers or block copolymers; polypropylene resins such as polypropylene alloy resins; butene homopolymers; butadiene, isoprene, etc. Examples thereof include homopolymers or copolymers of conjugated dienes. Among them, ethylene homopolymer, copolymer of ethylene and α-olefin other than ethylene copolymerizable with ethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, propylene homopolymer Preferably, at least one polyolefin resin selected from the group consisting of a polymer, a copolymer of propylene and an α-olefin other than propylene copolymerizable with the propylene, and a polypropylene alloy resin is preferably used. These polyolefin resin may be used independently and 2 or more types may be used together.

Examples of (meth) acrylic acid and (meth) acrylic acid ester that can be copolymerized with the olefinic monomer include compounds represented by the following general formula.
^{_{CH 2 = C (R 1)}} COO-R 2
In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a hydrocarbon group containing a functional group such as a halogen group, an amino group, or a glycidyl group. Represents a monovalent group selected from the group consisting of

The (meth) acrylic acid ester represented by the above general formula is not particularly limited. For example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic Sec-butyl (meth) acrylate t-butyl acid, (
Isoamyl acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, N-tridecyl (meth) acrylate, tristil (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, (meth)
Allyl acrylate, vinyl (meth) acrylate, benzyl (meth) acrylate, (meth)
Phenyl acrylate, 2-naphthyl (meth) acrylate, 24,6- (meth) acrylic acid
Trichlorophenyl, 2,4,6-tribromophenyl (meth) acrylate, isobornyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic acid 2
-Ethoxyethyl, (meth) acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polypropylene glycol monomethyl ether, (meth) acrylic acid tetrahydrofurfuryl,
2,3-dipromopropyl (meth) acrylate, 2-chloroethyl (meth) acrylate,
2,2,2-trifluoroethyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, glycidyl (meth) acrylate, 3-trimethoxysilylpropyl (meth) acrylate, 2- (meth) acrylic acid 2- Diethylaminoethyl, (meth) acrylic acid 2
-Dimethylaminoethyl, t-butylaminoethyl (meth) acrylate, etc. are mentioned.
These (meth) acrylic acid esters may be used alone or in combination of two or more.

Copolymer of ethylene and (meth) acrylic acid and / or (meth) acrylic acid ester or ethylene-vinyl acetate copolymer containing (meth) acrylic acid and / or (meth) acrylic acid ester or vinyl acetate The amount may be appropriately determined depending on the performance required for the intended decorative sheet, and is not particularly limited. Usually, the preferred lower limit is 0.1% by weight, and the preferred upper limit is 50% by weight. If it is less than 0.1% by weight, the effect of improving the flexibility of the sheet-like molded product may not be sufficiently obtained. If it exceeds 50% by weight, the heat resistance of the sheet-like molded product may be lowered. A more preferred lower limit is 5% by weight, and a more preferred upper limit is 30% by weight.

When a polyolefin resin having excellent flexibility is required, a copolymer of ethylene and an α-olefin other than ethylene is generally used. In particular, by increasing the α-olefin content, flexibility is improved, and the sheet is suitably used as a sheet that requires flexibility.
Although it does not specifically limit as alpha olefins other than the said ethylene, For example, propylene, 1-butene, 1-hexene, 4-methyl-1- pentene, 1-octene etc. are used suitably. These α-olefins other than ethylene may be used alone or in combination of two or more.

In the copolymer of ethylene and an α-olefin other than ethylene, α other than ethylene
-The content of olefin is not particularly limited, but the preferred lower limit is 0.1 wt%,
A preferred upper limit is 50% by weight. If it is less than 0.1% by weight, sufficient flexibility may not be obtained, and if it exceeds 50% by weight, the heat resistance may be lowered. A more preferred lower limit is 2% by weight, and a more preferred upper limit is 40% by weight.

The copolymer of ethylene and an α-olefin other than ethylene can be polymerized using a complex of a transition metal of Group IV, Group X or Group XI as a polymerization catalyst. The transition metal complex is a complex in which a ligand is bonded to a transition metal atom.

The ligand is not particularly limited, and examples thereof include a hydrocarbon group, a substituted hydrocarbon group, and a hydrocarbon-
Cyclopentadiene ring substituted by a substituted metalloid group, etc .; cyclopentadienyl oligomer ring; indenyl ring; indenyl ring substituted by hydrocarbon group, substituted hydrocarbon group, hydrocarbon-substituted metalloid group, etc .; chlorine, bromine, etc. Monovalent anion ligand; divalent anion chelate ligand; hydrocarbon group; alkoxide; arylamide; aryloxide;
Amido; phosphide; aryl phosphide; silyl group; substituted silyl group and the like. These ligands may be used alone or in combination of two or more.

The hydrocarbon group is not particularly limited, for example, methyl group, ethyl group, propyl group, butyl group, amyl group, isoamyl group, hexyl group, isobutyl group, hebutyl group, octyl group, nonyl group, decyl group, A cetyl group, 2-ethylhexyl group, a phenyl group, etc. are mentioned.
These hydrocarbon groups may be used independently and 2 or more types may be used together.

Specific examples of the transition metal complex to which the ligand is bonded are not particularly limited. For example, cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopenta). Dienyl) titanium dichloride, dimethylsilyltetramethylcyclopentadienyl-t-butylamidozirconium dichloride, dimethylsilyltetramethylcyclopentadienyl-t-butylamidohafnium dichloride, dimethylsilyltetramethylcyclopentadienyl-Pn -Butylphenylamidozirconium chloride, methylphenylsilyltetramethylcyclopentadienyl-t-butylamidohafnium dichloride, indenyl titanium tris (di-n
-Propylamide), indenyltitanium bis (di-n-butylamide) (di-n-propylamide) group IV transition metal complexes; bipyridine, substituted bipyridine, bisoxazoline, substituted bisoxazoline; general formula ArN = CR ³ CR ⁴ = NAr (wherein Ar represents an allyl group such as a phenyl group or a substituted phenyl group, and R ³ and R ⁴ represent a hydrogen atom, a halogen atom, an alkyl group, an allyl group, or R ³ , R ⁴ represents a bonded cyclic hydrocarbon group): various diimines: N, N′-dimethylamidinato, N, N′-diethylamidinato, N, N′-diisopropylamidina N, N′-di-t-butylamidinato,
N, N′-trifluoromethylamidinato, N, N′-diphenylamidinato, N, N ′
-Disubstituted phenylamidinato, N, N'-ditrimethylsilylamidinato, N, N'-dimethylbenzamidinato, N, N'-diethylbenzamidinato, N, N'-diisopropylbenzamidinato N, N′-di-t-butylbenzamidinato, N, N′-trifluoromethylbenzamidinato, N, N′-diphenylbenzamidinato, N, N′-ditrimethylsilylbenzamido Zinato; N, N′-disubstituted phenylbenzamidinato-coordinated nickel, palladium, copper, silver and other group X and group XI transition metal complexes. These transition metal complexes may be used alone or in combination of two or more. The transition metal complex can be usually obtained in the presence of a Lewis acid such as an organoaluminum compound or a boron compound.

Copolymers of ethylene and α-olefins other than ethylene polymerized in such a catalyst system can increase the content of α-olefins other than ethylene and control the composition distribution. Therefore, it is suitably used as a material for obtaining the decorative sheet of the present invention that can cope with a wide range of required flexibility and mechanical strength.

Further, when a polyolefin resin having excellent flexibility is required, a polyolefin alloy resin having a polyolefin resin as a main component and an elastomer component (rubber component) finely dispersed therein is used.

The method for finely dispersing the elastomer component, which is a rubber component, in the polyolefin resin as the main component is not particularly limited. For example, a method in which the elastomer component is added to the heated and melted polyolefin resin and uniformly co-kneaded. In addition, there is a method in which an elastomer component is added to the polymerization system of the polyolefin resin, and polymerization of the polyolefin resin and fine dispersion of the elastomer component are performed at the same time. The latter method is preferably employed because a polyolefin alloy resin finely dispersed in the resin can be obtained.

By using a polyolefin alloy resin in which the elastomer component, which is a rubber component, is highly finely dispersed, the resulting thermoplastic resin composition exhibits excellent flexibility and elongation without impairing other physical properties. It becomes.

Among the above-mentioned polyolefin-based alloy resins, since a thermoplastic resin composition exhibiting more excellent flexibility and elongation can be obtained, for example, other than propylene homopolymer, propylene and propylene copolymerizable with the propylene The main component is a polypropylene resin such as a copolymer of α-olefin, propylene-ethylene random copolymer or block copolymer,
A polypropylene alloy resin in which an elastomer component is finely dispersed is suitably used.

Among the polypropylene alloy resins, the elution amount at 10 ° C. or less is 30 to 80% by weight, and the elution amount at 10 ° C. or more and 70 ° C. or less is 5 to 5%. A polypropylene alloy resin mainly composed of 35% by weight of a polypropylene resin is more preferably used.

The difference due to the temperature of the elution amount by the cross fractionation chromatograph mainly indicates the difference in crystallinity of the polypropylene resin. That is, the polypropylene resin having the above elution amount is
Polypropylene alloy resin having a broad crystallinity distribution as a main component and having a polypropylene resin as a main component has little deterioration in physical properties even when highly loaded with a layered silicate or a flame retardant described later, and has excellent flexibility and Expresses elongation.

The measuring method of the elution amount by the said cross fractionation chromatograph is not specifically limited, For example, the following methods can be used. That is, first, after dissolving the polypropylene resin in, for example, o-dichlorobenzene at a temperature at which the polypropylene resin is completely dissolved, this solution is cooled at a constant rate, and a thin polypropylene is applied to the surface of the inert carrier prepared in advance. The system resin layer is formed in order of high crystallinity and large molecular weight. Next, the temperature is raised continuously or stepwise by the temperature rise separation method, and the concentration of the components that are sequentially eluted for each predetermined temperature range is detected.
The composition distribution (crystallinity distribution) is measured and the molecular weight of the components and the distribution are determined by high-temperature GPC.
Measure with

When the elution amount at 10 ° C. or less is less than 30% by weight among the total elution amounts by the cross fractionation chromatograph, the flexibility of the polypropylene resin becomes insufficient, so this polypropylene resin is the main component. Polypropylene-based resin may be difficult to be highly filled with layered silicate and flame retardant, and when the elution amount at 10 ° C. or less exceeds 80% by weight, the polypropylene-based resin becomes too flexible. The mechanical strength of the sheet-like molded product using a polypropylene-based alloy resin containing a resin as a main component may be insufficient.

Moreover, since the heat resistance of polypropylene resin becomes inadequate when the elution amount in excess of 10 degreeC and below 70 degreeC is less than 5 weight% among the total elution quantities by a cross fractionation chromatograph, this polypropylene resin The heat resistance of the sheet-like molded product using a polypropylene-based alloy resin containing as a main component may be insufficient, and if it exceeds 35% by weight, the flexibility of the polypropylene-based resin becomes insufficient. A polypropylene alloy resin containing a polypropylene resin as a main component may be difficult to highly fill with a layered silicate or a flame retardant.

The molecular weight and molecular weight distribution of the thermoplastic resin are not particularly limited, but the preferred lower limit of the weight average molecular weight is 5000, the preferred upper limit is 5,000,000, and the more preferred lower limit is 20,000.
A more preferable upper limit is 300,000. Moreover, the preferable minimum of molecular weight distribution calculated | required by a weight average molecular weight / number average molecular weight is 1.1, a preferable upper limit is 80, and a more preferable minimum is 1.
5. A more preferred upper limit is 40.

The thermoplastic resin may be blended with thermoplastic elastomers and oligomers for resin modification as needed within a range that does not impede achievement of the object of the present invention.
The thermoplastic elastomers are not particularly limited, and examples thereof include styrene elastomers, olefin elastomers, urethane elastomers, and polyester elastomers. These thermoplastic elastomers may be used alone or in combination of two or more. The oligomers are not particularly limited, and examples thereof include maleic anhydride-modified polyethylene oligomers. These oligomers may be used independently and 2 or more types may be used together. In addition, the thermoplastic elastomers and oligomers may be used alone or in combination.

In the above thermoplastic resin, a nucleating agent that can be a crystal nucleus for refining crystals as an auxiliary means for homogenizing physical properties as required, as long as it does not hinder the achievement of the subject of the present invention, an antioxidant (
(Anti-aging agent), heat stabilizer, light stabilizer, ultraviolet absorber, lubricant, flame retardant, antistatic agent, antifogging agent and other additives may be used alone or in combination.

The thermoplastic resin composition contains a layered silicate.
In the present specification, the layered silicate means a silicate mineral having an exchangeable metal cation between layers.
The layered silicate is not particularly limited, and examples thereof include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, and swelling mica. Among these, montmorillonite and / or swellable mica is preferably used. The layered silicate may be a natural product or a synthetic product. Moreover, these layered silicates may be used independently and 2 or more types may be used together.

As the layered silicate, it is preferable to use smectites or swelling mica having a large shape anisotropy effect defined by the following formula. By using a layered silicate having a large shape anisotropy effect, the mechanical strength of the thermoplastic resin composition becomes more excellent.
Shape anisotropy effect = area of crystal surface (A) / area of crystal surface (B) In the formula, the crystal surface (A) means the layer surface, and the crystal surface (B) means the side surface of the layer.

The shape of the layered silicate is not particularly limited, but the preferred lower limit of the average length is 0.01
The preferable upper limit is 3 μm, the preferable lower limit of the thickness is 0.001 μm, the preferable upper limit is 1 μm, the preferable lower limit of the aspect ratio is 20, and the preferable upper limit is 500.
The more preferable lower limit of the average length is 0.05 μm, the more preferable upper limit is 2 μm, the more preferable lower limit of the thickness is 0.01 μm, the more preferable upper limit is 0.5 μm, and the more preferable lower limit of the aspect ratio is 50, more A preferred upper limit is 200.

The exchangeable cation existing between the crystal layers of the layered silicate is a metal ion such as sodium or calcium existing on the crystal surface, and these metal ions have a cation exchange property with a cationic substance. Various substances having cationic properties can be trapped (intercalated) between the crystal layers of the layered silicate.

Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, A preferable minimum is 50 meq / 100g and an upper limit is 200 meq / 100g. When the amount is less than 50 meq / 100 g, the amount of the cationic substance that can be trapped between the crystal layers by cation exchange decreases, so the crystal layer may not be sufficiently nonpolarized. When the amount exceeds 200 meq / 100 g, The bonding strength between the crystal layers of the layered silicate becomes strong, and the crystal flakes may be difficult to peel off.

When a low-polarity resin such as a polyolefin resin is used as the thermoplastic resin, it is preferable that the layered silicate layer is previously cation-exchanged with a cationic surfactant to be hydrophobized. By making the layers of the layered silicate hydrophobic in advance, the affinity between the layered silicate and the thermoplastic resin is increased, and the layered silicate can be finely dispersed more uniformly in the thermoplastic resin.

The cationic surfactant is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts. Among them, a quaternary ammonium salt having an alkyl chain having 6 or more carbon atoms, that is, an alkyl ammonium salt having 6 or more carbon atoms is preferably used since the crystal layer of the layered silicate can be sufficiently nonpolarized.

The quaternary ammonium salt is not particularly limited. For example, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, Examples thereof include N-polyoxyethylene-N-lauryl N, N-dimethylammonium salt. These quaternary ammonium salts may be used alone or in combination of two or more.

The quaternary phosphonium salt is not particularly limited. For example, dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, trioctylmethylphosphonium salt, distearyldimethyl Examples thereof include phosphonium salts and distearyl dibenzylphosphonium salts. These quaternary phosphonium salts may be used alone,
Two or more types may be used in combination.

The layered silicate used in the present invention can be improved in dispersibility in the thermoplastic resin by chemical treatment as described above.
The chemical treatment is not limited to the cation exchange method using a cationic surfactant (hereinafter, also referred to as the chemical modification (1) method). For example, the chemical treatment (2) to chemical modification (shown below)
6) It can also be carried out by various chemical treatment methods. These chemical modification methods may be used alone or in combination of two or more. In addition, the layered silicate whose dispersibility in the thermoplastic resin is improved by the following various chemical treatment methods including the chemical modification (1) method is hereinafter also referred to as “organized layered silicate”.

In the chemical modification (2) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method can be combined with a functional group or a chemical bond. In this method, chemical treatment is performed with a compound having at least one functional group having high chemical affinity at the molecular end. Such a functional group that can be chemically bonded to a hydroxyl group, or a functional group that does not have a chemical bond but has high chemical affinity is not particularly limited. For example, an alkoxy group, a glycidyl group, a carboxyl group (dibasic acid (Including anhydrides), functional groups such as hydroxyl groups, isocyanate groups, and aldehyde groups, and other functional groups having high chemical affinity with hydroxyl groups. In addition, the functional group that can be chemically bonded to the hydroxyl group, or a compound having a functional group with high chemical affinity without chemical bonding is not particularly limited. Examples thereof include silane compounds having a group, titanate compounds, glycidyl compounds, carboxylic acids, alcohols and the like. These compounds may be used alone or in combination of two or more.

The silane compound is not particularly limited. For example, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyl Methyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxy Silane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, octadecyltrimethoxysilane, oct Decyl triethoxysilane, .gamma.-methacryloxypropyl methyl dimethoxy silane, .gamma.-methacryloxypropyl methyl diethoxy silane, .gamma.-methacryloxypropyl trimethoxysilane, .gamma.-methacryloxypropyl triethoxysilane, and the like. These silane compounds may be used alone or 2
More than one type may be used in combination.

In the chemical modification (3) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method can be chemically bonded to a functional group or a chemical bond. In this method, chemical treatment is performed with a compound having one or more functional groups and reactive functional groups having high chemical affinity at the molecular ends.

The chemical modification (4) method is a method in which the crystallized surface of the organically modified layered silicate chemically treated by the chemical modification (1) method is chemically treated with a compound having an anionic surface activity.

The chemical modification (5) method is a chemical treatment (4) method in which a chemical treatment is performed with a compound having one or more reactive functional groups in addition to the anion site in the molecular chain of the compound having anionic surface activity.

Compounds having an anionic surface activity in the chemical modification (4) method and the chemical modification (5) method,
The compound having an anionic surface activity and having one or more reactive functional groups other than the anion site in the molecular chain is not particularly limited as long as it can chemically treat the layered silicate by ionic interaction. Examples include sodium laurate, sodium stearate, sodium oleate, higher alcohol sulfates, secondary higher alcohol sulfates, and unsaturated alcohol sulfates. These compounds may be used alone or in combination of two or more.

In the chemical modification (6) method, the organically modified layered silicate chemically treated by any one of the chemical modification (1) method to the chemical modification (5) method is further used, for example, maleic anhydride-modified polyphenylene ether type. In this method, a composition containing a resin having a functional group capable of reacting with a layered silicate such as a resin is used as a dispersant. This improves the compatibility of both by mixing a dispersant that has a high affinity with the layered silicate and a high affinity with the thermoplastic resin, and reduces the energy required to disperse the layered silicate. It is a method to make it. As such a dispersant, maleic anhydride-modified polyolefin oligomers and the like are preferably used, and among them, AB type diblock polymers or diblock oligomers having different properties at both ends are preferably used. Both ends have both ends with different properties, a property having a high affinity for the layered silicate and a property having a high affinity for the thermoplastic resin, and A (layered silicate affinity site) -B (thermoplastic affinity site)
Since it is a type | mold, a suitable dispersion | distribution effect is acquired from being easy to exhibit affinity to each efficiently. A method for obtaining a highly dispersed state using such an AB type dispersant is not particularly limited, and examples thereof include melt kneading a thermoplastic resin and a layered silicate together with a dispersant in an extruder.

The layered silicate has an average interlayer distance of (001) plane measured by wide angle X-ray diffraction measurement method is 3
It is preferably at least nm and partly or entirely dispersed in 5 layers or less. More preferably, the average interlayer distance is 6 nm or more, and a part or all of the average interlayer distance is dispersed in 5 layers or less. In the present specification, the average interlayer distance of the layered silicate means an average interlayer distance when the layered silicate fine flaky crystal is used as a layer, and X-ray diffraction peak and transmission electron microscope photography, It can be calculated by a wide angle X-ray diffraction measurement method. Further, the dispersion state of the layered silicate is observed by using a transmission electron microscope at 50,000 to 100,000 times, and five layers out of the number (X) of layered silicate laminates that can be observed in a certain area. The number (Y) of the laminated assemblies dispersed below can be counted and calculated by the following formula.
Ratio of layered silicate dispersed in 5 layers or less (%) = (Y / X) × 100

When layered molecules of layered silicate, which is essentially a laminate of several tens of layers, peel and disperse, the interaction between the layered silicate crystal flakes becomes so negligible that crystal flakes are thermoplastic. It becomes a finely dispersed state at a certain distance and stabilizes. As a result, the layered silicate increases the average interlayer distance between the crystal flake layers and stabilizes dispersion, and at the time of combustion, it becomes easy to form a sintered body by the movement of the crystal flakes of the layered silicate. That is, the thermoplastic resin composition in which the lamellar silicate crystal flake layers are dispersed with an average interlayer distance of 3 nm or more, more preferably 6 nm or more, easily forms a sintered body that can be a flame retardant coating. Since this sintered body is formed at the early stage of combustion, not only the supply of oxygen from the outside world can be blocked, but also the flammable gas generated by the combustion can be blocked, and the heat generation of the thermoplastic resin composition Speed can be suppressed.
That is, it becomes possible to exhibit excellent fire spread prevention properties. Therefore, the decorative sheet of the present invention obtained by blending and dispersing such a layered silicate in a thermoplastic resin has extremely excellent flame retardancy,
Various properties such as mechanical strength and heat resistance are exhibited. In addition, when the average interlayer distance between the layered silicate crystal flake layers is 3 nm or more, preferably 6 nm or more, the layered silicate crystal flake layers are separated into layers, and the interaction between the layered silicate crystal flake layers is Since it weakens so that it can be almost ignored, there is an advantage that the dispersed state of the crystal flakes constituting the layered silicate in the thermoplastic resin progresses in the direction of crushing stabilization.

In addition, the fact that part or all of the layered silicate is dispersed in 5 layers or less means that part or all of the layered molecules of the layered silicate which is essentially a laminate of several tens of layers is peeled off. This means that it is widely dispersed, and this also means that the interaction between the crystal flake layers of the layered silicate is weakened, so that the same effect as described above can be obtained. Specifically, it is preferable that 10% or more of the layered silicate is dispersed in 5 layers or less, in which part or all of the layered silicate is dispersed in 5 layers or less. More preferably, 20% or more is dispersed in 5 layers or less. The above-mentioned effect can be obtained by dividing the number of layered silicate layers into 5 layers or less, but it is more preferably divided into 3 layers or less, and particularly preferably in a single layer shape. It is thinning.

In the above thermoplastic resin composition, the average interlayer distance between the layered silicate crystal flake layers is 3 nm or more, and a part or all of the layered silicate is dispersed in 5 layers or less, that is, thermoplasticity. If the layered silicate is highly dispersed in the resin, the interface area between the thermoplastic resin and the layered silicate increases. When the interface area between the thermoplastic resin and the layered silicate increases, the degree of restraint of the thermoplastic resin on the surface of the layered silicate increases, and mechanical strength such as elastic modulus improves. Moreover, when the degree of restraint of the thermoplastic resin on the surface of the layered silicate increases, the melt viscosity increases and the moldability also improves. Moreover, the gas barrier property can be expressed by the baffle effect of the layered silicate. Further, the fact that the layered silicate is present in the number of laminated layers of 5 layers or less is advantageous also from the viewpoint of maintaining the strength of the layered silicate itself, and is particularly advantageous for expressing the mechanical strength, particularly the elastic modulus. .

The more the layered silicate peels and the crystal flakes are dispersed in the thermoplastic resin, the smaller the average adjacent distance between the crystal flakes, and the formation of a sintered body by movement of the layered silicate crystal flakes during combustion occurs. It becomes easy to break. Moreover, the more the layered silicate crystal flakes are dispersed in the thermoplastic resin, the more significantly the elastic modulus and gas barrier properties of the thermoplastic resin composition are improved.

Any of the above phenomena is due to the fact that the interface area between the layered silicate and the thermoplastic resin increases as the dispersion of crystal flakes increases. That is, the mechanical strength such as the elastic modulus of the thermoplastic resin is increased by restraining the molecular motion of the thermoplastic resin at the adhesive surface between the thermoplastic resin and the layered silicate, so that the dispersion ratio of the crystal flakes is increased. The better, the greater the effect of increasing the mechanical strength of the thermoplastic resin composition.

In general, gas molecules are much easier to diffuse in polymers than inorganic materials,
When gas molecules diffuse in the thermoplastic resin, they diffuse while bypassing the inorganic substance. Therefore, also in this case, the higher the dispersion ratio of the lamellar silicate crystal flakes, the more efficiently the gas barrier property of the thermoplastic resin composition can be increased.

The lower limit of the amount of layered silicate in the thermoplastic resin composition is 0.1 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and the upper limit is 100 parts by weight. If it is less than 0.1 part by weight, it becomes difficult to form a continuous sintered body at the time of combustion, so the flame retardant effect is small. If it exceeds 100 parts by weight, mechanical strength and formability are impaired. Since it is too much, practicality becomes poor. The preferred lower limit is 1 part by weight, the preferred upper limit is 40 parts by weight, the more preferred lower limit is 4 parts by weight, the more preferred upper limit is 30 parts by weight, the still more preferred lower limit is 7 parts by weight, and the still more preferred upper limit is 20 parts by weight. is there. A continuous film having a high mechanical strength is formed when the amount is 4 to 30 parts by weight, and a continuous film having a higher mechanical strength is formed when the amount is 7 to 20 parts by weight.
The same applies to the organic layered silicate.

The method for dispersing the layered silicate in the thermoplastic resin is not particularly limited, for example, a method using the above-mentioned organic layered silicate; a method of foaming after kneading the thermoplastic resin and the layered silicate by a conventional method A method using a dispersant, and the like. By using these dispersion methods, the layered silicate can be more uniformly and finely dispersed in the thermoplastic resin.

A method of foaming after kneading the thermoplastic resin and the layered silicate by a conventional method will be described below. In this method, a thermoplastic resin is foamed using a foaming agent, and the foaming energy is converted into the dispersion energy of the layered silicate.
It does not specifically limit as said foaming agent, For example, a gaseous foaming agent, an easily volatile liquid foaming agent, a heat decomposable solid foaming agent etc. are mentioned. These foaming agents may be used alone or 2
More than one type may be used in combination.

A specific method for dispersing the layered silicate in the thermoplastic resin by foaming the thermoplastic resin in the presence of the layered silicate is not particularly limited. For example, the thermoplastic resin 10
After impregnating the composition consisting of 0 parts by weight and 0.1 to 100 parts by weight of the layered silicate with a gaseous foaming agent under high pressure or kneading a readily volatile liquid foaming agent, this gaseous foaming Dispersion method by forming a foam by evaporating an agent or a readily volatile liquid foaming agent in the above composition; a heat decomposable solid foaming agent is previously contained between the layers of the layered silicate, and the thermal decomposition thereof Examples thereof include a dispersion method by decomposing a mold-type solid foaming agent by heating to form a foamed structure.

The thermoplastic resin composition further contains a metal hydroxide.
The metal hydroxide has a role as a flame retardant and can make the flame retardant effect of the layered silicate more effective.
Although it does not specifically limit as said metal hydroxide, For example, magnesium hydroxide, aluminum hydroxide, calcium hydroxide etc. are used suitably. These metal hydroxides may be used alone or in combination of two or more.
The shape of the metal hydroxide is not particularly limited. The metal hydroxide may be subjected to a surface treatment.

The metal hydroxide preferably has a calendering aid treated on its surface.
As a result, the calendering aid can be uniformly dispersed in the resin, and the sheet-like molded body can be produced by a calendering method. Further, if a calendering aid having a function as a lubricant is used, the compatibility between the thermoplastic resin and the metal hydroxide can be improved.

Although it does not specifically limit as said calender shaping | molding adjuvant, For example, a fatty-acid type metal soap is used suitably. The fatty acid-based metal soap is not particularly limited, for example, calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, sodium stearate, lithium stearate, potassium stearate, calcium behenate, magnesium behenate, Zinc behenate, aluminum behenate, sodium behenate, lithium behenate, potassium aluminum behenate, sodium behenate, lithium behenate, potassium behenate, calcium 12-hydroxystearate, magnesium 12-hydroxystearate, 12-hydroxystearate Zinc acid, aluminum 12-hydroxystearate, sodium 12-hydroxystearate, lithium 12-hydroxystearate, 12-hydro Potassium aluminum Shisutearin acid, 1
Sodium 2-hydroxystearate, lithium 12-hydroxystearate, 12
-Potassium hydroxystearate, calcium montanate, magnesium montanate,
Examples thereof include zinc montanate, aluminum montanate, sodium montanate, lithium montanate, potassium aluminum montanate, sodium montanate, lithium montanate, and potassium montanate. Of these, calcium 12-hydroxystearate is preferably used. These calendering aids may be used alone or in combination of two or more.

The lower limit of the amount of the metal hydroxide in the thermoplastic resin composition is the thermoplastic resin 100.
0.1 parts by weight with respect to parts by weight, and the upper limit is 70 parts by weight. If the amount is less than 0.1 part by weight, a sufficient effect of improving flame retardancy cannot be obtained, and if it exceeds 70 parts by weight, the flexibility and elongation of the thermoplastic resin composition are extremely lowered. The preferred lower limit is 1 part by weight, the preferred upper limit is 65 parts by weight, the more preferred lower limit is 10 parts by weight, and the more preferred upper limit is 60 parts by weight.
Conventionally, in order to impart sufficient flame retardancy to a thermoplastic resin such as an olefin resin, it has been necessary to add a large amount of metal hydroxide to the thermoplastic resin component. However, in the decorative sheet of the present invention, by using the layered silicate and the metal hydroxide in combination, sufficient flame retardancy is imparted without adding a large amount of metal hydroxide, and by adding a large amount of flame retardant. It will not cause any harmful effects.

The thermoplastic resin composition is within a range that does not impair the object of the present invention.
One kind of various additives such as fillers, softeners, plasticizers, lubricants, antistatic agents, antifogging agents, colorants, antioxidants (anti-aging agents), heat stabilizers, light stabilizers, UV absorbers, etc. Or 2 or more types may be mix | blended.

The method for preparing the thermoplastic resin composition is not particularly limited. For example, a predetermined amount of a thermoplastic resin, a layered silicate, and a metal hydroxide, and one kind of various additives blended as necessary, or A method of directly blending and kneading two or more predetermined amounts at room temperature or under heating (direct kneading method); a predetermined amount of a layered silicate is previously blended into a predetermined amount of a thermoplastic resin and kneaded. Prepared a master batch, the master batch and the remainder of a predetermined amount of the thermoplastic resin and a metal hydroxide, and one or two or more predetermined amounts of various additives added as necessary,
A method of kneading at normal temperature or under heating (master batch method) and the like may be mentioned, and any method may be adopted.

The blending amount of the layered silicate in the masterbatch is not particularly limited, but the preferred lower limit is 1 part by weight and the preferred upper limit is 500 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If the amount is less than 1 part by weight, the convenience as a master batch that can be diluted to an arbitrary concentration may be lost. If the amount exceeds 500 parts by weight, the dispersibility of the master batch itself and, in particular, a predetermined blending depending on the thermoplastic resin may occur. The dispersibility of the layered silicate when diluted to the amount may deteriorate. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 300 parts by weight.

The specific production method of the composition by the direct kneading method or the master batch method is not particularly limited. For example, the thermoplastic resin composition is constituted by using a kneader such as an extruder, a two-roll, a Banbury mixer, or the like. Thermoplastic resin, layered silicate, metal hydroxide and various additives blended as needed uniformly melt-kneading at room temperature or under heating; thermoplastic resin, layered silicate, metal hydroxide In addition, a method of uniformly kneading various additives to be blended as necessary in a solvent in which they can be dissolved or dispersed may be mentioned, and any method may be adopted.

When a polyolefin resin is used as the thermoplastic resin, for example, a layered silicate containing a polymerization catalyst (polymerization initiator) such as a transition metal complex is used to form the olefin single resin constituting the polyolefin resin. By kneading the polymer and the layered silicate containing the polymerization catalyst (polymerization initiator) and polymerizing the olefin monomer, the production of the polyolefin resin and the production of the thermoplastic resin composition are simultaneously performed. The method performed may be used.

The decorative sheet of the present invention has an adhesive layer laminated on the sheet-like molded body.
It does not specifically limit as an adhesive which comprises the said adhesive layer, For example, an elastomer type (rubber type) adhesive, an acrylic resin type adhesive, a polyvinyl ether resin type adhesive, a silicone resin type adhesive etc. are mentioned.
The form of the pressure-sensitive adhesive is not particularly limited. For example, a solvent-type pressure-sensitive adhesive, a non-water emulsion-type pressure-sensitive adhesive, an emulsion-type pressure-sensitive adhesive, a dispersion-type pressure-sensitive adhesive, a hot-melt-type pressure-sensitive adhesive, such as an ultraviolet ray Monomer type or oligomer type pressure-sensitive adhesives that can be cured (polymerized) with energy rays. The pressure-sensitive adhesive may be a cross-linked pressure-sensitive adhesive, a non-cross-linked pressure-sensitive adhesive, a one-component pressure-sensitive adhesive, or a multi-component pressure-sensitive adhesive having two or more liquids. It may be.
Moreover, as said adhesive, what has a flame retardance is more preferable. Thereby, the flame retardance of the decorative sheet of the present invention becomes more excellent.
In addition, the pressure-sensitive adhesive layer has an inorganic substance such as a pigment, an ultraviolet absorber, a hindered amine light stabilizer (HALS), etc. for the purpose of improving weather resistance within a range that does not affect flame retardancy. It is good also as containing.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 10 μm in terms of the solid content thickness.
m, the preferred upper limit is 60 μm. If it is less than 10 μm, the adhesive strength may be insufficient, and if it exceeds 60 μm, the thickness of the decorative sheet of the present invention increases, which is disadvantageous for flame retardancy.

The decorative sheet of the present invention is 50 kW in a combustion test according to ASTM E 1354.
The combustion residue burned by heating for 30 minutes under the radiant heating condition of / m ² has a speed of 0.1.
The yield point stress when compressed at cm / s is preferably 4.9 kPa or more. 4.9k
If it is less than Pa, the combustion residue tends to collapse with a slight force, and the flame retardancy and fire spread prevention property of the sheet-like molded product may be insufficient. That is, in order for the decorative sheet of the present invention to fully exhibit the function as a flame retardant coating, it is preferable that the sintered body keeps its shape until the end of combustion. More preferably, it is 15.0 kPa or more.

The decorative sheet of the present invention is a decorative sheet having a thickness of 65 μm or more excluding the pressure-sensitive adhesive layer.
In accordance with 1182, when it is bonded to a non-combustible material and burned under a radiation heating condition of 50 kW / m ² , the time during which the maximum heat generation rate is continuously 200 kW / m ² or more in 20 minutes after the start of heating. Less than 10 seconds, the total calorific value is 8 MJ / m ² or less, and the thickness is 65
It is preferable that it is μm or more. In 20 minutes after the start of heating, if the time for which the maximum heat generation rate is continuously 200 kW / m ² or more is 10 seconds or more, or if the total heat generation exceeds 8 MJ / m ² , the flame retardancy and fire spread of the decorative sheet Insufficient prevention. When the thickness of the decorative sheet excluding the pressure-sensitive adhesive layer is less than 65 μm, the total calorific value and the maximum heat generation rate are naturally reduced because the amount of combustible material is small, but such an excessively thinned sheet Shaped molded products are not suitable for practical use because basic mechanical properties may be impaired, the finish may be affected by the state of the base, the finish may be uneven, and the concealment may be low, making it easy to pick up the color of the base putty. .

The decorative sheet of the present invention preferably has an average cessation time of 6.8 minutes or more in a gas toxicity test in accordance with ISO 1182, that is, a gas toxicity test. If it is less than 6.8 minutes, it means that harmful gas is generated at the time of combustion, and there is a risk of causing secondary disasters such as gas poisoning in the event of a fire.

The thickness of the decorative sheet of the present invention is not particularly limited as long as it is appropriately set according to the type and use, but the preferred lower limit is 65 μm and the upper limit is 300 μm. If it is less than 65 μm, the concealability of the underlying wall material pattern, etc. may be insufficient and may not be suitable for practical use as a decorative sheet, and it is difficult to maintain mechanical strength. If it exceeds 300 μm, combustible components per unit area The increase in the amount makes it difficult to suppress the flammability, and the load on the installer increases because the weight per unit area increases.

The decorative sheet of the present invention uses, for example, a layer made of a polyester-based resin as a transparent colored film layer, and a layer made of a thermoplastic resin composition as a colored film layer, for example, a colored film layer-printed layer-colored film layer. -It is good also as what laminated | stacked in order of the adhesion | attachment / adhesive layer. As described above, the decorative sheet of the present invention can obtain various physical properties and properties depending on the type and application.
In addition, the surface of the decorative sheet of the present invention may be coated or laminated with a film in order to impart functions such as stain resistance, weather resistance, scratch resistance, and slip resistance.

The method for producing the decorative sheet of the present invention is not particularly limited, for example, the corona treatment is performed on the side of the sheet made of polyester resin in contact with the printing layer, and the solvent-based adhesive is applied to the corona-treated surface. After drying, a printing layer is formed, and a sheet made of a thermoplastic resin composition subjected to corona treatment is laminated to form a sheet-like molded body, and a method of forming an adhesive layer on the sheet-like molded body, etc. Can be mentioned.

The method for producing a sheet comprising the thermoplastic resin composition is not particularly limited. For example, the composition produced in advance is melt-kneaded and extruded in an extruder, and is formed into a sheet using a T-die or a circular die. After the composition is dissolved or dispersed in a solvent such as an organic solvent,
Examples include a method of forming into a sheet form by a casting method; a calender forming method in which a composition is melt-kneaded and then subjected to roll forming by a calendering method using a roll forming machine. Especially, it is preferable to manufacture by the calendar molding method. Calender molding, in which molten resin is kneaded and stretched on a roll molding machine, has a low loss of raw materials when changing product types / resins when producing many product types. Excellent.
Conventionally, olefin-based resins have a low melt viscosity at a high temperature, and therefore, in the calender molding method, the molding adaptation temperature range is narrow and is not suitable for calendering. However, a calendar molding method can be performed by adding molding aids such as the above-described calender molding aids.
Moreover, it can produce also about the sheet | seat which consists of the said polyester-type resin by using the method similar to the sheet | seat which consists of the said thermoplastic resin composition.

The method for forming the pressure-sensitive adhesive layer is not particularly limited. For example, the pressure-sensitive adhesive is directly applied to one back surface (non-decorative surface) of the sheet-like molded body produced by the above-described method, and if necessary. Dry,
After forming the pressure-sensitive adhesive layer through steps such as cooling and irradiation with active energy rays, the surface of the release material such as release paper (release paper) or release film is laminated on the pressure-sensitive adhesive layer as necessary. Method (direct coating method): After forming the pressure-sensitive adhesive layer on the release-treated surface of the release material, this pressure-sensitive adhesive layer is laminated on one side of the sheet-like molded body produced by the above-described method, Transfer method to one side of sheet (
Transfer method) and the like. In addition, in order to further improve the adhesion to the pressure-sensitive adhesive layer, one side of the sheet-like molded body may be subjected to a ground treatment (pretreatment) such as corona discharge treatment or primer (primer coating) in advance. Good.

The solvent-based adhesive is not particularly limited, and examples thereof include 1-component or 2-component polyester-based adhesive, 1-component or 2-component acrylic adhesive, 1-component or 2-component urethane-based adhesive, and the like. .
The preferable lower limit of the thickness of the adhesive layer formed after drying the solvent-based adhesive is 5 μm, and the preferable upper limit is 15 μm. If the thickness is less than 5 μm, a sufficient adhesive effect cannot be exhibited, and if it exceeds 15 μm, there is a problem in terms of transparency and the like. A more preferable lower limit is 8 μm.
m, and a more preferable upper limit is 10 μm.
The method for applying the solvent-based adhesive is not particularly limited. For example, a gravure method,
Examples include the coater method.

Since the decorative sheet of the present invention has a layer made of a thermoplastic resin composition containing a specific amount of layered silicate and metal hydroxide, excellent flame retardancy, mechanical strength, heat resistance, etc. The various performances are expressed. Moreover, by using the layer which consists of polyester-type resin as a transparent layer for protecting a printing layer, while being excellent in transparency, it can be set as the transparent layer which has comparatively high flame retardance.
Therefore, since the decorative sheet of the present invention is a combination of a layer made of such a thermoplastic resin composition and a layer made of a polyester resin, it is the same as a decorative sheet made of a conventional vinyl chloride resin. Furthermore, it can have high flame retardancy and excellent design properties.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Example 1)
85.3 parts by weight of ethylene-ethyl acrylate copolymer (trade name “DPDJ6182”, manufactured by Nihon Unicar Co., Ltd.), maleic anhydride-modified polyethylene in a small extruder (trade name “TEX30”, manufactured by Nippon Steel Co., Ltd.) 7 parts by weight of oligomer (trade name “ER403A”, manufactured by Nippon Polyolefin Co., Ltd.), montmorillonite treated with organically with distearyldimethyl quaternary ammonium salt (trade name “New Sven D”, manufactured by Toyshun Mining Co., Ltd.) 7 7 parts by weight and magnesium hydroxide (trade name “Kisuma 5B”, manufactured by Kyowa Chemical Co., Ltd.)
The mixture was melt-kneaded and extruded into strands, and the extruded strands were pelletized with a pelletizer to produce thermoplastic resin composition pellets.
The obtained pellets were pressed and rolled with a hot press adjusted to 180 ° C. at the top and bottom to produce a plate-like molded body having a thickness of 3 mm and a thermoplastic resin sheet having a thickness of 100 μm.

One surface of the obtained thermoplastic resin sheet having a thickness of 100 μm was subjected to a corona discharge treatment so that the surface wetting index was 42 dyn / cm.
Then, an acrylic paint (trade name “POS”, manufactured by Teikoku Ink Co., Ltd.) was applied to the surface of the thermoplastic resin sheet subjected to corona discharge treatment so that the thickness after drying with a Mayer bar would be 1 μm. It dried and formed the printing layer. And, the stress at the time of 15% thickness and 2% elongation is 20 N / 1
A 0 mm polyester resin sheet (trade name “Tetron”, manufactured by Teijin Co., Ltd.) is bonded to the printing surface of the thermoplastic resin sheet, and press-bonded with a hot press adjusted to 180 ° C. at the top and bottom to produce a sheet-like molded product. did.

On the other hand, with respect to 100 parts by weight of the two-component curable acrylic resin-based adhesive, an isocyanate curing agent (
3 parts by weight of a trade name “L-55” (manufactured by Nippon Polyurethane Co., Ltd.), and a release thickness of 40 μm with a comma coater on the release treatment surface of the release paper that has been subjected to release treatment with a silicone resin release agent. The pressure-sensitive adhesive layer was formed by coating and drying. The obtained pressure-sensitive adhesive layer and the corona discharge-treated surface of the sheet-like molded body subjected to the corona discharge treatment were laminated to prepare a decorative sheet.

(Example 2)
Instead of 85.3 parts by weight of ethylene-ethyl acrylate copolymer “DPDJ6182”, ethylene-α-olefin copolymer (trade name “Kernel KF260”, manufactured by Nippon Polychem)
85.3 parts by weight is used, and the amount of magnesium hydroxide “Kisuma 5B” is 60 parts by weight. The printed layer formed on the thermoplastic resin sheet has a thickness of 30 μm and a stress at 2% elongation of 30%.
A pellet of a thermoplastic resin composition, a plate-shaped molded body, a sheet-shaped molded body, and a decorative sheet were prepared in the same manner as in Example 1 except that an N / 10 mm polyester resin sheet was bonded.

Example 3
Instead of 85.3 parts by weight of ethylene-ethyl acrylate copolymer “DPDJ6182”,
Of the total elution amount by cross-fractionation chromatograph, the elution amount at 0 to 10 ° C
Polypropylene alloy resin (trade name “ADFLEX KF084S”) composed mainly of a polypropylene resin having an elution amount of 9% by weight at 10% to 70 ° C.
Except that a polyester resin sheet having a thickness of 50 μm and a stress at 2% elongation of 40 N / 10 mm was bonded to the printing layer formed on the thermoplastic resin sheet using 85.3 parts by weight of Sun Allomer Co., Ltd. In the same manner as in Example 1, pellets of a thermoplastic resin composition, a plate-shaped molded body, a sheet-shaped molded body, and a decorative sheet were produced.

(Example 4)
Instead of 85.3 parts by weight of the polypropylene-based alloy resin “KF084S”, 77.6 parts by weight of a random propylene resin (trade name: “Sun Allomer PC630A”, manufactured by Sun Allomer), 7 parts by weight of maleic anhydride-modified polyethylene oligomer “ER403A” Instead, 7.0 parts by weight of a diblock oligomer on both ends (trade name “CB-OM12”, manufactured by Kuraray Co., Ltd.) was used, and the blended amount of organically treated montmorillonite “New Sven D” was 15.4 parts by weight. The printed layer formed on the thermoplastic resin sheet has a thickness of 65 μm and a stress of 2N when stretched by 55%.
A pellet of a thermoplastic resin composition, a plate-shaped molded body, a sheet-shaped molded body, and a decorative sheet were prepared in the same manner as in Example 1 except that a polyester resin sheet of / 10 mm was bonded.

(Example 5)
67.6 parts by weight of the ethylene-ethyl acrylate copolymer “DPDJ6182” and 5 parts by weight of the maleic anhydride-modified polyethylene oligomer “ER403A”
The amount of organically treated montmorillonite “New Sven D” is 15.4 parts by weight, and further, 12 parts by weight of random propylene resin “Sun Aroma PC630A” is blended, and the printed layer formed on the thermoplastic resin sheet is thick. 65μm, stress at 2% elongation is 55N / 10mm
Except that the polyester-based resin sheet was laminated, pellets, a plate-shaped molded body, a sheet-shaped molded body, and a decorative sheet of a thermoplastic resin composition were produced in the same manner as in Example 1.

(Examples 6 to 10)
Instead of montmorillonite “New Sven D”, which is organically treated with distearyldimethyl quaternary ammonium salt, swellable fluorine mica (trade name “Somasif”, which is organically treated with distearyldimethyl quaternary ammonium salt. Except that MAE-100 "(manufactured by Co-op Chemical Co., Ltd.) was used, pellets of a thermoplastic resin composition, a plate-shaped molded body, a sheet-shaped molded body, and a decorative sheet were produced in the same manner as in Examples 1-5. As the polyester resin sheet, a sheet having a thickness of 65 μm and a stress at 2% elongation of 55 N / 10 mm was used.

(Examples 11 to 15)
Instead of montmorillonite “New Sven D” treated with distearyldimethyl quaternary ammonium salt, swellable fluorine mica “Somasif MAE-100” treated with distearyldimethyl quaternary ammonium salt. ”And magnesium hydroxide“
Instead of Kisuma 5B, calcium 12-hydroxystearate (sample name “CS
-6 ", magnesium hydroxide surface-treated with Nitto Kasei Co., Ltd. (trade name" Magsees N-4 ")
The pellets of the thermoplastic resin composition, the plate-shaped molded body, the sheet-shaped molded body, and the decorative sheet were produced in the same manner as in Examples 1 to 5 except that “made by Kamishima Chemical Co., Ltd.” was used. As the polyester resin sheet, a sheet having a thickness of 65 μm and a stress at 2% elongation of 55 N / 10 mm was used.

(Comparative Example 1)
In a small extruder “TEX30”, ethylene-ethyl acrylate copolymer “DPDJ618”
2 ”95 parts by weight, 5 parts by weight of maleic anhydride-modified polyethylene oligomer“ ER403A ”, 40 parts by weight of magnesium hydroxide“ Magse's N-4 ”surface-treated with 12-hydroxycalcium stearate“ CS-6 ” The mixture was melt-kneaded at a temperature of 170 ° C. and extruded into a strand shape, and the extruded strand was pelletized with a pelletizer to produce a pellet of a thermoplastic resin composition. Except having used the obtained pellet, it carried out similarly to Example 1, and produced the plate-shaped molded object, the sheet-shaped molded object, and the decorative sheet.
The polyester resin sheet has a thickness of 125 μm and a stress at 2% elongation of 100%.
The thing of N / 10mm was used.

(Comparative Example 2)
In a small extruder “TEX30”, an ethylene-α-olefin copolymer “Kernel KF26”
0 "100 parts by weight, 7.7 parts by weight of swellable fluorine mica (trade name" Somasif ME-100 ", manufactured by Coop Chemical Co., Ltd.), which has not been subjected to organic treatment, is fed and melt-kneaded at a preset temperature of 170 ° C. The pellets were extruded into strands, and the extruded strands were pelletized with a pelletizer to produce pellets of the thermoplastic resin composition.
Except having used the obtained pellet, it carried out similarly to the comparative example 1, and produced the plate-shaped molded object, the sheet-shaped molded object, and the decorative sheet.
The polyester resin sheet has a thickness of 10 μm and a stress at 2% elongation of 4 N / 1.
The one with 0 mm was used.

(Comparative Example 3)
In a small extruder “TEX30”, polypropylene alloy resin “KF084S” 87.3
12 parts by weight, 7.7 parts by weight of swellable fluorine mica "Somasif MAE-100" subjected to organic treatment, and 5.0 parts by weight of diblock oligomer "CB-OM12" on both ends are fed.
-Magnesium hydroxide surface treated with calcium hydroxystearate "CS-6"
120 parts by weight of “Mc Seeds N-4” was blended, melted and kneaded at a set temperature of 170 ° C., extruded into a strand, and the extruded strand was pelletized with a pelletizer to prepare a pellet of a thermoplastic resin composition.
Except having used the obtained pellet, it carried out similarly to the comparative example 1, and produced the plate-shaped molded object, the sheet-shaped molded object, and the decorative sheet.
The polyester resin sheet has a thickness of 20 μm and a stress at 2% elongation of 20 N /
A 10 mm one was used.

(Comparative Example 4)
In a small extruder “TEX30”, 50 parts by weight of polypropylene alloy resin “KF084S” and 60 parts by weight of swellable fluorine mica “Somasif MAE-100” subjected to organic treatment are fed and melted at a set temperature of 170 ° C. The mixture was kneaded and extruded into strands, and the extruded strands were pelletized with a pelletizer to produce thermoplastic resin composition pellets.
Except having used the obtained pellet, it carried out similarly to the comparative example 1, and produced the plate-shaped molded object, the sheet-shaped molded object, and the decorative sheet.
The polyester resin sheet has a thickness of 20 μm and a stress at 2% elongation of 20 N /
A 10 mm one was used.

(Comparative Example 5)
In a small extruder “TEX30”, random type polypropylene resin “Sun Allomer PC63”
“0A” 92.3 parts by weight, calcium carbonate (trade name “CALCIES P”, manufactured by Kamishima Chemical Co., Ltd.)
7 parts by weight was fed, melted and kneaded at a set temperature of 170 ° C., extruded into a strand, and the extruded strand was pelletized with a pelletizer to produce pellets of a thermoplastic resin composition.
Except having used the obtained pellet, it carried out similarly to the comparative example 1, and produced the plate-shaped molded object, the sheet-shaped molded object, and the decorative sheet.
The polyester resin sheet has a thickness of 20 μm and a stress at 2% elongation of 20 N /
A 10 mm one was used.

The average interlayer distance of the layered silicate in the plate-like molded bodies produced in Examples 1 to 15 and Comparative Examples 1 to 5,
The yield point stress and elongation at break of the combustion residue were measured and evaluated by the following methods. Examples 1 to 1
5 and the decorative sheets prepared in Comparative Examples 1 to 5 were evaluated for exothermic test, gas toxicity test, 2% modulus, and curved surface workability by the following methods.
These results are shown in Tables 1-4.

(1) Using a layered silicate average interlayer distance X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation), 2θ of a diffraction peak obtained from diffraction of a layered surface of a layered silicate in a plate-shaped molded body is measured. The (001) plane spacing (d) of the layered silicate was calculated by the following black diffraction formula, and the obtained d was the average interlayer distance (nm).
It was.
λ = 2 dsin θ
In the formula, λ is 0.154, d represents the interplanar spacing of the layered silicate, and θ represents the diffraction angle.

(2) Yield point stress of combustion residue 100 mm × 100 in accordance with ASTM E 1354 “Building Material Flammability Test Method”
It is 50 kW / by a cone calorimeter on a plate-shaped molded body cut to mm (thickness 3 mm).
After burning by radiating m ² heat rays, the strength of the combustion residue is reduced to 0.1 cm using an intensity measuring device.
The yield point stress (kPa) of the combustion residue was measured.

(3) Elongation at break In accordance with JIS K-6301 “Vulcanized Rubber Physical Test Method”, using a dumbbell-shaped No. 3 test piece cut out from a plate-shaped molded body, in an atmosphere of 20 ° C. to 50% RH At a pulling speed of 50 mm
A tensile test was performed at a rate of 1 minute, and the elongation at break (%) was measured.

(4) Exothermic test In accordance with ISO 1182, the sheet-like molded product was made of a non-combustible material (100 × 100 × 12.5).
mm) and then burned for 20 minutes under the condition of 50 kW / m ² . The time when the maximum heat generation rate at this time was continuously 200 kW / m ² or more and the total heat generation amount were measured.

(5) Gas Hazard Test According to ISO 1182, the decorative sheet is made of a non-combustible material (220 × 220 × 12.5 m
It was bonded to a gypsum board and heated with LP gas (propane gas with a purity of 95% or more) for 3 minutes, and then immediately heated at 1.5 kW for 3 minutes with electric heating. This combustion gas was introduced into a test box on which the mouse was placed, and the average action stop time of the mouse for 15 minutes from the start of heating was measured. The average action stoppage time was 6.8 minutes or more.

(6) 2% modulus The stress at the time of 2% elongation of the decorative sheet was measured according to JIS K-6734 “Hard vinyl chloride sheet and film test method”.

(7) Curved surface workability was evaluated by using a squeegee, which is a curved surface workability construction jig, to place the decorative sheet along the bent portion of the curved surface workability evaluation jig as shown in FIG. The evaluation criteria are as follows.
○: Compared with a polyvinyl chloride resin sheet (trade name “Palois”, manufactured by Sekisui Chemical Co., Ltd.)
The curved surface construction was inferior.
Δ: Compared with a polyvinyl chloride resin sheet (trade name “Palois”, manufactured by Sekisui Chemical Co., Ltd.)
The seat was low and the curved surface workability was slightly inferior.
X: The softness | flexibility of a decorative sheet was scarce, it was difficult to make it fit along the bending part of the jig | tool for curved surface workability evaluation, and it could not be provided as a product practically.

As shown in Tables 1 to 3, in the sheet-like molded bodies produced in Examples 1 to 15, the average interlayer distance of the layered silicate was 3 nm or more, so that a sintered body that can be a flame retardant coating can be easily formed. Formed.
Since the yield point stress of this combustion residue was as extremely high as 19 kPa or more, it was excellent in film formation and fire spread prevention. Moreover, it originated in the thickness of a polyester-type resin sheet and the stress at the time of 2% extending | stretching being in the fixed range, and it became excellent in curved surface workability. Furthermore, Examples 1 to
The decorative sheet produced in No. 15 exhibited excellent exothermic test results, gas toxicity test results, and a 2% modulus value.

On the other hand, as shown in Table 4, the decorative sheet produced in Comparative Example 1 also had a poor exothermic test result because no combustion residue was produced.
Moreover, in the decorative sheet produced in Comparative Example 2, sufficient flame retardancy was not obtained because no metal hydroxide was added.
Moreover, in the decorative sheet produced in Comparative Example 3, since the amount of metal hydroxide added was excessive, the elongation at break was significantly reduced.
Further, in the decorative sheet produced in Comparative Example 4, since the amount of swellable fluorine mica added was excessive, the elongation at break was lowered, the density was remarkably increased, and the flexibility was lowered.
Furthermore, since the decorative sheet produced in Comparative Example 5 was added with calcium carbonate instead of swellable fluorine mica, an effective film was not formed, and the flammability could not be controlled.
In addition, the decorative sheets prepared in Comparative Examples 1, 3, and 4 have poor curved workability due to the thick polyester resin sheet used and the low stress at 2% elongation, and lack practicality. It was.

According to the present invention, it has excellent flame retardancy and fire spread prevention property, expresses excellent flame retardancy effect and fire spread prevention effect due to shape retention effect during combustion, mechanical strength and stability, especially necking and sink marks are less, Furthermore, it is possible to provide a decorative sheet that is excellent in design like the conventional vinyl chloride resin sheet.

It is a side view which shows the jig | tool for curved surface workability evaluation.

Claims (10)

A decorative sheet comprising a sheet-like molded article having a multilayer structure and an adhesive layer laminated on the sheet-like molded article,
The sheet-like molded body has at least a layer made of a polyester-based resin and a layer made of a thermoplastic resin composition,
The layer made of the polyester resin is on the surface opposite to the side on which the pressure-sensitive adhesive layer is laminated,
The thermoplastic resin composition has a layered silicate content of 0.1 to 10 with respect to 100 parts by weight of the thermoplastic resin.
A decorative sheet comprising 0 part by weight and 0.1 to 70 parts by weight of a metal hydroxide. The layer made of polyester resin has a thickness of 15 to 70 μm and a stress at 2% elongation of 2
The decorative sheet according to claim 1, wherein the decorative sheet is 0 to 60 N / 10 mm. The decorative sheet according to claim 1 or 2, wherein the thermoplastic resin is a polyolefin resin. Polyolefin resins include ethylene homopolymer, copolymer of ethylene and α-olefin other than ethylene copolymerizable with ethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, propylene And a copolymer of propylene and an α-olefin other than propylene copolymerizable with the propylene, and at least one selected from the group consisting of polypropylene-based alloy resins. Item 1. A decorative sheet according to item 1, 2 or 3. 5. The decorative sheet according to claim 1, 2, 3 or 4, wherein the layered silicate is montmorillonite and / or swellable mica. 6. The decorative sheet according to claim 1, 2, 3, 4 or 5, wherein the layered silicate contains an alkyl ammonium ion having 6 or more carbon atoms. The layered silicate has an average interlayer distance of 3 nm on the (001) plane measured by wide-angle X-ray diffraction measurement.
It is above, and one part or all part is disperse | distributing to 5 layers or less,
The decorative sheet according to 2, 3, 4, 5 or 6. In a combustion test according to ASTM E 1354, the yield point stress when a combustion residue burned by heating for 30 minutes under a radiant heating condition of 50 kW / m ² is compressed at a speed of 0.1 cm / s is 4.9 kPa. It is the above, The decorative sheet of Claim 1, 2, 3, 4, 5, 6 or 7. A decorative sheet having a thickness of 65 μm or more excluding the adhesive layer is based on ISO 1182,
When bonded to the non-combustible material burns with radiant heating condition of 50 kW / m ^2, heating starts after 2
The time during which the maximum heat generation rate is continuously 200 kW / m ² or more in 0 minutes is less than 10 seconds, and the total heat generation amount is 8 MJ / m ² or less, 4, 5
, 6, 7 or 8. The decorative sheet according to claim 9, wherein the decorative sheet passes a gas toxicity test in accordance with ISO 1182.

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