JPH09226071A - Decorative film/sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative film/sheet with good transparency of the surface layer, excellent V-cut processability and wrapping processability and no problem on discarding. SOLUTION: A decorative film/sheet using a film or a sheet consisting of a polypropylene resin consisting of a propylene homopolymer with a pentad fraction based on<13> C-NMR spectra of 15-50% in rrrr/(1-mmmm), a meltincr peak temp. (Tm) measured by DSC of at least 150 deg.C and a melting enthalpy (ΔH) of at most 100J/g and/or a propylene copolymer contg. at most 4wt.% other olefin unit or a resin compsn. of 99-60wt.% this polypropylene resin and 1-40wt.% thermoplastic elastomer copolymer as the surface layer and/or a base material and a decorative material prepd. by sticking this decorative film/ sheet on a wooden base material, a metal base material and an inorg. base material, are provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic film / sheet and a cosmetic material. More specifically, the surface layer has good transparency and is excellent in bending workability, V-cut workability and lapping workability, and when incinerated. TECHNICAL FIELD The present invention relates to a laminated decorative film / sheet which does not generate a chlorine gas or the like and thus has no problem of disposal, and a decorative material using the laminated decorative film / sheet.

[0002]

2. Description of the Related Art Conventionally, as a decorative surface plate for furniture or kitchen cabinets, a decorative film or sheet having a grain pattern printed on a base material made of a wood-based material is generally bonded with an adhesive. The structure is used. The decorative film / sheet used for such a surface decorative plate usually has lapping processability, that is, if the base material has an uneven portion or a complicated shape, it can be attached according to the shape, V There is a demand for cutting workability, that is, workability when V-cutting is applied to a surface decorative plate after lamination and the box is assembled or the end portion is bent. Specifically, it is required that the folded portion of the decorative film / sheet does not suffer from inconveniences such as cracking, cutting, and whitening.

In order to impart V-cut workability and lapping workability to the decorative film / sheet, a vinyl chloride resin film / sheet has been generally used so far. However, this vinyl chloride resin has poor weather resistance and stain resistance, needs a thickness to obtain strength during V-cut processing, and generates chlorine gas during combustion, so its disposal is a problem. There is. Various proposals have been made so far in order to improve these problems, but none of them have been sufficiently satisfactory. For example, in Japanese Patent Laid-Open No. 3-202347, a thermoplastic resin is used instead of the vinyl chloride resin, but in this case, there is a problem that a two-layer structure is formed in order to obtain strength and the manufacturing process is increased. . In JP-A-6-262729, an acrylic resin is used, but this resin has high water absorption, and warpage may occur due to a difference in dimensional stability. In Japanese Patent Laid-Open No. 7-246684,
Although a thermosetting resin is used, this resin has a drawback that it is difficult to handle during production. In addition, JP-A-7-17005, JP-A-7-24979,
Polyester resins are used in JP-A-7-137205 and JP-A-7-232415, and polypropylene resin or polyethylene resin is used in JP-A-6-198831. However, these resins have sufficient flexibility. Absent.

[0004]

Under these circumstances, the present invention is excellent in bending workability, V-cut workability, lapping workability, and the like, and has a good surface layer transparency, and at the time of incineration. It is an object of the present invention to provide a decorative film / sheet which does not generate a chlorine gas or the like and has no problem of disposal, and a decorative material such as a decorative wood material using the decorative film / sheet.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a laminated structure composed of a surface layer, an adhesive layer, a pattern layer, an adhesive layer and a base material, Or in a decorative film / sheet having a laminated structure consisting of a surface layer, an adhesive layer and a pattern layer, as a surface layer or a base material,
It has been found that the object can be achieved by using a film or sheet made of a specific polypropylene resin or a resin composition containing the polypropylene resin and a thermoplastic elastomer copolymer in a specific ratio.
The present invention has been completed based on such findings.
That is, the present invention relates to a decorative film sheet having a surface layer, an adhesive layer, a picture layer, a laminated structure composed of an adhesive layer and a base material, or a laminated structure composed of a surface layer, an adhesive layer and a picture layer. On the layer and / or the substrate,
(A) (a) In the pentad fraction by isotope carbon nuclear magnetic resonance ( ¹³ C-NMR) spectrum, rrrr /
(1-mmmm) × 100 is 15 to 50%, (b) the melting peak temperature (Tm) measured by a differential scanning calorimeter (DSC) is 150 ° C. or higher, and (c) the enthalpy of fusion measured by DSC ( (H) a polypropylene-based resin comprising a propylene homopolymer having 100 J / g or less and / or a propylene-based copolymer containing 4% by weight or less of another olefin unit, or (B) the (A) composition. The present invention provides a decorative film / sheet comprising a film or sheet comprising a resin composition comprising 99 to 60% by weight of the polypropylene resin and 1 to 40% by weight of a thermoplastic elastomer copolymer. Also, the present invention
The present invention also provides a decorative wood material, a decorative metal material, and a decorative inorganic material obtained by adhering the above decorative film / sheet to a wood, metal or inorganic substrate.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The decorative film / sheet of the present invention is a laminated structure comprising a surface layer, an adhesive layer, a picture layer, an adhesive layer and a base material, or a surface layer, an adhesive layer and a picture layer. It has a structure. In the present invention, the surface layer and / or the base material in the decorative film / sheet is a homopolymer of propylene having a specific property, which is the component (A) shown below, and / or other contents of 4% by weight or less. A polypropylene resin comprising a propylene copolymer containing an olefin unit, or a film or sheet comprising a resin composition comprising the polypropylene resin of the component (A) which is the component (B) and a thermoplastic elastomer copolymer is provided. Used. Here, the specific properties of the propylene homopolymer or propylene-based copolymer as the component (A) refer to the properties shown in (a) to (c) below. First,
(A) In the pentad fraction by isotope carbon nuclear magnetic resonance ( ¹³ C-NMR) spectrum, rrrr / (1-m
mmm) × 100 must be in the range of 15 to 50%. If this value is less than 15%, the heat resistance will be insufficient, and if it exceeds 50%, the flexibility will be insufficient and V-cut workability and lapping workability will deteriorate. From the viewpoint of the balance between heat resistance and flexibility, preferable rrrr / (1-mmm
m) × 100 is in the range of 20-40%. Where rr
rr is 5 which is a side chain with respect to a main chain formed by a carbon-carbon bond composed of any five consecutive propylene units.
Mmmm means a three-dimensional structure in which two methyl groups are alternately located in opposite directions or the ratio thereof, and mmmm means any continuous 5
It means a three-dimensional structure in which all five methyl groups, which are side chains, are located in the same direction with respect to the main chain formed by carbon-carbon bonds composed of one propylene unit, or the ratio thereof.

This rrrr / (1-mmmm) ×
100 is a value measured as follows. That is,
Using JNM-FX-200 (manufactured by JEOL Ltd., ¹³ C-nuclear resonance frequency 50.1 MHz), measurement mode: complete proton decoupling method, pulse width: 6.9 μs (45 °), pulse repetition time: 3 s, Accumulation number: 10,000 times, solvent: 1,2,4-trichlorobenzene / deuterated benzene (9
0/10% by volume), sample concentration 250 mg / 2.5 ml solvent, measurement temperature: 130 ° C., ¹³ C-NM
R measurement was performed, and the pentad fraction was measured by the difference in chemical shift due to the stereoregularity of the methyl group, that is, from the area intensity ratio of each peak of mmmm to mrrm appearing in the 22.5 to 19.5 ppm region, and rrrr was measured. / (1-mm
The value of (mm) × 100 was determined. mmmm: 21.86 ppm mmmr: 21.62 ppm mmrr: 21.08 ppm mmrm + rrmr: 20.89 ppm rrrr: 20.36 ppm mrrm: 19.97 ppm

Next, (b) a differential scanning calorimeter (DS)
It is necessary that the melting peak temperature (Tm) measured in C) is 150 ° C. or higher. If Tm is less than 150 ° C, sufficient heat resistance cannot be obtained. This Tm is usually 150-1
It is in the range of 65 ° C. The Tm is Perkin-
Measurement was performed using DSC-7 manufactured by Elmer, and JIS
It is the value obtained as the temperature of the melting peak according to K-7121. Further, (c) the melting enthalpy (ΔH) measured by DSC must be 100 J / g or less. When ΔH exceeds 100 J / g, flexibility is impaired and V-cut workability and lapping workability deteriorate. Further, if this ΔH is too small, the strength will be insufficient, so the preferable ΔH is in the range of 10 to 100 J / g. In addition, the ΔH is D manufactured by Perkin-Elmer.
It is a value obtained by measuring using SC-7 and as the total heat energy absorbed during crystal melting in accordance with JIS K-7122. The DSC measurement was carried out under the conditions of holding the sample at 230 ° C. for 3 minutes, lowering the temperature to 50 ° C. at 10 ° C./minute, holding the sample for 3 minutes, and raising the temperature to 230 ° C. at 10 ° C./minute.

The propylene homopolymer as the component (A) and the propylene-based copolymer containing 4% by weight or less of another olefin unit have a boiling n-heptane-soluble content of 7 to 50% by weight. Those in the range are preferable. If the boiling n-heptane-soluble content is less than 7% by weight, flexibility may be insufficient and V-cut processability and lapping processability may be deteriorated. If it exceeds 50% by weight, sufficient mechanical strength and heat resistance may be obtained. I can not get sex. From the viewpoint of the balance of flexibility, mechanical strength and heat resistance, the more preferable boiling n-heptane soluble content is in the range of 10 to 40% by weight. The boiling n-heptane soluble content is a value obtained by calculating the soluble content from the extraction residual quantity after extraction with boiling n-heptane for 6 hours using a Soxhlet extraction tester. Further, in the propylene homopolymer and the propylene-based copolymer containing 4% by weight or less of another olefin unit, carbons having a methyl group of a side chain are usually arranged adjacent to each other in the propylene chain part. No, that is, there is no reverse coupling and they are lined up in alternating order. That is, in the present invention, each propylene unit has a head-to-tail (he
connected by ad-tail) connection, head-head
There is virtually no bond or tail-tail bond.

In the propylene-based copolymer containing 4% by weight or less of the other olefin units, examples of the olefin comonomer forming the other olefin unit include ethylene; butene-1; pentene-1. ;
4-methyl-1-pentene; hexene-1; heptene-
1; octene-1, nonene-1, decene-1 and other α-
Olefins can be mentioned. Of these, ethylene is preferred. These olefins may be used alone or in combination of two or more. Further, it is necessary to use the olefins of these comonomers such that the content of units derived from the olefins in the obtained propylene-based copolymer is 4% by weight or less. In the present invention, the polypropylene resin used as the component (A) preferably has a melt index (MI) in the range of 0.1 to 50 g / 10 minutes. If this MI is less than 0.1 g / 10 minutes, molding is difficult, and if it exceeds 50 g / 10 minutes, the mechanical properties of the obtained film or sheet will be insufficient. From the viewpoint of the balance between the moldability and the mechanical properties of the film or sheet, the MI is more preferably 0.2 to 30 g / 10 minutes.
This MI complies with JIS K7210, and the load
The values are measured under the conditions of 2.16 kgf and temperature of 230 ° C. The polypropylene resin as the component (A) in the present invention can be produced by, for example, a gas phase one-step polymerization method, a slurry one-step polymerization method, a gas phase multi-step polymerization method, a slurry multi-step polymerization method, or a blending method. For example, when it is produced by a polymerization method, it is composed of (a) (i) a solid catalyst component composed of magnesium, titanium, a halogen atom and an electron donor, and (ii) a crystalline polyolefin which is optionally used. A solid component, (b) an organoaluminum compound, (c) a general formula (I)

[0011]

Embedded image

[Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is 0. ~ (6-m)
Indicates an integer. ] Homopolymerization of propylene or copolymerization of propylene with other olefins in the presence of a catalyst system comprising an alkoxy group-containing aromatic compound represented by You can do it. The solid component (a) is composed of a solid catalyst component of component (i) consisting of magnesium, titanium, a halogen atom and an electron donor, and a crystalline polyolefin of component (ii) which is optionally used. . The solid catalyst component of component (i) contains magnesium, titanium, a halogen atom and an electron donor as essential components, and can be prepared by contacting a magnesium compound, a titanium compound and an electron donor. it can. In this case, the halogen atom is included as a halide in the magnesium compound and / or the titanium compound.

Examples of the magnesium compound include magnesium dihalides such as magnesium dichloride,
Magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, dialkoxy magnesium such as diethoxy magnesium, diallyloxy magnesium, alkoxy magnesium halide,
Examples include aryloxy magnesium halides, dialkyl magnesiums such as ethylbutyl magnesium, alkyl magnesium halides, or reaction products of organomagnesium compounds with electron donors, halosilanes, alkoxysilanes, silanols, aluminum compounds, and the like. Magnesium dihalide,
Dialkoxy magnesium, dialkyl magnesium,
Alkyl magnesium halides are preferred. These magnesium compounds may be used alone or in combination of two or more. Further, as the magnesium compound, a reaction product of metallic magnesium and halogen and / or a halogen-containing compound and alcohol can also be used. The metallic magnesium used at this time is not particularly limited, and metallic magnesium having an arbitrary particle size, for example, granular, ribbon-like, powder-like or the like can be used. Further, the surface state of the magnesium metal is not particularly limited, but it is preferable that the surface of the surface is not coated with magnesium oxide. Further, any alcohol can be used, but it has 1 to 6 carbon atoms.
It is preferable to use the lower alcohols mentioned above, and ethanol is particularly preferable because it gives a solid catalyst component that remarkably improves the expression of the catalytic performance. The purity and the water content of the alcohol are not limited, but when an alcohol having a high water content is used, magnesium hydroxide is formed on the surface of metal magnesium. Therefore, it is preferable to use an alcohol having a water content of 1% by weight or less, particularly 2000 ppm or less. Preferably, the lower the water content, the more advantageous.

The type of halogen and / or halogen-containing compound is not limited, and any compound containing a halogen atom in its molecule can be used as the halogen-containing compound. In this case, the type of halogen atom is not particularly limited, but chlorine, bromine or iodine, particularly iodine is preferably used. Among the halogen-containing compounds, halogen-containing metal compounds are particularly preferable. The state, shape, particle size, etc. are not particularly limited and may be arbitrary, for example, alcohol solvent (eg, ethanol).
It can be used in the form of a solution in. The amount of alcohol used is usually 2 to 100 with respect to 1 mol of magnesium metal.
It is selected in the range of 5 to 50 mol, preferably 5 to 50 mol. If the amount of alcohol is too large, it tends to be difficult to obtain a magnesium compound having a good morphology, and if it is too small, the reaction with metallic magnesium may not be carried out smoothly. The halogen and / or the halogen-containing compound is usually, for each gram atom of metallic magnesium,
As a halogen atom, 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.0
Used at a rate of 01 gram atom or more. Below 0.0001 gram atom, when the obtained magnesium compound is used without pulverization, the loading amount, activity, stereoregularity,
The morphology of the produced polymer is lowered, and the pulverization process becomes indispensable, which is not preferable. Further, by appropriately selecting the amount of halogen and / or the halogen-containing compound used, the particle size of the obtained magnesium compound can be arbitrarily controlled.

The reaction itself of the magnesium metal, the alcohol, the halogen and / or the halogen-containing compound can be carried out by a known method. For example, it is a method of obtaining a desired magnesium compound by reacting metallic magnesium, an alcohol, a halogen and / or a halogen-containing compound under reflux, usually for about 20 to 30 hours until generation of hydrogen gas is not observed. Specifically, for example, when iodine is used as the halogen, a method in which metallic magnesium and solid iodine are put into an alcohol and then heated and refluxed, and an alcohol solution of metallic magnesium and iodine is dropped into the alcohol and then added. Examples thereof include a method of heating and refluxing, a method of dropping an alcohol solution of iodine while heating an alcohol solution containing metallic magnesium, and the like. Both methods are preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas, optionally using an inert organic solvent (for example, saturated hydrocarbon such as n-hexane). Metal magnesium,
Regarding the introduction of the alcohol, the halogen and / or the halogen-containing compound, it is not necessary to add the entire amount to the reaction tank from the beginning, and it may be added in a divided manner. A particularly preferred form is a method in which the alcohol is charged in its entirety from the beginning, and the magnesium metal is divided and charged several times.

In such a case, it is possible to prevent a temporary large amount of hydrogen gas from being generated, which is very desirable from the viewpoint of safety. Also, the size of the reaction tank can be reduced. Furthermore, it becomes possible to prevent the entrainment of alcohol, halogen and / or halogen-containing compound caused by the temporary large generation of hydrogen gas. The number of divisions is
It may be determined in consideration of the scale of the reaction tank, and usually 5 to 10 times is preferable considering the complexity of the operation. Further, it goes without saying that the reaction itself may be a batch type or a continuous type. Furthermore, as a modified method, a small amount of metallic magnesium is first added to the alcohol that has been entirely added from the beginning, the product produced by the reaction is separated and removed in another tank, and then a small amount of metallic magnesium is added again. It is also possible to repeat. When the magnesium compound thus obtained is used for the next preparation of the solid catalyst component, a dried one may be used, or a magnesium compound that has been filtered and washed with an inert solvent such as heptane may be used. In any case, the obtained magnesium compound can be used in the next step without pulverization or classification operation for adjusting the particle size distribution.

Examples of the titanium compound include tetramethoxytitanium, tetraethoxytitanium and tetra-titanium.
n-propoxytitanium, tetraisopropoxytitanium,
Tetra-n-butoxy titanium, tetraisobutoxy titanium, tetracyclohexyloxy titanium, tetraphenoxy titanium and other tetraalkoxy titanium, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other tetrahalogenated titanium, methoxytitanium trichloride. , Trihalogenated monoalkoxytitanium such as ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide, dimethoxytitanium dichloride,
Dihalogenated dialkoxytitanium such as diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, diethoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, tri-n- Examples thereof include monohalogenated trialkoxy titanium such as butoxytitanium chloride, and of these, a high halogen content titanium compound, particularly titanium tetrachloride is preferable. These titanium compounds may be used alone or in combination of two or more.

As the electron donor, those exemplified later as the electron donating compound of the component (d) can be used. The solid catalyst component (i) can be prepared by a known method (JP-A-53-43094, JP-A-55-135).
102, JP-A-55-135103, JP-A-56-18606, JP-A-56-166205.
JP-A-57-63309, JP-A-57-63309
190004, JP-A-57-300407, and JP-A-58-47003). The composition of the solid catalyst component (i) thus prepared usually has a magnesium / titanium atomic ratio of 2 to 100,
The halogen / titanium atomic ratio is in the range of 5 to 100, and the electron donor / titanium molar ratio is in the range of 0.1 to 10. Examples of the crystalline polyolefin of the component (ii) used as necessary in the preparation of the solid component (a) include polyethylene, polypropylene, polybutene, poly-4-methyl-
A crystalline polyolefin obtained from an α-olefin having 2 to 10 carbon atoms such as 1-pentene can be mentioned. This crystalline polyolefin is (1) a method of prepolymerizing an olefin in the presence of (1) a combination of the solid catalyst component, an organoaluminum compound and an electron-donating compound used as necessary (preliminary polymerization method). ), (2) In the crystalline powder such as crystalline polyethylene or polypropylene having a uniform particle size, (i) the solid catalyst component and an organoaluminum compound and an electron donating compound (melting point 100 ° C. or higher) optionally used. Can be obtained by using a method of dispersing and (dispersion method), (3) a method of combining the method of (1) and the method of (2), and the like. In the prepolymerization method (1), the aluminum / titanium atomic ratio is usually 0.1 to 100, preferably 0.5 to
The electron donating compound / titanium molar ratio is selected in the range of 0 to 50, preferably 0.1 to 2.
In (a) solid component, (i) solid catalyst component and (ii)
Regarding the ratio with the crystalline polyolefin, the weight ratio of the component (ii) to the component (i) is usually 0.33 to 200,
It is preferably selected in the range of 0.10 to 50.

Next, the organoaluminum compound used as the component (b) is represented by the general formula (II) AlR ³ _p X _3-p (II) [wherein R ³ has 3 to 20 carbon atoms]. An alkyl group or an aryl group having 6 to 20 carbon atoms, X is a halogen atom, and p is 1 to 3
Indicates the number of ] Can be mentioned. For example, triisopropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trioctyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride,
Dialkyl aluminum monohalides such as diisobutyl aluminum monochloride and dioctyl aluminum monochloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, and the like can be preferably used. These aluminum compounds may be used alone or in combination of two or more.

In the catalyst system of the present invention, the component (c) is represented by the general formula (I)

[0021]

Embedded image

[Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is 0. ~ (6-m)
Indicates an integer. ] An alkoxy group-containing aromatic compound represented by the following is used.

Specific examples of the alkoxy group-containing aromatic compound include m-methoxytoluene; o-methoxyphenol; m-methoxyphenol; 2-methoxy-4-.
Methylphenol; vinylanisole; p- (1-propenyl) anisole; p-allylanisole; 1,3-
Bis (p-methoxyphenyl) -1-pentene; 5-allyl-2-methoxyphenol; 4-hydroxy-3-
Methoxybenzyl alcohol; methoxybenzyl alcohol; nitroanisole; monoalkoxy compounds such as nitrophenetole; o-dimethoxybenzene; m-dimethoxybenzene; p-dimethoxybenzene; 3,4-
Dimethoxytoluene; 2,6-dimethoxyphenol;
Dialkoxy compounds such as 1-allyl-3,4-dimethoxybenzene, 1,3,5-trimethoxybenzene; 5
-Allyl-1,2,3-trimethoxybenzene; 5-allyl-1,2,4-trimethoxybenzene; 1,2,3
-Trimethoxy-5- (1-propenyl) benzene;
1,2,4-trimethoxy-5- (1-propenyl) benzene; 1,2,3-trimethoxybenzene; 1,2,
Examples thereof include trialkoxy compounds such as 4-trimethoxybenzene, and among these, dialkoxy compounds and trialkoxy compounds are preferable. These alkoxy group-containing aromatic compounds may be used alone,
Two or more kinds may be used in combination.

Further, in the catalyst, an electron donating compound is used as the component (d) if necessary. The electron donating compound is a compound containing oxygen, nitrogen, phosphorus, sulfur, silicon, and the like. Basically, a compound having a performance of improving regularity in propylene polymerization is considered.
Examples of such electron-donating compounds include organosilicon compounds, esters, thioesters, amines,
Ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides,
Examples thereof include aldehydes, organic acids and azo compounds.

For example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane. , Phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexylmethyldimethoxysilane and other organosilicon compounds, monomethylphthalate, monoethylphthalate, monopropylphthalate, monobutylphthalate, monoisobutylphthalate, monoamylphthalate, monoisoamylphthalate, monomethylterephthalate , Monoethyl terephthalate, monopropyl terephthalate, monobutyl terephthalate, Roh isobutyl terephthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, methyl ethyl phthalate, methyl isobutyl phthalate,
Methyl propyl phthalate, ethyl butyl phthalate,
Ethyl isobutyl phthalate, ethyl propyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl isobutyl terephthalate, methyl propyl terephthalate, ethyl butyl terephthalate, ethyl isobutyl terephthalate, ethyl propyl terephthalate, propyl Isobutyl terephthalate,
Dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methyl isobutyl isophthalate, methyl propyl isophthalate, ethyl butyl isophthalate, ethyl isobutyl isophthalate, ethyl propyl isophthalate, propyl isobutyl isophthalate Aromatic dicarboxylic acid ester such as phthalate,
Methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, Ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, toluyl Methyl acid, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate,
Monoesters such as ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethyl naphthoate, γ-butyrolactone,
δ-valerolactone, coumarin, phthalide, esters such as ethylene carbonate, benzoic acid, organic acids such as p-oxybenzoic acid, succinic anhydride, benzoic anhydride, p-anhydride
Acid anhydrides such as toluic acid, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone and other ketones, acetaldehyde, propionaldehyde, octyl aldehyde,
Aldehydes such as tolaldehyde, benzaldedo, and naphthylaldehyde, acetyl chloride, acetyl bromide, propionyl chloride, butyryl chloride, isobutyryl chloride, 2-methylpropionyl chloride,
Valeryl chloride, isovaleryl chloride, hexanoyl chloride, methylhexanoyl chloride, 2-ethylhexanoyl chloride, octanoyl chloride, decanoyl chloride, undecanoyl chloride, hexadecanoyl chloride, octadecanoyl chloride, benzylcarbonyl Chloride, cyclohexanecarbonyl chloride, malonyl dichloride, succinyl dichloride, pentanedioleyl dichloride, hexanedioleyl dichloride, cyclohexanedicarbonyldichloride, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride , Benzene-1,2,4-
Acid halides such as tricarbonyl trichloride,
Methyl ether, ethyl ether, isopropyl ether, n-butyl ether, isopropyl methyl ether, isopropyl ethyl ether, t-butyl ethyl ether, t-butyl-n-propyl ether, t-butyl-n-butyl ether, t-amyl methyl ether,
Ethers such as t-amyl ethyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, tributylamine, N, N′-dimethylpiperazine, Amine such as tribenzylamine, aniline, pyridine, pyrroline, tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, tolunitrile, 2,2′-azobis (2-methylpropane), 2,2′-azobis (2 -Ethyl propane),
An azo compound in which a sterically hindering substituent is bonded to an azo bond such as 2,2′-azobis (2-methylpentane) is exemplified.

Of these, organosilicon compounds, esters, ketones, ethers, thioethers, acid anhydrides and acid halides are preferable, and particularly diphenyldimethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane and the like. An organosilicon compound,
Aromatic dicarboxylic acid diesters such as di-n-butyl phthalate and diisobutyl phthalate, and alkyl esters of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid and toluic acid are preferable. These electron donating compounds may be used alone or in combination of two or more. Regarding the amount of each component used in the catalyst system, (a) the solid component is converted to titanium atoms and is usually 0.0 per 1 liter of the reaction volume.
An amount is used such that it is in the range of 005 to 1 mol. Further, (b) the organoaluminum compound is aluminum /
The ratio of titanium atoms is usually 1 to 3000, preferably 40.
An amount of ˜800 is used, and if the amount deviates from the above range, the catalytic activity may be insufficient. Furthermore, the molar ratio of the alkoxy group-containing aromatic compound (c) to the titanium atom in the solid component (a) is generally 0.01 to
It is used in a ratio of 500, preferably 1 to 300. If this amount is less than 0.01, the physical properties of the polymer produced may be deteriorated, and if it exceeds 500, the catalytic activity may be insufficient.

In the present invention, the polypropylene resin as the component (A) is obtained by homopolymerizing propylene or copolymerizing propylene with a small amount of other olefins in the presence of the catalyst system, for example, by a one-step polymerization method. It can be manufactured. The polymerization method is not particularly limited, and slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization, suspension polymerization and the like can be used. When carrying out the polymerization by gas phase polymerization, the polymerization pressure is usually 10 to 45 kg / cm ² , preferably 20 to
The polymerization temperature is 30 kg / cm ² , and the polymerization temperature is usually selected in the range of 40 to 90 ° C, preferably 60 to 75 ° C. The molecular weight of the polymer can be adjusted by known means, for example, adjusting the hydrogen concentration in the polymerization vessel. It can also be adjusted by producing a (co) polymer having a relatively high molecular weight in the polymerization step and melt-kneading the obtained (co) polymer in the presence of an organic peroxide. Polymerization time is 5 minutes to 10 minutes
It is appropriately selected depending on the time.

In the polymerization, the respective components constituting the catalyst system, that is, the components (a) to (d) are mixed in a predetermined ratio and brought into contact with each other, and then the raw material monomers are immediately introduced,
The polymerization may be started, or the raw material monomer may be introduced after aging for about 0.2 to 3 hours after the contact. further,
This catalyst component can be supplied by suspending it in an inert solvent or an olefin as a raw material monomer. Post-treatment after the polymerization can be performed by a conventional method. That is, in the gas phase polymerization method, after the polymerization, a nitrogen stream or the like may be passed through the polymer powder discharged from the polymerization vessel in order to remove unreacted monomers and the like contained therein. If desired, pelletizing may be carried out by an extruder, and in this case, a small amount of water, alcohol or the like may be added in order to completely deactivate the catalyst. In the bulk polymerization method, after polymerization, the unreacted monomer may be completely separated from the polymer discharged from the polymerization vessel, and then pelletized.

In the present invention, the polypropylene resin as the component (A) may be used as the surface layer or the film or sheet of the substrate, and the polypropylene resin as the component (B) and the thermoplastic elastomer. You may use the resin composition with a copolymer. The thermoplastic elastomer copolymer used as the component (B) exhibits the characteristics of thermoplastic resin such as plasticity and fluidity required at the molding processing temperature, and exhibits rubber-like physical properties at room temperature before or after molding. It means the copolymer shown. Examples of such thermoplastic elastomer copolymers include styrene-diene copolymer elastomers and hydrogenated products thereof, ethylene-α-olefin copolymer elastomers having 3 or more carbon atoms, ethylene-α-olefins having 3 or more carbon atoms. Examples thereof include olefin-polyene copolymer elastomers and hydrogenated products thereof, ethylene-unsaturated carboxylic acid-α, β-unsaturated carboxylic acid ester copolymer elastomers, and acrylonitrile copolymer elastomers.

Examples of the styrene-diene copolymer elastomers include block copolymers of aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene and conjugated diene compounds such as butadiene and isoprene. . Styrene is particularly preferable as the aromatic compound, and examples of the form of the block copolymer include a single block copolymer, a teleblock copolymer, a radial teleblock copolymer, and a multiblock copolymer. . The content of the aromatic vinyl compound unit in the styrene-diene copolymer elastomer is preferably in the range of 10 to 50% by weight, and in this case, 10
If it is less than 50% by weight, the moldability of the obtained composition tends to be poor, and if it exceeds 50% by weight, the low-temperature impact resistance tends to decrease. Further, by highly hydrogenating the conjugated diene unit portion of the block copolymer, it is also possible to reduce unsaturated groups in the main chain and improve heat resistance.
Particularly, a styrene-ethylene-butylene-styrene copolymer elastomer is suitable.

The ethylene-C3 or more α-olefin copolymer elastomer is, for example, a copolymer of ethylene and propylene, butene-1, hexene-1, octene-1, etc. or ethylene, propylene and butene-1. And copolymers thereof. As such,
It may be copolymerized by two-step polymerization in the presence of the component (A), or may be copolymerized by the elastomer alone. In the case of, it is a copolymer elastomer having an ethylene unit content of approximately 10 to 80% by weight, and an ethylene-propylene copolymer (ethylene unit content of 20
~ 70 wt%) is the most typical. In this case, the ethylene unit content is usually about 20 to 90% by weight, preferably 30 to 85% by weight.

The ethylene-C3 or more α-olefin-polyene copolymer elastomer has 3 carbon atoms.
Examples of the above α-olefin include propylene, butene-1, hexene-1, heptene-1, octene-1,
Nonene-1, decene-1, undecene-1, dodecene-
1 or the like may be used alone or in combination of two or more. Examples of the polyene include conjugated dienes such as butadiene, isoprene and piperylene, 1,4-hexadiene; 1,6
-Octadiene; 2-methyl-1,5-hexadiene;
6-methyl-1,5-heptadiene; 7-methyl-1,
6-octadiene; cyclohexadiene; dicyclopentadiene; methyltetrahydroindene; 5-ethylidene-2-norbornene; 5-methylene-2-norbornene; 5-isopropylidene-2-norbornene; 6-chloromethyl-5-isopropenyl- Non-conjugated dienes such as 2-norbornene, 2,3-diisopropylidene-5
-Norbornene; 2-ethylidene-3-isopropylidene-5-norbornene; 2-propenyl-2,2-norbornene; 1,3,7-octatriene; 1,4,9-
One or two or more trienes such as decatriene can be used, and among these, a diene compound of a conjugated diene or a non-conjugated diene is preferable. It is advantageous to adjust the copolymerization amount of the polyene so that the iodine value of the copolymer is 30 or less, preferably in the range of 5 to 25, in order to effectively exhibit the properties as an elastomer. . Further, hydrogenation may be performed so that the iodine value is within the above range.

Further, ethylene-unsaturated carboxylic acid-α,
Examples of the unsaturated carboxylic acid used in the β-unsaturated carboxylic acid ester copolymer elastomer include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid,
Fumaric acid, itaconic acid, crotonic acid, isocrotonic acid,
Examples thereof include citraconic acid, sorbic acid, mesaconic acid, angelic acid, and the like. These may be used alone or in combination of two or more. As the α, β-ethylenically unsaturated carboxylic acid ester, for example, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, isocrotonic acid, etc., preferably having 3 to 8 carbon atoms. α, β-ethylenically unsaturated carboxylic acids and monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and n-propyl alcohol, dihydric alcohols such as ethylene glycol and propylene glycol, polyhydric alcohols such as glycerin and pentaerythritol. And the like. These esters may be used alone or in combination of two or more. Furthermore, as the copolymerized elastomer, if desired, a derivative obtained by copolymerizing a derivative of the unsaturated carboxylic acid, such as an acid anhydride, an amide, an imide, or a metal salt, can also be used.

The copolymer elastomer has ethylene units of 50 to 95% by weight and unsaturated carboxylic acid units of 1 to 1.
Preference is given to those which contain 0% by weight and 4 to 49% by weight of α, β-ethylenically unsaturated carboxylic acid ester units, are copolymerized randomly and have elastomeric properties. When the content of the ethylene unit exceeds 95% by weight,
α, β-ethylenically unsaturated carboxylic acid ester unit is 4
If it is less than 50% by weight, the elastomeric properties may not be sufficiently expressed. Impact resistance tends to decrease. 1% by weight of unsaturated carboxylic acid unit
If less than 10% by weight, the crosslinkability is poor, and if more than 10% by weight, the elastomer properties are not sufficient.

On the other hand, as the acrylonitrile copolymer elastomer, for example, a copolymer of an unsaturated nitrile such as acrylonitrile or methacrylonitrile and a chain diene such as 1,3-butadiene or 1,3-hexadiene,
Examples thereof include acrylonitrile-1,3-butadiene-maleic anhydride terpolymers and copolymers in which the double bond is saturated by highly hydrogenating the diene portion of these copolymers. The properties of the thermoplastic elastomer copolymer according to the present invention are not particularly limited, but the Mooney viscosity at 100 ° C. is about 10 to 80, the tensile elongation is 500% or more, and the glass transition temperature is Is -20 [deg.] C. or less, and is particularly preferable in that it contributes to softening of the polypropylene resin as the component (A) without lowering the heat resistance thereof. Among the above thermoplastic elastomer copolymers, from the viewpoints of flexibility, moldability, heat resistance, etc., ethylene-α-olefin copolymer elastomers having 3 or more carbon atoms, ethylene-α-olefins having 3 or more carbon atoms Hydrogenated products of a diene-based copolymer elastomer, a styrene-diene-based copolymer elastomer, and a styrene-diene-based copolymer elastomer are preferable. These thermoplastic elastomer copolymers may be used alone or in combination of two or more.

In the resin composition of the component (B) in the present invention, the blending ratio of both components is 99 to 60% by weight of the polypropylene resin of the component (A), and the thermoplastic elastomer copolymer is 1%. -40% by weight. When the amount of the thermoplastic elastomer copolymer exceeds 40% by weight, the transparency is lowered and the flexibility is excessive. If it is less than 1% by weight, the effect of blending the thermoplastic elastomer copolymer cannot be sufficiently exhibited. In the present invention, a film or sheet made of the polypropylene resin as the component (A) or the resin composition as the component (B) is used for the surface layer and / or the base material of the decorative film / sheet. When molding a sheet, in the polypropylene resin or resin composition, to the extent that the object of the present invention is not impaired,
Procell oil, other thermoplastic resins, modified polyolefins, various stabilizers, inorganic or organic fillers, if desired,
An antistatic agent, a chlorine scavenger, an anti-blocking agent, an antifogging agent, an organic flame retardant, a flame retardant aid, a processing aid, a blooming inhibitor, a wax and the like can be added.

As the above-mentioned process oil, those which are usually used as a softening agent during processing of synthetic rubber can be applied as they are. By using this process oil,
In the component (B), the movement of the molecules of the thermoplastic elastomer copolymer during the kneading of both components is improved, and the heat of kneading due to internal friction can be reduced. Further, it contributes to improvement of molding processability of the component (A) and the component (B), flexibility of the molded product, tensile strength, abrasion resistance and the like. This process oil can be applied to both mineral oils and synthetic oils, and specific examples of mineral oils include distillate oils obtained by distilling paraffin-based crude oil, intermediate-based crude oil or naphthene-based crude oil under atmospheric pressure. The refined oil of the distillate obtained by the vacuum distillation of the pressure distillation residual oil, the deep dewaxed oil and the like can be mentioned. Examples of the synthetic oil include alkylbenzene, polybutene, poly (α-olefin) and the like.

The characteristics required of the process oil applicable to the present invention are not particularly limited,
In particular, when kneading both components in the component (B), those having a kinematic viscosity at 40 ° C. of 10 to 1000 cSt, particularly 20 to
The one having 700 cSt is preferably used. Examples of the other thermoplastic resin include high-pressure low-density polyethylene, high-density polyethylene, other polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, and the like.
An ethylene-butene-1 copolymer which is a copolymer not belonging to the thermoplastic elastomer copolymer used in the component (B),
Examples thereof include linear ethylene-α-olefin copolymers such as ethylene-hexene-1 copolymer and ethylene-octene-1 copolymer, acrylic resins, ABS resins, polyesters and polycarbonates.

Among these, polyolefin resins such as various polyethylenes, other polypropylenes and polybutenes are preferable from the viewpoint of compatibility, and polyethylene and ethylene-α-olefin copolymers are particularly preferable. Examples of the modified polyolefin include polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-non-conjugated diene compound copolymer (eg EPDM), ethylene-aromatic monovinyl compound-conjugated diene compound. Polyolefins such as copolymer rubbers can be used for unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid, anhydrides of unsaturated carboxylic acids such as maleic anhydride, and unsaturated carboxylic acids such as methyl acrylate and monomethyl maleate. Ester, acrylic acid amide,
Examples thereof include those chemically modified with an amide of an unsaturated carboxylic acid such as maleic acid monoamide, an imide of an unsaturated carboxylic acid such as maleimide or N-butylmaleimide, and the like. As the chemical modification method, for example, a method of reacting the polyolefin with a unsaturated carboxylic acid or a derivative thereof in a suitable solvent using a radical generator such as benzoyl peroxide can be used.

As the above-mentioned various stabilizers, it is most common to use stabilizers against oxidative deterioration, heat deterioration, etc., for example, phenolic stabilizers, organic phosphite stabilizers,
A thioether stabilizer, a hindered amine stabilizer, etc. can be used. As a phenolic stabilizer,
Conventionally known compounds such as 2,6-di-t-butyl-4
-Methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl -4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t
-Butylphenol, 2-t-butyl-2-ethyl-6
-T-octylphenol, 2-isobutyl-4-ethyl-5-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, dl-α-tocopherol, t
-Butylhydroquinone, 2,2'-methylenebis (4-
Methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'- Thiobis (4-methyl-6
-T-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-
Cresol], 2,2'-ethylidene bis (4,6-di-t-butylphenol), 2,2'-butylidene bis (2-t-butyl-4-methylphenol), 1,1,
3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylenebis [3- (3,5-di-t-butyl- 4-Hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4
-Hydroxybenzylphosphonate-diethyl ester, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate,
1,3,5-Tris [(3,5-di-t-butyl-4-
Hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate,
2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5
-Triazine, tetrakis [methylene-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate] methane, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, bis (3,5-di-t-butyl-4) -Ethyl hydroxybenzylphosphonate) nickel, bis [3,3-bis (3-
t-butyl-4-hydroxyphenyl) butyric acid] glycol ester, N, N′-bis [3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-oxamide bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], bis [2 -T-butyl-4
-Methyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene,
3,9-Bis [1,1-dimethyl-2- [β- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4
-[2- (3,5-Di-t-butyl-4-hydroxyhydrocinnamoyloxy)] ethoxyphenyl] propane and stearyl-β- (4-hydroxy-3,5-di-t-butylphenol) propionate Β-
(3,5-di-t-butyl-4-hydroxyphenyl)
Examples include propionic acid alkyl ester. Among these, 2,6-di-t-butyl-4-methylphenol, stearyl-β- (4-hydroxy-3,5-
Di-t-butylphenol) propionate, 2,2 '
-Ethylidene bis (4,6-di-t-butylphenol) and tetrakis [methylene-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
Methane is preferred.

Examples of the organic phosphite-based stabilizer include trioctyl phosphite, trilauryl phosphite, tris tridecyl phosphite, tris isodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, Phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) ) Phosphite, tris (butoxyethyl) phosphite, tetratridecyl-4,4'-butylidenebis (3-methyl-6-t-butylphenol) -diphosphite, 4,
4'-isopropylidene-diphenol alkyl phosphite (where alkyl has about 12 to 15 carbon atoms),
4,4'-isopropylidene bis (2-t-butylphenol) ・ di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl)-
1,1,3-tris (2-methyl-5-t-butyl-4
-Hydroxyphenyl) butanediphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl)
Phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidene bis (3-methyl-
6-t-Butylphenol)], 1,6-hexanediol diphosphite, hexatridecyl-1,1,3-
Tris (2-methyl-4-hydroxy-5-t-butylphenol) diphosphite, Tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite, Tris (1,3-distearoyloxyisopropyl) Phosphite, 9,10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite, distearyl pentaerythritol di Phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl 4,4'-isopropylidene diphenol pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite , Screw (2,
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and phenylbisphenol-A-pentaerythritol diphosphite. Among these, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediene Phosphite is preferable, and tris (2,4-di-t-butylphenyl) phosphite is particularly preferable.

Further, as the organic thioether stabilizer, it is preferable to use a polyhydric alcohol ester of dialkylthiodipropionate and alkylthiopropionic acid. The dialkylthiodipropionate used here is preferably a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms, and the polyhydric alcohol ester of alkylthiopropionic acid is an alkyl group having 4 to 20 carbon atoms. Polyhydric alcohol esters of alkylthiopropionic acids having groups are preferred. In this case, examples of the polyhydric alcohol that constitutes the polyhydric alcohol ester include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and trishydroxyethyl isocyanurate.

Examples of such dialkylthiodipropionate include dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate. On the other hand, as the polyhydric alcohol ester of alkylthiopropionic acid, for example, glycerin tributyl thiopropionate, glycerin trioctyl thiopropionate, glycerin trilauryl thiopropionate, glycerin tristearyl thiopropionate, trimethylolethane tributyl. Thiopropionate, trimethylolethane trioctyl thiopropionate, trimethylol ethane trilauryl thiopropionate, trimethylol ethane tristearyl thiopropionate, pentaerythritol tetrabutyl thiopropionate,
Pentaerythritol tetraoctyl thiopropionate, pentaerythritol tetralauryl thiopropionate, pentaerythritol tetrastearyl thiopropionate, etc. can be mentioned. Among these, dilauryl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetralauryl thiopropionate are preferable.

Examples of hindered amine stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2, succinate. 2,6,6-Tetramethylpiperidine polycondensate, poly [6- (1,1,
3,3-Tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [2,2 6,6-Tetramethyl-4-piperidyl) imino], tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) -1,2,3,4-butane tetracarboxylate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis- (1,2,6,6-pentamethyl-4-piperidyl ) -2- (3,5-di-t-
Butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1'-
(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), (mixed 2,2,6,6
-Tetramethyl-4-piperidyl / tridecyl) -1,
2,3,4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [2 , 2,6,6-Tetramethyl-4-piperidyl / β, β, β ′, β′-Tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] Diethyl] -1,2,3,4
-Butane tetracarboxylate, mixed [1,
2,2,6,6-pentamethyl-4-piperidyl / β,
β, β ', β'-tetramethyl-3,9- [2,4,
8,10-Tetraoxaspiro (5,5) undecane]
Diethyl] -1,2,3,4-butane tetracarboxylate, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,
2,2,6,6-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5-triazine-
2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,
6,6-Tetramethyl-4-piperidyl) imide],
N, N'-bis (2,2,6,6-tetramethyl-4-
Piperidyl) hexamethylenediamine and 1,2-dibromoethane condensate, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2
2,6,6-Tetramethyl-4-piperidyl) imino]
Examples include propionamide.

Among these hindered amine stabilizers, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [6 -(1,1,3,3-
Tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2
2,6,6-Tetramethyl-4-piperidyl) imino], tetrakis (2,2,6,6-tetramethyl-4)
-Piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,6,6-pentamethyl-4)
-Piperidyl) -2- (3,5-di-t-butyl-4-
Hydroxybenzyl) -2-n-butylmalonate,
1,1 '-(1,2-ethanediyl) bis (3,3,
5,5-Tetramethylpiperazinone), (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (Mixed 1, 2,2,6,6-Pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butane tetracarboxylate, mixed [2,2,2]
6,6-Tetramethyl-4-piperidyl / β, β,
β ', β'-tetramethyl-3,9- [2,4,8,1
0-Tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethyl-
4-piperidyl / β, β, β ′, β′-tetramethyl-
3,9- [2,4,8,10-Tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-
Butane tetracarboxylate, N, N'-bis (3-
Aminopropyl) ethylenediamine-2,4-bis [N
-Butyl-N- (1,2,6,6-pentamethyl-4-
Piperidyl) amino] -6-chloro-1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5
-Triazine-2,4-diyl] [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N'-bis (2,2,6,6-tetramethyl-4 -Piperidyl) hexamethylenediamine and 1,2-dibromoethane condensate, [N- (2,2,
6,6-Tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide is preferred.

Examples of the inorganic fillers include spherical fillers, plate fillers and fibrous fillers. Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, pearlite,
Shirasu balloon, sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, crystalline zeolite, amorphous zeolite and the like, plate fillers such as talc and mica, and fibrous fillers such as Needle-like materials such as wollastonite, magnesium oxysulfate, potassium titanate fibers, fibrous materials such as fibrous calcium carbonate, and even completely fibrous materials such as glass fibers. To be On the other hand, examples of the organic filler include wood particles such as wood powder and cotton powder, fir shell powder, crosslinked rubber powder, plastic powder and collagen powder. Examples of the flame retardant include hydrated aluminum, hydrated gypsum, zinc borate, barium borate, borax, kaolin, clay, calcium carbonate, alumite, basic magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like. Can be mentioned. Incidentally, among these fillers, those which adversely affect the transparency are exclusively filled not in the surface layer but in the base material.

In the present invention, in order to form a film or sheet used for the surface layer and / or the base material, for example, first,
Various additives are optionally added to the polypropylene resin as the component (A), or the thermoplastic elastomer copolymer and various additives are optionally added to the polypropylene resin as the component (A), and the mixture is mixed with a tumbler blender or a Henschel mixer. A molding material is prepared by mixing, or after mixing, melt kneading and granulating using a single-screw extruder or a multi-screw extruder, or melt kneading and granulating with a kneader, Banbury mixer or the like. Next, it is advantageous that the molding material is processed into a film or sheet having a thickness of about 0.03 to 0.5 mm by a molding method such as cast molding, inflation molding and calender molding. The film or sheet thus obtained is treated by corona treatment, ozone treatment,
It is desirable to perform surface treatment such as plasma treatment. When this film or sheet is used as a substrate, a hiding effect may be imparted by adding a pigment during molding. The decorative film / sheet of the present invention may be a so-called doubling film having a laminated structure consisting of a surface layer, an adhesive layer, a picture layer, an adhesive layer and a substrate, or may be a surface layer, an adhesive layer and It may be a so-called back print film having a laminated structure composed of a picture layer (printed directly on the surface layer and having no substrate).

Examples of the adhesive layer in the above decorative film / sheet include polyurethane resin, epoxy resin, acrylic resin, vinyl resin, vinyl acetate resin, polyester resin, ethylene-vinyl acetate copolymer resin, A known adhesive containing acrylic-vinyl acetate copolymer resin, polyamide resin, ionomer resin or the like as a main component, or modified polyolefin having a thickness of 1 to 2
Preferable ones are about 0 μm. Here, as the modified polyolefin, for example, polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-non-conjugated diene compound copolymer (for example, EPDM), ethylene-aromatic monovinyl compound-conjugated diene Compounds Polyolefin such as rubber, unsaturated carboxylic acid such as acrylic acid, methacrylic acid and maleic acid, anhydride of unsaturated carboxylic acid such as maleic anhydride, unsaturated carboxylic acid such as methyl acrylate and monomethyl maleate Of the above, an amide of an unsaturated carboxylic acid such as an acrylic acid amide, a maleic acid monoamide, or an imide of an unsaturated carboxylic acid such as a maleimide or N-butylmaleimide.

The form of the adhesive at the time of processing is not particularly limited, and may be liquid, semi-molten, or film / sheet. When there are two adhesive layers, the first adhesive layer and the second adhesive layer may be made of the same material or different materials. On the other hand, the pattern layer is provided with a print expressing, for example, wood grain, stone pattern, surface pattern of natural leather, cloth pattern, abstract pattern, etc. There is no particular limitation as a binder of the ink for providing these pattern patterns. , For example, polyurethane resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin / acrylic resin, chlorinated polypropylene resin,
Any of acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, acetylcellulose resin, etc. may be used. Further, a colorant such as a pigment or dye, an extender pigment, a solvent and the like are appropriately mixed in the ink. The thickness of this pattern layer is usually 1 to 5 μm.
It is a degree.

In the present invention, the pattern layer having a two-layer structure of a pattern layer and a masking layer is particularly preferable.
As the ink used for forming the concealing layer, a mixture of a binder with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent is used. As the binder, the same binders as those exemplified as the binder of the ink used for providing the pattern layer can be mentioned. As the hiding layer, a solid printing layer having a thickness of about 1 to 20 μm is suitable. This hiding layer is provided as a lower layer of the pattern layer.
Furthermore, in the decorative film / sheet of the present invention, an acrylic resin or a polyurethane resin is optionally added on the surface layer for the purpose of improving abrasion resistance, weather resistance, embossability, scratch resistance, stain resistance and the like. Thickness of 1 to 20
A top coat layer having a thickness of about μm may be formed. If desired, the surface layer may be embossed or the recess may be filled with wiping ink or the like.

The method for producing the decorative film / sheet of the present invention is not particularly limited as long as it has a laminated structure, and is not particularly limited. For example, a surface layer, an adhesive layer, a pattern layer, an adhesive agent. Those having a laminated structure composed of layers and a base material are advantageously manufactured by the following two methods. First, as a first method, an adhesive layer, a pattern layer, and an adhesive layer are sequentially laminated on a substrate by a general printing method such as gravure printing, screen printing, offset printing, and flexo printing, and then an adhesive is formed. On the layer, (1) a method of laminating a film or sheet to be a surface layer by thermal lamination, (2) a method of laminating a film or sheet to be a surface layer by dry lamination or wet lamination, (3) surface layer General printing method such as gravure printing, screen printing, offset printing, flexo printing on the film or sheet to be used,
Alternatively, a method in which an adhesive layer having the same composition is provided by a coating method such as roll coating, and the adhesive layers are overlapped and bonded by thermal lamination or the like, (4) a method of forming a surface layer by extrusion lamination of a resin to be a surface layer , Etc. are used.

Next, as a second method, an adhesive layer and a pattern layer are sequentially laminated on a substrate by a general printing method such as gravure printing, screen printing, offset printing, flexographic printing, and then (1) ) An adhesive layer is provided on the film or sheet to be the surface layer by a general printing method such as gravure printing, screen printing, offset printing, flexographic printing or a coating method such as roll coating,
Then, a method in which this is laminated so that the adhesive layer is in contact with the pattern layer and laminated by thermal lamination or the like, and an adhesive layer is formed on the film or sheet to be the surface layer by the same method as (2) and (1). And a method of laminating by dry lamination or wet lamination, (3) a method of extruding and laminating a resin to be an adhesive layer in a molten state between a picture layer and a film or sheet to be a surface layer (extrusion lamination), (4) A method of forming the adhesive layer and the surface layer by coextrusion direct lamination of the resin to be the adhesive layer and the surface layer is used.

The present invention also provides a decorative material obtained by adhering the thus obtained decorative film / sheet to various substrates. Examples of materials used as the base material of the decorative material include wood base materials such as wood, plywood, laminated wood, particle boards and hard boards, metal base materials such as steel plates, stainless steel plates, and aluminum plates, and gypsum, for example. Examples include inorganic base materials such as boards. In order to produce a cosmetic material, the above base material,
The decorative film sheet may be laminated with an adhesive so that the base material or the pattern layer faces each other. At this time, the adhesive used is not particularly limited and can be appropriately selected and used from conventionally known adhesives.

[0054]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Production of Propylene Homopolymer Preparation of Magnesium Compound After a glass reactor equipped with a stirrer and having an internal volume of about 6 liters was sufficiently replaced with nitrogen gas, about 2,430 ethanol was added thereto.
g, 20 g of iodine and 160 g of metallic magnesium were charged, heated with stirring, and reacted under reflux conditions until hydrogen gas was not generated from the inside of the system to obtain a solid reaction product. The reaction liquid containing this solid reaction product was dried under reduced pressure to obtain a magnesium compound. Preparation of solid catalyst component (a) 160 g of the magnesium compound (not crushed) obtained above, 800 ml of purified heptane, and silicon tetrachloride were placed in a glass reactor having an internal volume of 5 liters, which was sufficiently replaced with nitrogen gas. Charge 24 ml and diethyl phthalate 23 ml, keep the system temperature at 80 ° C., add 770 ml titanium tetrachloride with stirring and react at 110 ° C. for 2 hours, then separate solid components and purify at 90 ° C. Wash with heptane. Further, 1,220 ml of titanium tetrachloride was added, and the mixture was reacted at 110 ° C. for 2 hours and then thoroughly washed with purified heptane to obtain a solid catalyst component (a).

Gas phase polymerization In a polymerization tank having an internal volume of 200 liters, 6.0 g / hour of the solid catalyst component (a) obtained above, 0.2 mol / hour of triisobutylaluminum (TIBA), 1-allyl-3. ，
4-dimethoxybenzene (ADMB) 0.006 mol / hour, cyclohexylmethyldimethyoxysilane (CHMD
MS) was supplied at 0.03 mol / hour and 43 kg / hour of propylene, and polymerization was carried out at 70 ° C. and 28 kg / cm ² G.
The amount of polymer produced was 30 kg / hour. The polymer obtained by this polymerization is a propylene homopolymer, and its intrinsic viscosity [η] (135 ° C, in decalin) is
It was 5.04 deciliter / g. The amount of the boiling n-heptane insoluble component of the homopolymer was 88.2% by weight, [η] of the boiling n-heptane insoluble component was 5.42 deciliter / g, and the boiling n-heptane-soluble component [ η] is 2.
It was 07 deciliter / g. On the other hand, the Pendad fraction rrrr / (1-mmmm) × 100 calculated from the ¹³ C-NMR spectrum of the homopolymer was 24.2%, and the melting peak temperature (Tm) measured by DSC was 15%.
The enthalpy of fusion (ΔH) was 8.7 ° C. and 80.7 J / g. In addition, no reverse bond was observed in the head-to-tail bond of propylene. 2,5-Dimethyl-2,5-di- (t-butylperoxy) -hexane was mixed with the obtained polypropylene powder, and an antioxidant,
After adding the heat stabilizer and the chlorine scavenger, it was extruded with a 40 mmφ extruder to obtain pellets. The melt index (MI) of this pellet was 2.5 g / 10 minutes. Although the above polymer was decomposed with peroxide to have a low molecular weight, there was no change in the above-mentioned Pendad fraction, melting peak temperature and melting enthalpy even with this low molecular weight polymer.

(2) Molding of surface layer film The propylene homopolymer pellets obtained in (1) above were molded with a 90 mmφ cast molding machine at a resin temperature of 250.
A film having a thickness of 100 μm was formed under the conditions of ° C and a take-up speed of 10 m / min. Simultaneously with the molding, this film was subjected to embossing on one side and was subjected to double-sided corona treatment (5.0 kW). The wettability index of the corona-treated surface (obtained according to JIS K6768) was 50 dyne / cm. (3) Lamination of Adhesive Layer On the smooth surface side of the film obtained in (2) above, a primer having a vinyl chloride-vinyl acetate copolymer resin as a main component is used, and an adhesive having a thickness of 3 μm is obtained by gravure printing. Layers were provided. (4) Production of printing film (pattern layer) A primer containing a vinyl chloride-vinyl acetate copolymer resin as a main component and a vinyl chloride-vinyl acetate copolymer resin as a binder on a colored high-density polyethylene film having a thickness of 90 μm. The inks to be used are sequentially laminated by gravure printing,
Further, a primer containing a vinyl chloride-vinyl acetate copolymer resin as a main component was similarly laminated to produce a printing film. The total thickness of this printing film was 100 μm.

(5) Lamination of the surface layer film and the printing film The adhesive layer surface of the surface layer film obtained in the above (3) and the adhesive layer surface of the printing film obtained in the above (4) are overlapped, and 120 The sheets were pasted through a hot roll at ℃ to obtain a decorative sheet. (6) Adhesion to plywood and evaluation of secondary processability The decorative film obtained in (5) above had good transparency of the surface layer, and depth was imparted to the pattern layer. Moreover, the flexibility was equivalent to that of a conventional decorative film made of a polyvinyl chloride film. An adhesive containing an ethylene-vinyl acetate copolymer resin as a main component was used, and the above-mentioned decorative film was laminated on a medium-density particle board having irregularities so that its colored high-density polyethylene layer was in contact. Moreover, it stuck similarly on the board on a flat plate, and V cut processing was performed. There were no cracks or whitening in the bent portion, and the lapping workability and V-cut workability were good.

Example 2 (1) Lamination by Coextrusion Direct Lamination The propylene homopolymer obtained in Example 1- (1) and 80% by weight of this polymer were modified with a maleic anhydride-modified polyolefin [manufactured by Idemitsu Petrochemical Co., Ltd.]. Polytac E-10
0] Adhesive resin obtained by mixing 20% by weight was co-extruded and subjected to ozone treatment.
It was laminated with the printing film of 1. to obtain a decorative film. The resin temperature of the molten resin at the time of coextrusion was 290 ° C., and the thickness of the obtained decorative film was 160 μm. (2) Adhesion of plywood and evaluation of secondary processability The decorative film obtained in (1) above had good transparency of the surface layer, and depth was imparted to the pattern layer. Moreover, the flexibility was equivalent to that of a conventional decorative film made of a polyvinyl chloride film. An adhesive containing an ethylene-vinyl acetate copolymer resin as a main component was used, and the above-mentioned decorative film was laminated on a medium-density particle board having irregularities so that its colored high-density polyethylene layer was in contact. Moreover, it stuck similarly on the board on a flat plate, and V cut processing was performed. There were no cracks or whitening in the bent portion, and the lapping workability and V-cut workability were good.

Example 3 (1) Preparation of Backprint Film The film obtained in Example 1- (2) was used as a surface layer, and a vinyl chloride-vinyl acetate copolymer resin was used as a main component on the smooth surface side. Using a primer, an ink with a vinyl chloride-vinyl acetate copolymer resin as a binder, an adhesive layer and a pattern layer are sequentially laminated by gravure printing, and further, a mixture of the above ink and a pigment is used for gravure printing. A solid coating layer was laminated to produce a decorative film. (2) Adhesion to plywood and evaluation of secondary processability The decorative film obtained in (1) above had good transparency of the surface layer, and the pattern layer had depth. Moreover, the flexibility was equivalent to that of a conventional decorative film made of a polyvinyl chloride film. An adhesive containing ethylene-vinyl acetate copolymer resin as a main component was used, and the above-mentioned decorative film was laminated on a medium density particle board having irregularities so that the solid coating layer surface was in contact. Moreover, it stuck similarly on the board on a flat plate, and V cut processing was performed. There were no cracks or whitening in the bent portion, and the lapping workability and V-cut workability were good.

Comparative Example (1) Molding of surface layer film Polypropylene resin [Sumitomo Chemical Co., Ltd. Nobren FL
6315G, melting peak temperature (Tm): 140 ° C] 90
40% by dry blending 10% by weight with 10% by weight of a thermoplastic elastomer [Kuraray Co., Ltd. High Blur HVS-3].
A film having a thickness of 80 μm was formed by a mmφ cast molding machine under the conditions of a resin temperature of 230 ° C. and a take-up speed of 5 m / min. The film was textured on one side and corona treated on both sides (4.5 kW). The wetting index of the corona-treated surface was 49 dyne / cm. (2) Lamination of adhesive layer On the smooth surface side of the film obtained in (1) above, a primer having a vinyl chloride-vinyl acetate copolymer resin as a main component is used, and a 3 μm-thick adhesive is formed by gravure printing. An agent layer was provided. (3) Preparation of printing film (pattern layer) A primer containing a vinyl chloride-vinyl acetate copolymer resin as a main component and a vinyl chloride-vinyl acetate copolymer resin as a binder on a colored high-density polyethylene film having a thickness of 90 μm. Gradually print the inks to be used,
Further, a primer containing a vinyl chloride-vinyl acetate copolymer resin as a main component was similarly laminated to produce a printing film. The total thickness of this printing film was 100 μm.

(4) Lamination of the surface layer film and the printing film: The adhesive layer surface of the surface layer film obtained in the above (2) and the adhesive layer surface of the printing film obtained in the above (3) are overlapped and 120 ° C. Then, the sheets were pasted through a hot roll to obtain a decorative sheet. (5) Adhesion to plywood and evaluation of secondary processability The decorative film obtained in (4) above has a slightly poor transparency of the surface layer, but has the same flexibility as a conventional decorative film made of a polyvinyl chloride film. there were. An adhesive containing ethylene-vinyl acetate copolymer resin as a main component was used, and the above-mentioned decorative film was laminated on a medium-density particle board having uneven portions so that the colored high-density polyethylene layer was in contact with the decorative film. Also, stick it on a flat board in the same way,
V-cut processing was performed. However, when the lapping process and the V-cut process were performed at a low temperature, whitening was observed in the bent portion. The above results are summarized in Table 1.

[0062]

[Table 1]

[0063]

EFFECTS OF THE INVENTION The decorative film / sheet of the present invention has good transparency of the surface layer, is excellent in V-cut processability and wrapping processability, and does not generate chlorine gas during incineration. It has extremely high commercial value, such as none. Since the decorative film / sheet of the present invention has the above-mentioned excellent characteristics, it can be suitably used, for example, as a furniture member, a cabinet such as a refrigerator or a television, an interior material for construction, and the like.

Claims (7)

[Claims] 1. A decorative film sheet having a surface layer, an adhesive layer, a picture layer, a laminated structure comprising an adhesive layer and a base material, or a laminated structure comprising a surface layer, an adhesive layer and a picture layer, wherein the surface layer Or (A) on the substrate or both
(A) In the pentad fraction by isotope carbon nuclear magnetic resonance ( ¹³ C-NMR) spectrum, rrrr / (1-m
mmm) × 100 is 15 to 50%, (b) Melting peak temperature (Tm) measured by a differential scanning calorimeter (DSC)
Homopolymer of propylene having a melting enthalpy (ΔH) measured by DSC of 150 ° C or higher and (C) DSC of 100 J / g or less, and / or a propylene-based copolymer containing 4% by weight or less of another olefin unit. Or a film or sheet comprising (B) a resin composition comprising 99 to 60% by weight of the polypropylene resin as the component (A) and 1 to 40% by weight of a thermoplastic elastomer copolymer. Cosmetic film / sheet characterized by 2. The polypropylene resin as the component (A) has a melting enthalpy (ΔH) of 10 to 100 in (c).
The decorative film / sheet according to claim 1, which is J / g. 3. A thermoplastic elastomer copolymer comprising an ethylene-C3 or more α-olefin copolymer elastomer, an ethylene-C3 or more α-olefin-diene copolymer elastomer, and a styrene-diene copolymer. The decorative film / sheet according to claim 1, wherein the decorative film / sheet is at least one selected from hydrogenated products of polymerized elastomers and styrene-diene copolymerized elastomers. 4. The decorative film sheet according to claim 1, wherein the pattern layer has a two-layer structure of a pattern layer and a masking layer. 5. A decorative wood material obtained by adhering the decorative film or sheet according to claim 1 to a wood base material. 6. A decorative metal material obtained by adhering the decorative film or sheet according to claim 1 to a metal substrate. 7. A decorative inorganic material obtained by adhering the decorative film or sheet according to claim 1 to an inorganic substrate.