JP2002144502A - Decorative film/sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative film/sheet having good transparency of a surface layer, and excellent workability for V cutting and wrapping, which does not have problems of disposing. SOLUTION: The decorative film/sheet has a laminated structure comprising a surface layer, and adhesive layer, a pattern layer, an adhesive layer and a base, or a laminated structure comprising a surface layer, an adhesive layer and a pattern layer. The surface layer or the base, or both the layers are formed of a film or a sheet composed of a resin composition containing a propylene polymer [I] of 1-99 wt.% wherein (1) a meso pentad fraction (mmmm) is 0.2-0.6, and (2) a racemic pentad fraction (rrrr) and (1-mmmm) satisfy [rrrr/(1-mmmm)]<=0.1, and an olefin based resin [II] of 99-1 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative film / sheet and a decorative material, and more particularly, to a surface layer having good transparency, excellent bending workability, V-cut workability, lapping workability, and incineration. TECHNICAL FIELD The present invention relates to a laminated decorative film / sheet which does not have a problem of disposal because chlorine gas and the like are not generated, and a decorative material using the same.

[0002]

2. Description of the Related Art Conventionally, a decorative film or sheet obtained by printing a woodgrain pattern or the like on a substrate made of a wood-based material has been bonded with an adhesive as a surface decorative plate for a cabinet of furniture or kitchen products. A structure is used. A decorative film or sheet used for such a surface decorative board usually has a lapping processability, that is, when the substrate has an uneven portion or a complicated shape, a processability capable of bonding according to the shape, V Cut workability, that is, suitability for assembling a box or bending a terminal end by performing V-cut processing on a surface decorative plate after lamination is required. Specifically, it is required that no inconvenience such as cracking, cutting, and whitening occur in the bent portion of the decorative film / sheet. Until now, in order to impart V-cut workability and wrapping workability to a decorative film / sheet, a film / sheet made of a vinyl chloride resin has been generally used. However, this vinyl chloride resin has poor weather resistance and stain resistance, and requires a thickness to obtain strength during V-cut processing, and generates chlorine gas during combustion. I have. For this reason, decorative films and sheets using a polyolefin resin instead of a vinyl chloride resin have been developed. For example, JP-A-7-2
In JP-A-4979, a polypropylene-based resin or a polyester-based resin is used, but those that can be used for the base sheet are limited to opaque polyolefin-based resin films.

[0003]

Under such circumstances, the present invention is excellent in bending workability, V-cut workability, lapping workability, etc., has a good surface layer transparency, and can be used in incineration. It is an object of the present invention to provide a decorative film or sheet which does not generate a chlorine gas and thus does not have a problem of disposal, and a decorative material such as a decorative wood material, a decorative steel plate, a decorative inorganic material using the decorative film or sheet.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a laminated structure comprising a surface layer, an adhesive layer, a picture layer, an adhesive layer and a base material, Or, in a decorative film or sheet having a laminated structure composed of a surface layer, an adhesive layer and a picture 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 resin composition containing a specific propylene polymer and an olefin-based resin. The present invention
It has been completed based on such knowledge. That is,
The present invention provides a decorative film or sheet having a surface layer, an adhesive layer, a pattern layer, a laminated structure composed of an adhesive layer and a substrate, or a laminated structure composed of a surface layer, an adhesive layer and a pattern layer. The following (1)
And (2) the (1) mesopentad fraction (mmmm) is 0.2 to 0.6 (2) the racemic pentad fraction (rrrr) and (1-mm
mm) that satisfies the following relationship: [rrrr / (1-mmmm)] ≤1 to 99% by mass of propylene polymer [I] satisfying 0.1 and a resin containing 99 to 1% by mass of olefin-based resin [II] Another object of the present invention is to provide a decorative film or sheet using a film or sheet made of the composition. The present invention also provides a decorative wood material, a decorative metal material, and a decorative inorganic material obtained by bonding the decorative film / sheet to a wood, metal, or inorganic substrate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The specific propylene polymer [I] used in the resin composition forming the decorative film / sheet of the present invention is a propylene polymer satisfying the following (1) and (2). (1) The mesopentad fraction (mmmm) is 0.2 to 0.6. (2) The racemic pentad fraction (rrrr) and (1-mm)
mm) satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 As the propylene polymer in the present invention, the above-mentioned (1)
And (2), but the mesopentad fraction (m
mmm) is preferably from 0.3 to 0.6, more preferably from 0.4 to 0.5, and the racemic pentad fraction (rrrr) and (1-
mmr) is preferably [rrrr / (1-mmmm)] ≦ 0.08, more preferably [rrrr / (1-mmmm)] ≦ 0.06, and [rrrr / (1-mmm)
m)] ≦ 0.05 is particularly preferred.

When the propylene polymer [I] satisfies the above relationship, the resulting resin composition has an excellent balance between the amount of sticky components, low elastic modulus and transparency. That is, the elasticity is low, the softness (also called flexibility) is excellent, the sticky component is small, and the surface characteristics are small (for example, the transfer of the sticky component to bleed or other products is small).
And excellent transparency. Mesopentad fraction of the propylene polymer (mmmm)
Is less than 0.2, it may cause stickiness. If it exceeds 0.6, the elastic modulus increases, which is not preferable. If the [rrrr / (1-mmmm)] of the propylene polymer exceeds 0.1, it causes stickiness.

The mesopendad fraction (mmmm fraction) used in the present invention refers to A. Zamberli (A. Za).
"Macromolecule"
s, 6, 925 (1973) ", and is a meso fraction in pentad units in a polypropylene molecular chain measured by a signal of a methyl group in a ¹³ C-NMR spectrum. When this is increased, it means that stereoregularity is increased. Similarly, the racemic pentad fraction (rrrr fraction) is a racemic fraction in pentad units in a polypropylene molecular chain. [Rrrr / (1
-Mmmm)] is an index obtained from the above-mentioned fraction in the pentad unit and representing the uniformity of the stereoregularity distribution of the propylene polymer. When this value is increased, the stereoregularity distribution is expanded, and a mixture of high stereoregularity PP and APP is obtained as in the case of conventional polypropylene produced using an existing catalyst system, meaning that stickiness increases and transparency decreases. I do. The measurement of the ¹³ C-NMR spectrum was performed by A.
"Macr" by A. Zambelli and others.
Omolecules, 8, 687 (1975) ", according to the following apparatus and conditions.

Apparatus: JNM-EX40 manufactured by JEOL Ltd.
Type 0 ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / ml Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10000 times As the propylene polymer [I] in the present invention, in addition to the above requirements, (3) intrinsic viscosity [η] measured in tetralin at 135 ° C. is 1.0. It is preferably from 3.0 to 3.0 deciliter / g. Among them, the amount is more preferably 1.0 to 2.5 deciliter / g, and particularly preferably 1.1 to 2.2 deciliter / g. When the intrinsic viscosity [η] is less than 1.0 deciliter / g,
Stickiness may occur. On the other hand, if it exceeds 3.0 deciliters / g, the flowability may be reduced and the moldability may be poor.

Further, in addition to the requirements of the above (1), (2) and (3), (4) the amount of the component (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass. Are preferable, and 30 to 100% by mass is more preferable,
Particularly preferred is 50 to 100% by mass, most preferably 60 to 100% by mass. W25 refers to the amount (mass) of a component that is eluted without being adsorbed by the packing material at a TREF column temperature of 25 ° C. in an elution curve determined by temperature-raising chromatography under the operating method, apparatus configuration, and measurement conditions described in Examples. %). W25 is an index indicating whether or not the propylene polymer is soft. In the present invention, if W25 is less than 20%, flexibility may be lost, which is not preferable.

The propylene polymer [I] of the present invention preferably further satisfies any of the following requirements. The molecular weight distribution (Mw / Mn) measured by the gel permeation (GPC) method is 4 or less, more preferably 3.
It is 5 or less, particularly preferably 3 or less. Molecular weight distribution (M
If (w / Mn) exceeds 4, stickiness may occur. Note that the above Mw / Mn is determined by a gel permeation chromatography (GPC) method described in Examples. When the melting endothermic amount ΔH by DSC measurement is 30 J / g or less, flexibility is excellent and preferable. ΔH is an index indicating whether the material is soft or not, and as this value increases, the elastic modulus increases,
It means that the softness is reduced. The melting point (Tm) and the crystallization temperature (Tc) may or may not be present, but it is preferable not to have a softness point or to have a low value, especially the Tm is 100 ° C. or less.
Note that ΔH, Tm, and Tc are D
Determined by SC measurement. The tensile modulus is preferably 100 MPa or less, more preferably 70 MPa or less.

The propylene polymer [I] used in the present invention may be any one satisfying the above (1) and (2). As long as the object of the present invention is not impaired, 2 mass% of a comonomer other than propylene is used. % Or less. As comonomer, ethylene,
1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. In the present invention, one or more of these can be used. Propylene polymer [I] used in the present invention
Is produced by polymerizing or copolymerizing propylene using a metallocene catalyst obtained by combining (A) a transition metal compound forming a crosslinked structure through two crosslinking groups and (B) a cocatalyst. The method is preferred. Specifically, the general formula (I)

[0012]

Embedded image

[Wherein M is a group 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Ligand selected from the group consisting of a group, a hydrocarbon group and a silicon-containing group
And A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Y are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR¹-, -PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹-
And R¹Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
A hydrocarbon group or a halogen-containing hydrocarbon having 1 to 20 carbon atoms
Denote radicals, which may be the same or different
Good. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. Transition metallization represented by
Compound (A), and the transition metal compound or the component (A).
Capable of forming an ionic complex by reacting with derivatives of
Selected from (B-1) and aluminoxane (B-2)
In the presence of a polymerization catalyst containing the co-catalyst component (B),
A method of polymerizing or copolymerizing pyrene is exemplified.

A specific example of the transition metal compound represented by the general formula (I) is (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,2′-dimethylsilylene) (2,
1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5
-Benzoindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di-i-propylindenyl) ) Zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-
Dimethylsilylene) bis (5,6-benzoindenyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis ( 3-
Methylindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride , Etc. and those obtained by substituting zirconium in these compounds with titanium or hafnium.

Next, the component (B-1) of the component (B) includes triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, Examples thereof include methyl tetraphenylborate (tri-n-butyl) ammonium and benzyltetraphenylborate (tri-n-butyl) ammonium. (B-1) may be used alone, or two or more kinds may be used in combination. On the other hand, as the aluminoxane of the component (B-2),
Methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and the like are mentioned. These aluminoxanes may be used alone or in a combination of two or more. As the polymerization catalyst, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B).

As the organoaluminum compound of the component (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutyl Aluminum hydride,
Examples thereof include diethyl aluminum hydride and ethyl aluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more. Here, in the polymerization of propylene, at least one of the catalyst components can be used by being supported on a suitable carrier.

The polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Legitization is particularly preferred. The polymerization temperature is usually -100 to 2
At 50 ° C., the usage ratio of the catalyst to the reaction raw material is such that the raw material monomer / the component (A) (molar ratio) is preferably 1 to 10%.
^8, it is preferable that the particular 100 to 10 ^5. Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is usually
Normal pressure to 20 MPa (gauge).

The olefin resin [I] used in the present invention
I] includes polypropylene resin, propylene-ethylene copolymer, propylene-ethylene-diene copolymer, polyethylene, ethylene / α-olefin copolymer, ethylene-vinyl acetate copolymer, hydrogenated styrene elastomer, modified And polyolefins.
These may be used alone or in a combination of two or more. Further, a resin composition of these olefin-based resin and thermoplastic elastomer can also be used. In the present invention, a polypropylene resin is preferred.

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. Polyolefins such as compound copolymer rubbers are converted to 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. And amides of unsaturated carboxylic acids such as esters of acrylic acid and amides of maleic acid, and imides of unsaturated carboxylic acids such as maleimide and N-butylmaleimide. As the chemical modification method, for example, a method of reacting the polyolefin with the unsaturated carboxylic acid or a derivative thereof using a radical generator such as benzoyl peroxide in an appropriate solvent can be used.

The resin composition used in the present invention comprises 1 to 99% by mass of the propylene polymer [I] and 99 to 1% by mass of the olefin resin [II]. Preferably, it is composed of 10 to 80% by mass of the propylene polymer [I] and 90 to 20% by mass of the olefin resin [II]. More preferably, it comprises 25 to 75% by mass of the propylene polymer [I] and 75 to 25% by mass of the olefin resin [II]. Particularly preferably, it is composed of 40 to 75% by mass of the propylene polymer [I] and 60 to 25% by mass of the olefin resin [II].

(Method for Producing Resin Composition) The resin composition used in the present invention comprises 1 to 99% by mass of the propylene polymer [I] and 99 to 1% by mass of the olefin resin [II], and if desired. Dry blending with various additives used using a Henschel mixer or the like, a single-screw or twin-screw extruder,
The mixture may be melt-kneaded by a Banbury mixer or the like, or may be a mixture obtained by adding various additives to the propylene polymer [I] and / or the olefin-based resin [II], and then blending and melt-kneading. Further, a master batch may be used. Examples of various additives used as desired include various stabilizers, softeners, inorganic fillers, organic fillers, pigments, foaming agents, flame retardants, and other nucleating agents. As the above-mentioned various stabilizers, the use of a stabilizer against oxidative deterioration, heat deterioration and the like is most common, and examples thereof include phenol-based stabilizers, organic phosphite-based stabilizers, thioether-based stabilizers, and hindered amine-based stabilizers. Can be used.

As the phenol-based stabilizer, those known in the art, for example, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-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-tert-butylphenol, 2-tert-butyl-2-ethyl-6-tert-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'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-butylidenebis (2-t
-Butyl-4-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triethylene glycol-bis [3-
(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-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-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,
3,5-tris (2,6-dimethyl-3-hydroxy-
4-tert-butylbenzyl) isocyanurate, 1,3
5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-tert-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-tert-butyl-4-hydroxyphenyl) propionate] methane, bis (3,5-di -T-butyl-4-hydroxybenzylphosphonate ethyl) calcium, bis (3,5-
Ethyl di-tert-butyl-4-hydroxybenzylphosphonate) nickel, bis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid] glycol ester, N, N'-bis [3 -(3,5-di-t
-Butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-oxamidobis [ethyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], bis [2-tert-butyl-4-methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4
-Hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- [2-
Β- (such as (3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)] ethoxyphenyl] propane and stearyl-β- (4-hydroxy-3,5-di-t-butylphenol) propionate 3,5-
Di-t-butyl-4-hydroxyphenyl) 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'-ethylidenebis (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, for example, trioctyl phosphite, trilauryl phosphite, tristridecyl 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-tert-butylphenol) -diphosphite, 4,
4'-isopropylidene-diphenol alkyl phosphite (where alkyl has about 12 to 15 carbon atoms),
4,4'-isopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl)-
1,1,3-tris (2-methyl-5-t-butyl-4
-Hydroxyphenyl) butane diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl)
Phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidenebis (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'-biphenylenediphosphonite, distearylpentaerythritol di Phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl / 4,4'-isopropylidenediphenol / 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'-biphenylenediphosphite is preferred, and tris (2,4-di-t-butylphenyl) phosphite is particularly preferred. Further, as the organic thioether-based stabilizer, it is preferable to use a polyhydric alcohol ester of dialkylthiodipropionate and alkylthiopropionic acid. As the dialkylthiodipropionate used here, the carbon number is 6 to
A dialkylthiodipropionate having an alkyl group of 20 is preferable, and a polyhydric alcohol ester of an alkylthiopropionic acid is preferably a polyhydric alcohol ester of an alkylthiopropionic acid having an alkyl group having 4 to 20 carbon atoms. In this case, examples of the polyhydric alcohol constituting the polyhydric alcohol ester include glycerin, trimethylolethane, trimethylolpropane,
Examples thereof include pentaerythritol and trishydroxyethyl isocyanurate.

Examples of such dialkylthiodipropionates include dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate. On the other hand, polyhydric alcohol esters of alkylthiopropionic acid include, for example, glycerin tributylthiopropionate, glycerin trioctyl thiopropionate, glycerin trilauryl thiopropionate, glycerin tristearyl thiopropionate, trimethylolethane tributyl Thiopropionate, trimethylol ethane trioctyl thiopropionate, trimethylol ethane trilauryl thiopropionate, trimethylol ethane tristearyl thiopropionate, pentaerythritol tetrabutyl thiopropionate,
Examples thereof include pentaerythritol tetraoctylthiopropionate, pentaerythritol tetralauryl thiopropionate, and pentaerythritol tetrastearyl thiopropionate. Among these, dilauryl thiodipropionate, distearyl thiodipropionate and pentaerythritol tetralauryl thiopropionate are preferred.

Examples of the hindered amine stabilizer 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) imide], tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, 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
-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-butanetetracarboxylate, 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) condensate of hexamethylenediamine and 1,2-dibromoethane, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,
2,6,6-tetramethyl-4-piperidyl) imino]
Propionamide and the like can be mentioned.

Among these hindered amine-based stabilizers, in particular, polycondensate of dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate, 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) imide], 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-butanetetracarboxylate, 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-
Butanetetracarboxylate, 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.

As the softening agent, a process oil is preferable. As the process oil, those usually used as a softening agent at the time of processing a synthetic rubber can be directly applied. As the process oil, any of mineral oil and synthetic oil can be applied. Specific examples of the mineral oil include a distillate obtained by distilling a paraffin-based crude oil, an intermediate-based crude oil or a naphthenic-based crude oil under normal pressure, and the normal pressure. Examples include refined oil and deeply dewaxed oil obtained by distilling residual distillation oil under reduced pressure. Examples of the synthetic oil include alkylbenzene, polybutene, poly (α-olefin) and the like. The characteristics required for the process oil applicable to the present invention are not particularly limited, but the kinematic viscosity at 40 ° C. is 10%.
0-10000 mm ² / sec, especially 200-7
000 mm ² / sec is preferably used.

Examples of the inorganic filler include a spherical filler, a plate-like filler and a fibrous filler. Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, perlite, shirasu balloon, sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, crystalline zeolite, and amorphous zeolite. As a plate-like filler,
For example, talc and mica are used as fibrous fillers. For example, needle-like ones such as wollastonite, magnesium oxysulfate, potassium titanate fiber,
A fibrous material such as fibrous calcium carbonate, and a completely fibrous material such as glass fiber can be used. On the other hand, examples of the organic filler include wood particles such as wood powder and cotton powder, fir hull powder, crosslinked rubber powder, plastic powder, collagen powder, and the like. Examples of the flame retardant include aluminum hydrate, gypsum, zinc borate, barium borate, borax, kaolin, clay,
Calcium carbonate, alunite, basic magnesium carbonate,
Examples include calcium hydroxide and magnesium hydroxide. Among these additives, those that adversely affect the transparency are filled not only in the surface layer but also in the base material.

Specific examples of the nucleating agent in the present invention include:
High melting point polymer, organic carboxylic acid or its metal salt,
Aromatic sulfonate or its metal salt, organic phosphoric acid compound or its metal salt, dibenzylidene sorbitol or its derivative, rosin acid partial metal salt, inorganic fine particles, imides, amides, quinacridones, quinones or mixtures thereof Is mentioned. Examples of the high melting point polymer include polyolefins such as polyethylene and polypropylene, polyvinylcycloalkanes such as polyvinylcyclohexane and polyvinylcyclopentane, syndiotactic polystyrene, poly3-methylpentene-1, and poly3
-Methylbutene-1, polyalkenylsilane and the like. As metal salts, aluminum benzoate, p-
Examples include aluminum t-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate, and the like.

As dibenzylidene sorbitol or a derivative thereof, dibenzylidene sorbitol, 1,3:
2,4-bis (o-3,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-2,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o- 4-ethylbenzylidene) sorbitol, 1,
3: 2,4-bis (o-4-chlorobenzylidene) sorbitol, 1,3: 2,4-dibenzylidene sorbitol and the like. Further, specifically, there may be mentioned, for example, Gelol MD or Gelol MD-R (trade name) manufactured by Shin Nippon Rika (manufactured). Examples of rosin acid partial metal salts include Pine Crystal KM1600, Pine Crystal KM1500, and Pine Crystal KM1 manufactured by Arakawa Chemical Industries, Ltd.
300 (product name) and the like. As the inorganic fine particles, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite,
Aluminum powder, alumina, silica, diatomaceous earth, titanium oxide, magnesium oxide, pumice powder, pumice balloon,
Examples include aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, and molybdenum sulfide. Examples of the amide compound include dianilide adipate and dianilide sperate. One of these nucleating agents may be used, or two or more of them may be used in combination. In the propylene-based resin composition of the present invention, it is preferable to use inorganic fine particles such as an organic metal phosphate salt and / or talc represented by the following general formula as a nucleating agent, because it does not generate odor. This propylene-based resin composition is suitable for use in foods.

[0032]

Embedded image

(Wherein, R ¹⁸ is a hydrogen atom or a carbon number of 1 to 4)
R ¹⁹ and R ²⁰ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
It represents an aryl group or an aralkyl group. M represents any one of an alkali metal, an alkaline earth metal, aluminum and zinc. When M is an alkali metal, m is 0, n
Represents 1; n represents 1 or 2 when M is an alkaline earth metal or zinc; m represents 1 when n is 1; m represents 0 when n is 2; Represents 1 and n represents 2. ) Specific examples of metal organic phosphates include ADK STAB NA
-11 and ADK STAB NA-21 (manufactured by Asahi Denka Co., Ltd.). Further, in the resin composition according to the present invention, it is preferable to use the above-mentioned inorganic fine particles such as talc as a nucleating agent, since when formed into a film, the film has excellent slip properties and improves properties such as printing properties. Further, the use of the above-mentioned dibenzylidene sorbitol or a derivative thereof as a nucleating agent is preferable because of excellent transparency. Further, it is preferable to use the above-mentioned amide compound as a nucleating agent because of its excellent rigidity. The resin composition according to the present invention is excellent in moldability, less sticky, and excellent in softness and transparency.

In the present invention, in order to form a film or a sheet used for the surface layer and / or the base material, the above resin composition is formed to a thickness of 0.03 by a molding method such as cast molding, inflation molding and calendering. It is advantageous to process the film or sheet into a thickness of about 0.5 mm.
The film or sheet obtained in this way has adhesiveness,
In order to improve printability and the like, it is desirable to perform surface treatment such as corona treatment, ozone treatment, and 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 has a surface layer,
One having a laminated structure composed of an adhesive layer, a picture layer, an adhesive layer and a substrate, a so-called doubling film, or one having a laminated structure composed of a surface layer, an adhesive layer and a picture layer, a so-called backing It may be a print film (printed directly on the surface layer and has no base material).

As the adhesive layer in the decorative film / sheet, for example, a polyurethane resin, an epoxy resin, an acrylic resin, a vinyl resin, a vinyl acetate resin, a polyester resin, an 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 a modified polyolefin having a thickness of 1 to 2
Those having a thickness of about 0 μm can be preferably mentioned. Here, as the modified polyolefin, for example, polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-nonconjugated diene compound copolymer (eg, EPDM), ethylene-aromatic monovinyl compound-conjugated diene Polyolefins such as compound copolymer rubbers are converted to 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. And amides of unsaturated carboxylic acids such as esters of acrylic acid and amides of maleic acid, and imides of unsaturated carboxylic acids such as maleimide and N-butylmaleimide.

The form of the adhesive at the time of processing is not particularly limited, and may be any of liquid, semi-molten, and 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, a grain pattern, a stone pattern, a surface pattern of natural leather, a grain pattern, an abstract pattern, and the like, and 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 one of acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, acetylcellulose resin and the like can be used. The ink is appropriately mixed with a coloring agent such as a pigment and a dye, an extender pigment, a solvent, and the like. The thickness of the pattern layer is usually 1 to 5 μm.
It is about.

In the present invention, it is particularly preferable that the picture layer has a two-layer structure of a picture pattern layer and a concealing layer.
As the ink used for forming the concealing layer, an ink obtained by appropriately mixing a binder with a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like is used. Examples of the binder include the same binders as those exemplified as the binder for the ink used for providing the picture pattern layer. As the concealing layer, a solid printing layer having a thickness of about 1 to 20 μm is suitable. This concealing layer is provided as a lower layer of the picture pattern layer.
Further, in the decorative film or sheet of the present invention, an acrylic resin or a polyurethane resin may be optionally provided on the surface layer for the purpose of improving abrasion resistance, weather resistance, embossing property, scratch resistance, stain resistance and the like. Thickness 1-20 consisting of
A top coat layer of about μm may be formed. The surface layer may be subjected to embossing, if desired, or its concave portion 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 the method has the above-mentioned laminated structure, and examples thereof include, but are not limited to, for example, a surface layer, an adhesive layer, a picture layer, and an adhesive. Those having a laminated structure composed of a layer and a substrate are advantageously produced by the following two methods. First, as a first method, an adhesive layer, a picture layer and an adhesive layer are sequentially laminated on a base material by a general printing method such as gravure printing, screen printing, offset printing, flexographic printing, and the like. (1) A method of bonding a film or sheet to be a surface layer by thermal lamination or the like on the layer, (2) A method of bonding a film or sheet to be a surface layer by dry lamination or wet lamination or the like, (3) Surface layer General printing methods such as gravure printing, screen printing, offset printing, flexographic printing, etc.
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 picture layer are sequentially laminated on a base material by a general printing method such as gravure printing, screen printing, offset printing, flexographic printing, and the like. ) An adhesive layer is provided on a film or sheet serving as a 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.
Next, this is laminated so that the adhesive layer is in contact with the picture layer and bonded by thermal lamination or the like. (2) An adhesive layer is formed on a film or sheet to be a surface layer by the same method as (1). (3) a method of extruding and bonding in a molten state a resin to be an adhesive layer 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 co-extrusion 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 bonding the decorative film / sheet thus obtained to various substrates. Examples of the material used for the base material of the decorative material include wood, plywood, laminated wood, wood base materials such as particle board and hard board, metal base materials such as steel plate, stainless steel plate and aluminum plate, and gypsum, for example. An inorganic base material such as a board may be used. To manufacture a cosmetic material,
The decorative film / sheet may be laminated using an adhesive such that the base material or the pattern layer faces the decorative film / sheet. At this time, the adhesive used is not particularly limited, and may be appropriately selected from conventionally known adhesives.

[0041]

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 Polymer Pellets (A) Synthesis of Complex Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2'-dimethylsilylene) (2,
3.0 g (6.97 mmol) of lithium salt of 1'-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF and cooled to -78 ° C. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane is slowly added dropwise and stirred at room temperature for 12 hours. The solvent is distilled off, 50 ml of ether is added, and the mixture is washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried, and the solvent was removed. 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was removed. (Yield 84
%). Next, the (1,2′-dimethylsilylene) (2,1′-) obtained above was placed in a Schlenk bottle under a nitrogen stream.
3.04 g (5.88 mmol) of dimethylsilylene) -bis (3-trimethylsilylmethylindene) and 50 ml of ether are added. Cool to -78 ° C and n-Bu
Li (1.54M in hexane) was added to 7.6 ml (1
After adding 1.7 mmol), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of a lithium salt as an ether adduct (yield 73%).
The result of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) is: δ 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.
10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (q, 4H, methylene), 6.2-7.7
(M, 8H, Ar-H). The lithium salt obtained above was dissolved in 50 ml of toluene under a nitrogen stream. After cooling to −78 ° C., a toluene (20 ml) suspension of zirconium tetrachloride (1.2 g, 5.1 mmol) previously cooled to −78 ° C. was added dropwise. After the addition, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off.
The obtained residue was recrystallized from dichloromethane to give 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 3
3 mmol) (26% yield). ¹ H-NMR (9
0 MHz, CDCl ₃ ) gives: δ
0.0 (s, 18H, trimethylsilyl), 1.02, 1.1
2 (s, 12H, dimethylsilylene), 2.51 (dd,
4H, methylene), 7.1-7.6 (m, 8H, Ar-H)
Met.

Polymerization of Propylene In a stainless steel autoclave with a stirrer and having an internal volume of 10 liters, 4 liters of n-heptane, 2 mmoles of triisobutylaluminum, and 2 mmoles of methylaluminoxane (manufactured by Albemarle Co.) were obtained as described above.
2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl)
2 micromoles of zirconium dichloride were charged sequentially. Then, after introducing 0.06 MPa (gauge) of hydrogen, the temperature was raised to 60 ° C., and the total pressure was 0.8.
Propylene gas was introduced up to MPa (gauge).
During the polymerization, propylene was supplied by a pressure regulator so that the total pressure became 0.8 MPa (gauge). Polymerization temperature 60 ° C
After conducting polymerization for 30 minutes, the content was taken out and dried under reduced pressure to obtain a propylene polymer. Granulation Perform the following additive formulation on the obtained propylene polymer,
Single screw extruder (manufactured by Tsukada Juki Seisakusho: TLC 35-20)
), And extruded and granulated to produce a propylene polymer pellet (A). About the obtained pellet (A),
The evaluation was made according to the following “Evaluation of resin properties of propylene polymer”. Table 1 shows the results.

(Formulation of additives) Phenolic antioxidant: Ciba Specialty Chemicals, Irganox 1010; 500 ppm Phosphorus antioxidant: Ciba Specialty Chemicals, Irgafos 168; 1,000 ppm

(2) Evaluation of Resin Properties of Propylene Polymer Measurement of [η] It was measured at 135 ° C. in a tetralin solvent using a VMR-053 automatic viscometer manufactured by Rigo Co., Ltd. Measurement of Pentad Fraction It was measured by the method described in the text of the specification. Measurement of melt flow rate (MFR) 230 ° C, load 21.1 according to JIS K7210
Measured at 8N. Measurement of molecular weight distribution (Mw / Mn) Mw / Mn was measured by an apparatus described below.

GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C. Flow rate: 1.0 Milliliter / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0)

DSC measurement Differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-
7) Using a 10 mg sample at 230 ° C. in a nitrogen atmosphere for 3
After melting for 1 minute, the temperature was lowered to 0 ° C at 1 ° C / minute,
After holding at 0 ° C for 3 minutes, the temperature was raised at 10 ° C / minute, and the melting endotherm obtained was ΔH. The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as melting point: Tm. Furthermore, after holding at 230 ° C. for 3 minutes, the temperature is lowered to 0 ° C. at 10 ° C./min. The peak top of the maximum peak of the crystallization exothermic curve obtained at this time was defined as crystallization temperature: Tc. Temperature rising fractionation chromatograph The amount W25 (% by mass) of the component eluted without being adsorbed by the filler at the TREF column temperature of 25 ° C. in the elution curve was determined as follows. (A) Operation method A sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, held for 30 minutes, and the sample is adsorbed on a filler. Thereafter, the column was heated to 135 ° C. at a heating rate of 40 ° C./hour.
The temperature was raised to ℃ to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6φ x 150mm) manufactured by GL Sciences Flow cell: 1mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1μm column filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: within ± 0.2 ° C.

[0047]

[Table 1]

(3) Formation of surface layer film Propylene polymer pellet (A) obtained in (1) above
50 mass% and 50 mass% of polypropylene (F-704NP manufactured by Idemitsu Petrochemical Co., Ltd.) were blended, and the resin temperature was 250 ° C. and the take-off speed was 10 by a 90 mmφ cast molding machine.
A film having a thickness of 100 μm was formed under the conditions of m / min.
This film was subjected to graining on one side at the same time as molding, and corona treatment was performed on both sides under the condition of 5.0 kW. The wetting index (measured according to JIS K6768) of the corona-treated surface was 500 μN / cm. (4) Lamination of Adhesive Layer On the smooth surface side of the film obtained in (3) above, an adhesive having a thickness of 3 μm by gravure printing using a primer containing vinyl chloride-vinyl acetate copolymer resin as a main component. Layers were provided. (5) Production of a printed film (pattern layer) A primer mainly composed of a vinyl chloride-vinyl acetate copolymer resin and a binder of a vinyl chloride-vinyl acetate copolymer resin on a colored high-density polyethylene film having a thickness of 90 μm. Ink to be laminated sequentially by gravure printing,
Further, a primer mainly composed of a vinyl chloride-vinyl acetate copolymer resin was similarly laminated to produce a printed film. The total thickness of the printed film was 100 μm.

(6) Lamination of the surface layer film and the print film The adhesive layer surface of the surface layer film obtained in the above (4) and the adhesive layer surface of the print film obtained in the above (5) are superposed, and Lamination was performed through a hot roll at ℃ to obtain a decorative sheet. (7) Adhesion to plywood and evaluation of secondary workability The decorative film obtained in the above (6) had extremely good surface layer transparency, and had a luxurious depth in the picture layer. Further, the flexibility was superior to that of a conventional decorative film made of a polyvinyl chloride film. Using an adhesive mainly composed of an ethylene-vinyl acetate copolymer resin, the decorative film was laminated on a medium-density particle board having irregularities so that the colored high-density polyethylene layer was in contact with the decorative film. Further, it was similarly laminated on a 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 extremely good.

Example 2 (1) Lamination by Coextrusion Direct Lamination 50% by mass of the propylene polymer pellet (A) obtained in Example 1- (1) and polypropylene [F-704NP manufactured by Idemitsu Petrochemical Co., Ltd.] And a propylene polymer pellet (A) 40% by mass.
An adhesive resin obtained by mixing 40% by mass of polypropylene F-704NP and 20% by mass of a maleic anhydride-modified polyolefin [Polytack E-100 manufactured by Idemitsu Petrochemical Co., Ltd.] is coextruded and subjected to ozone treatment. After doing
The printed film of Example 1- (5) was laminated with a decorative film. The resin temperature of the molten resin during co-extrusion is 2
At 90 ° C., the thickness of the obtained decorative film was 160 μm. (2) Adhesion of plywood and evaluation of secondary workability The decorative film obtained in the above (1) had a very good surface layer transparency, and the pattern layer had a luxurious depth. Further, the flexibility was superior to that of a conventional decorative film made of a polyvinyl chloride film. Using an adhesive mainly composed of an ethylene-vinyl acetate copolymer resin, the decorative film was laminated on a medium-density particle board having irregularities so that the colored high-density polyethylene layer was in contact with the decorative film. Further, it was similarly laminated on a 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 extremely good.

Example 3 (1) Production of back print film The film obtained in Example 1- (3) was used as a surface layer, and on the smooth surface side, a vinyl chloride-vinyl acetate copolymer resin was used as a main component. A primer to be used, using an ink having a vinyl chloride-vinyl acetate copolymer resin as a binder, sequentially laminating an adhesive layer and a picture layer by gravure printing, and further using a mixture of the above ink and a pigment, by gravure printing. A decorative film was prepared by laminating a solid coating layer. (2) Adhesion to plywood and evaluation of secondary workability The decorative film obtained in the above (1) had extremely good transparency of the surface layer, and had a luxurious depth in the picture layer. Further, the flexibility was superior to that of a conventional decorative film made of a polyvinyl chloride film. Using an adhesive mainly composed of an ethylene-vinyl acetate copolymer resin, the decorative film was laminated on a medium-density particle board having an uneven portion so that the solid coating layer surface was in contact with the decorative film. Further, it was similarly laminated on a 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 extremely good.

Example 4 In Example 1, except that the pellet (A) was 70% by mass and the polypropylene F-704NP was 30% by mass,
In the same manner as in Example 1, a decorative film was produced, bonded to a plywood, and evaluated for secondary workability. The obtained decorative film had extremely good transparency of the surface layer, and had a high-quality depth in the picture layer. Further, the flexibility was superior to that of a conventional decorative film made of a polyvinyl chloride film. There were no cracks or whitening in the bent portion, and the lapping workability and V-cut workability were extremely good. Example 5 In Example 1, except that the pellet (A) was 30% by mass and the polypropylene F-704NP was 70% by mass,
In the same manner as in Example 1, a decorative film was produced, bonded to a plywood, and evaluated for secondary workability. The obtained decorative film had good surface layer transparency, and the pattern layer had depth. Moreover, the flexibility was equivalent to that of a conventional decorative film made of a polyvinyl chloride film. There were no cracks or whitening in the bent portion, and the lapping workability and V-cut workability were good.

Comparative Example 1 (1) Formation of Surface Layer Film Polypropylene resin [Noblen FL manufactured by Sumitomo Chemical Co., Ltd.]
6315G, melting peak temperature (Tm): 140 ° C] 90
Dry blending of 10% by mass of a thermoplastic elastomer [Hybler HVS-3 manufactured by Kuraray Co., Ltd.]
Using a mmφ cast molding machine, a film having a thickness of 80 μm was formed at a resin temperature of 230 ° C. and a take-up speed of 5 m / min. This film was subjected to graining on one side and corona treatment (4.5 kW) on both sides. The corona treated surface had a wetting index of 490 μN / cm. (2) Lamination of Adhesive Layer On the smooth surface side of the film obtained in the above (1), a primer having a thickness of 3 μm is attached by gravure printing using a primer mainly composed of a vinyl chloride-vinyl acetate copolymer resin. An agent layer was provided. (3) Production of print film (pattern layer) A primer mainly composed of vinyl chloride-vinyl acetate copolymer resin and a binder of vinyl chloride-vinyl acetate copolymer resin on a colored high-density polyethylene film having a thickness of 90 μm. Ink to be laminated sequentially by gravure printing,
Further, a primer mainly composed of a vinyl chloride-vinyl acetate copolymer resin was similarly laminated to produce a printed film. The total thickness of the printed 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 superimposed at 120 ° C. Were laminated through a hot roll to obtain a decorative sheet. (5) Adhesion to plywood and evaluation of secondary workability The decorative film obtained in (4) above has a somewhat poor transparency of the surface layer, but the flexibility is equivalent to that of a conventional decorative film made of a polyvinyl chloride film. there were. Using an adhesive mainly composed of an ethylene-vinyl acetate copolymer resin, the decorative film was laminated on a medium-density particle board having an uneven portion so that the colored high-density polyethylene layer was in contact therewith. In addition, it is similarly stuck on a board on a flat plate,
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. Table 2 summarizes the above results.

[0055]

[Table 2]

[0056]

The decorative film / sheet of the present invention has good transparency of the surface layer, excellent V-cut workability, wrapping workability, etc., and does not generate chlorine gas during incineration. It has a very high commercial value. Since the decorative film / sheet of the present invention has the above-mentioned excellent characteristics, it can be suitably used for, for example, furniture members, cabinets such as refrigerators and televisions, and building interior materials.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08L 23/02 C08L 23/02 4J128 23/10 23/10 F term (reference) 2B002 AA03 DA04 2B250 AA13 BA02 FA09 GA08 HA01 4F100 AA00C AK03A AK03B AK07A AK07B AK07K AL05A AL05B AP00C BA02 BA03 BA07 BA10A BA10B BA10C BA13 BA16 GB08 GB48 GB81 HB31 JA06A JA06B JA20A JA20B JL01 JN01 YY00A YY00B 4J002 BB05X BB06X BB12W BB12X BB14W BB15W BB15X BB20X BB21X BC02X FD010 FD030 FD200 GF00 GL00 4J028 AA01A AB00A AB01A AC01A AC19A AC20A AC27A AC28A AC31A AC41A AC45A AC49A BA00A BA01B BA02B BB00A BB01B BB02B BC15B BC16B BC17B BC19B BC25B BC29B EA01 EB02 EB04 EB05 EB07 EB08 EB09 EB10 EC01 AC01 AC01 AC01 AC01 FA01 FA01 FA02 FA04 BA02B BB00A BB01B BB02B BC15B BC16B BC17B BC19B BC25B BC29B EA01 EB02 EB04 EB05 EB07 EB08 EB09 EB10 EC01 EC02 FA01 FA02 FA04 FA07

Claims (9)

[Claims] 1. A decorative film or sheet having a laminated structure composed of a surface layer, an adhesive layer, a pattern layer, an adhesive layer and a substrate, or a laminated structure composed of a surface layer, an adhesive layer and a pattern layer. Alternatively, the following (1) and (2): (1) the mesopentad fraction (mmmm) is 0.2 to 0.6, or (2) the racemic pentad fraction (rrrr) and (1) -Mm
mm) that satisfies the following relationship: [rrrr / (1-mmmm)] ≤1 to 99% by mass of propylene polymer [I] satisfying 0.1 and a resin containing 99 to 1% by mass of olefin-based resin [II] A decorative film or sheet using a film or sheet comprising the composition. 2. The decorative film according to claim 1, wherein the surface layer is a film or sheet comprising a resin composition containing a propylene polymer [I] and an olefin resin [II].
Sheet. 3. The propylene polymer [I] further satisfies the following (3) (3): intrinsic viscosity [η] measured in tetralin at 135 ° C. of 1.0 to 3.0 deciliter / g. 3. The decorative film or sheet according to claim 1, which is a propylene polymer. 4. A propylene polymer which further satisfies the following (4) (4) a component amount (W25) eluted at 25 ° C. or lower in temperature rising chromatography (W25) of 20 to 100% by mass in the propylene polymer [I]. The decorative film / sheet according to any one of claims 1 to 3, which is a united product. 5. The propylene polymer [I] is polymerized using a metallocene catalyst comprising a transition metal compound having a crosslinked structure through two crosslinking groups and a cocatalyst. 5. The decorative film or sheet according to any one of 4. 6. The decorative film or sheet according to claim 1, wherein the picture layer has a two-layer structure of a picture layer and a concealing layer. 7. A decorative wooden material obtained by bonding the decorative film or sheet according to claim 1 to a wooden substrate. 8. A decorative metal material obtained by bonding the decorative film or sheet according to claim 1 to a metal substrate. 9. A decorative inorganic material obtained by bonding the decorative film or sheet according to claim 1 to an inorganic substrate.