JP2002144505A - Polyolefin-based laminated soft sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin-based soft sheet having excellent surface hardness, glossiness, transparency, softness, and surface appearance. SOLUTION: The laminated sheet has an inside layer and surface layers of both surface sides. The surface layers are composed by using a propylene- based polymer which is manufactured by using a metallocene catalyst, and has a durometer hardness of 60 or higher and a Q value of 1.5-3.5. The inside layer is composed by using an ethylene-α-olefin random copolymer which has an ethylene unit of 50-98 wt.%, a density of 0.860-0.910 g/cm3, and an MFR of 1-50 g/10 min., and is polymerized preferably by using the metallocene catalyst. As a result, the laminated soft sheet having a surface roughness of 25 nm or less, a tension modulus of 200 MPa or less, and a haze per 100 μm thickness of 1.5% or less can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin laminated soft sheet excellent in surface hardness, surface gloss, flexibility and transparency.

[0002]

2. Description of the Related Art Conventionally, as a soft sheet, a soft vinyl chloride resin containing a plasticizer has been widely used. However, soft vinyl chloride resin has various negative factors, such as poor appearance due to bleed-out of plasticizers and monomers, and acid rain resulting from the generation of hydrogen chloride during incineration becomes a social problem. It is in the state where it was.

[0003] On the other hand, low-density polyethylene, ethylene-
Ethylene-based products such as vinyl acetate copolymers and ionomers have been developed. However, when these soft resins mainly composed of ethylene are processed into a sheet, transparency, surface gloss and the like are inferior to the soft vinyl chloride resin sheet, and the surface hardness of the sheet is not sufficient and the surface is easily damaged. There are drawbacks.

On the other hand, it has been proposed to use a propylene-based resin having a high surface hardness, but the propylene-based resin has a drawback of insufficient flexibility. As a means for imparting flexibility to the propylene-based resin, a propylene-α-olefin copolymer containing an α-olefin as a comonomer can be used, but a large amount of α-olefin is required to impart flexibility. As in the case of the ethylene resin, the surface hardness decreases.

The present inventors have obtained a three-layer laminated sheet using a specific polyolefin to obtain a soft sheet having high surface hardness, excellent gloss, transparency and flexibility. And proposed (JP-A-2000-6336). The present inventors have conducted further development based on the above-mentioned prior invention, and as a result, the surface appearance and surface gloss can be remarkably improved by forming the surface layer with a specific propylene polymer, and the sheet can be easily formed. Have been found, and the present invention has been completed.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to surface hardness,
An object of the present invention is to provide a polyolefin-based soft sheet having excellent gloss, transparency, flexibility, and surface appearance.

[0007]

That is, the present invention provides a laminated sheet having at least an inner layer as a constituent layer and surface layers provided on both surfaces of the inner layer, wherein the surface layer is a metallocene catalyst. And a Q value of 1.
It is formed of a propylene polymer having a durometer hardness of 5 to 3.5 and a durometer hardness of 60 or more. And the tensile elastic modulus of the sheet is 200 MPa or less, preferably 150 MPa.
Hereinafter, haze is 1.5% or less per 100 μm thickness,
A polyolefin-based laminated soft sheet having a surface roughness of preferably 1.2% or less and a surface roughness of 25 nm or less, preferably 20 nm or less.

The polyolefin-based laminated soft sheet of the present invention has high flexibility with a tensile modulus of 200 MPa or less, high transparency with a haze per 100 μm of 1.5% or less, and surface roughness of 25 nm or less. High surface hardness of 60 or more in durometer hardness. A polyolefin-based soft sheet having all of such high flexibility, transparency, and surface hardness has been found for the first time in the present invention.

[0009]

Embodiments of the present invention will be described below. The laminated soft sheet of the present invention is a laminated sheet having, as constituent layers, at least an inner layer and surface layers provided on both surface sides of the inner layer.

Among the physical properties of the surface layer, durometer hardness is a hardness measured according to JIS-K7215, tensile modulus is a value measured according to JIS-K7127, and haze ( haze) is JI
The value measured according to S-K7105, surface gloss is J
The value measured according to IS-K7105 and the surface roughness are J
Center line average roughness (R) measured according to IS-B0601
a) is shown respectively.

The laminated soft sheet having such physical properties, which has been found for the first time in the present invention, can be obtained by using appropriate resin materials for the surface layer and the inner layer.

(1) Surface Layer The surface layer of the present invention is produced using a metallocene catalyst and has a Q value of 1.5 to 3.5, preferably 1.7 to 3.
3. Durometer hardness is 60 or more, preferably 63 to
73.
Here, the Q value is defined as the ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC), and is a measure of the molecular weight distribution. The smaller the Q value, the sharper the molecular weight distribution.

Examples of the propylene-based polymer include a propylene homopolymer, a random copolymer of propylene and ethylene or another α-olefin, or a mixture thereof.

The comonomer in the random copolymer is preferably ethylene or an α-olefin having 4 to 12 carbon atoms.
1, pentene-1, hexene-1, 4-methyl-pentene-1 and the like. In the random copolymer, a preferable ratio of a structural unit derived from propylene (hereinafter, referred to as a “propylene unit”) is 90 to 9 in all the structural units.
It is 9% by weight, and the structural unit derived from the α-olefin (hereinafter, referred to as “comonomer unit”) is 1 to 10% by weight.

Among these, a particularly preferred propylene polymer used in the present invention is a random copolymer of propylene and ethylene and / or butene-1. The propylene-based polymer is preferably JIS-
The density measured according to K7112 (23 ° C.) is 0.
880-0.905 g / cm ³ , more preferably 0.8
85 to 0.904 g / cm ³ , more preferably 0.8
90 to 0.903 g / cm ³ . If the density is higher than the above range, the flexibility is insufficient, and if the density is lower than the above range, the surface hardness is insufficient.

The propylene-based polymer is JIS-K7
The MFR (melt flow rate) measured in accordance with No. 210 (230 ° C., 2.16 kg load) is preferably 1
５０50 g / 10 min, more preferably 1.5 to 40 g / 1
0 minutes, more preferably 2 to 30 g / 10 minutes. M
If the FR exceeds the above range, the melt tension becomes insufficient and the extrudability of the sheet becomes poor, and if the MFR is less than the above range, the flow becomes poor at the time of forming the laminated sheet and the thickness varies.
The Q value is 1.5 to 3.5, preferably 1.8 to
Selected from the range of 3.3. The melt viscosity is 4
500-8000 poise, preferably 4800-700
It is selected from the range of 0 poise. A propylene-based polymer having such various physical properties can be easily produced by polymerizing propylene or the like using a metallocene catalyst described later.

The metallocene catalyst used in the present invention is a catalyst comprising a metallocene-based transition metal compound (A) and an ion-exchange layered silicate (B) or, if necessary, (A) and (B). And a catalyst further containing an organoaluminum compound (C). Hereinafter, these may be referred to as component A, component B, and component C.

First, the metallocene transition metal compound (A)
Will be described. Component A is represented by the following general formula (1) or (2). _{Q (C 5 H 4-a} R 1 a) (C 5 H 4-b R 2 b) MeXY (1) (C 5 H 4-a R 1 a) (C 5 H 4-b R 2 b) MeXY (2) _{[wherein, C 5 H 4-a R} 1 a and ^{_{C 5 H 4-b R 2}} b each represent a conjugated five-membered ring ligands, Q is two conjugated five-membered ring ligand A divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms Wherein Me represents zirconium or hafnium; X and Y each independently represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms,
0 alkoxy group, C1-20 alkylamide group, trifluoromethanesulfonic acid group, C1-20
Or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. R ¹ and R ² are substituents on the conjugated five-membered ligand, and each independently has 1 to 1 carbon atoms.
20 hydrocarbon groups, halogen groups, alkoxy groups, silicon-containing hydrocarbon groups, phosphorus-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups or boron-containing hydrocarbon groups. Two adjacent R ¹ or two R ² may be bonded to each other to form a ring. a and b are integers satisfying 0 ≦ a ≦ 4 and 0 ≦ b ≦ 4. However, the two five-membered ring ligands having R ¹ and R ² are asymmetric with respect to the plane containing Me in terms of their relative positions via the group Q. ]

[0019] Q is as described above, a bonding group for cross-linking two conjugated five-membered ring ligand ^{_{C 5 H 4-a R 1}} a and ^{_{C 5 H 4-b R 2}} b, specifically Specifically, for example, (A) carbon number 1-2
0, preferably 1 to 6 divalent hydrocarbon groups, specifically, for example, an alkylene group, a cycloalkylene group, an arylene and the like, a (II) hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Having a silylene group, (c) having 1 to 2 carbon atoms
There are 0, preferably 1 to 12, germylene groups having hydrocarbon groups. Regardless of the number of carbon atoms, the distance between the two bonds of the divalent Q group is about 4 atoms or less, especially 3 atoms or less when Q is chain-like. In the case of having a group, it is preferable that the cyclic group is not more than about +2 atoms, and particularly preferably the cyclic group alone. Therefore, in the case of an alkylene group, ethylene and isopropylidene (the distance between bonds is 2 atoms and 1 atom), in the case of a cycloalkylene group, cyclohexylene (the distance between bonds is only a cyclohexylene group) and in the alkylsilylene group, In this case, dimethylsilylene (the distance between bonds is 1 atom) is preferable. Me is titanium, zirconium or hafnium, preferably zirconium or hafnium.

X and Y may be each independently, that is, they may be the same or different, and (A) hydrogen, (B) halogen (fluorine, chlorine, bromine or iodine, preferably chlorine), (C) carbon number 1 A hydrocarbon group having 1 to 20 carbon atoms, (d) an alkoxy group having 1 to 20 carbon atoms, (e) an alkylamide group having 1 to 20 carbon atoms, (f) a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, (g) It represents a silicon-containing hydrocarbon group having 1 to 20 carbon atoms or a (thi) trifluoromethanesulfonic acid group.

R ¹ and R ² are substituents on the conjugated five-membered ring ligand, each independently being a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, an alkoxy group having 1 to 20 carbon atoms. Group, silicon-containing hydrocarbon group having 3 to 20 carbon atoms, 2 carbon atoms
A phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group having 2 to 20 carbon atoms, or a boron-containing hydrocarbon group having 2 to 20 carbon atoms. Further, two adjacent R ¹ or two R ² may be bonded at the ω-terminal to form a ring together with a part of the cyclopentadienyl group. As a typical example of such a case, two adjacent R ¹ (or R ² ) on the cyclopentadienyl group share a double bond of the cyclopentadienyl group to form a fused six-membered ring. (Ie, an indenyl group and a fluorenyl group) and those forming a fused seven-membered ring (ie, an azulenyl group). a and b are 0 ≦ a ≦ 4, 0 ≦ b
It is an integer satisfying ≦ 4.

Non-limiting examples of the metallocene compound represented by the general formula (1) include the following. In addition, these compounds are indicated by only chemical names, but needless to say, the three-dimensional structure has the asymmetry referred to in the present invention. Although only the case where zirconium is used as Me is exemplified, hafnium may be directly substituted instead.

Transition metal compounds having two silylene bridged five-membered ring ligands, such as (1) dimethylsilylenebis (1-indenyl) zirconium dichloride, (2) dimethylsilylenebis {1-
(2-methyl-4-phenyl-4H-azulenyl) {zirconium dichloride, (3) dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride, (4) methylphenylsilylene Bis {1- (2,4-dimethylindenyl)}
Zirconium dichloride, (5) methylphenylsilylene bis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride, (6) dimethylsilylenebis {1- (2-methyl-4-phenylindenyl) ) {Zirconium dimethyl, (7) dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azulenyl)} zirconium dichloride, (8) dimethylsilylene} 1- (2-ethyl-4-phenyl-4, 5,6
7,8-pentahydroazulenyl) {1- (2,3,
5-trimethylcyclopentadienyl) {zirconium dichloride, (9) dimethylsilylenebis} 1- (2-
Ethyl-4- (pentafluorophenyl) indenyl) zirconium dichloride.

A five-membered ring ligand bridged with an alkylene group is
Transition metal compounds having, for example, (1) ethylene-
1,2-bis (1-indenyl) zirconium dichloride, (2) ethylene-1,2-bis {1- (2,4-dimethylindenyl)} zirconium dichloride, (3)
Ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, (4) ethylene-1,2-bis {1- (2-methyl-4,5-benzoindenyl) )} Zirconium dichloride, (5) ethylene-1,2-bis [1- {2-methyl-4- (4-
Chlorophenyl) -4H-azulenyl}] zirconium dichloride.

A transition metal compound having a five-membered ring ligand bridged by a hydrocarbon residue containing germanium, aluminum, boron, phosphorus or nitrogen, for example, (1) dimethylgermylene bis (1-indenyl) zirconium dichloride, (2) dimethylgermylenebis {1- (2-methyl-4-phenyl-4H-azulenyl)} zirconium dichloride, (3) dimethylgermylenebis {1- (2)
-Methyl-4,5-benzoindenyl) zirconium dichloride, (4) phenylphosphinobis (1-indenyl) zirconium dichloride, (5) phenylaminobis (1-indenyl) zirconium dichloride and the like. Among these complexes, particularly preferred are complexes having an azulene skeleton.

As the metallocene transition metal compound represented by the general formula (2), the following compounds can be exemplified. (1) bis (1-indenyl) zirconium dichloride, (2) bis {1- (2-methyl-4-phenyl-4)
H-azulenyl) {zirconium dichloride, (3) bis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride, (4) bis {1-
(2,4-dimethylindenyl)} zirconium dichloride, (5) bis [1,1 ′-{2-methyl-4- (4
-Chlorophenyl) -4H-azulenyl}] zirconium dichloride (6) bis [1,1 '-{2-methyl-4
-(4-chloro-2-naphthyl) -4H-azulenyl}] zirconium dichloride (7) bis {1,1'-
(2-ethyl-4-phenyl-4H-azulenyl) ニ ル zirconium dichloride (8) bis ｛1,1 ′-(2-methyl-4-phenylhexahydroazulenyl)｝ zirconium dichloride (9) bis [1,1 '-{2-methyl-4- (4-chlorophenyl) hexahydroazulenyl}] zirconium dichloride (10) bis [1,1'
-{2-methyl-4- (4-chloro-2-naphthyl) hexahydroazulenyl}] zirconium dichloride (1
1) bis (1-fluorenyl) zirconium dichloride, (12) bis {1- (2-methyl-4-phenyl-)
4H-fluorenyl) zirconium dichloride. Here, only the case of zirconium as Me has been exemplified,
Alternatively, hafnium can be directly substituted and named.

The metallocene transition metal compound represented by the general formula (1) is effective in producing both a propylene polymer constituting the surface layer and an ethylene / α-olefin copolymer constituting the inner layer. is there. On the other hand, the metallocene transition metal compound represented by the general formula (2) is mainly used for producing an ethylene / α-olefin copolymer constituting an inner layer.

Next, the ion-exchange layered silicate (B) will be described. The ion-exchangeable phyllosilicate is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and refers to a contained ion-exchangeable silicate. Most ion-exchanged phyllosilicates occur naturally mainly as a main component of clay minerals, but these ion-exchanged phyllosilicates are not limited to those of natural origin but are artificially synthesized. You may. Specific examples include dickite, nacrite, kaolinite,
Kaolin group such as anoxite, metahalloysite, halloysite, serpentine group such as chrysotile, lizardite, antigolite, montmorillonite, zaukonite,
Smectites such as beidellite, nontronite, saponite, hectorite, and stevensite, vermiculites such as vermiculite, mica such as mica, illite, sericite, chlorite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite , Talc and chlorite. These may form a mixed layer.

Among these, montmorillonite, zaukonite, beidellite, nontronite, saponite,
Smectites such as hectorite, stevensite, bentonite and teniolite, vermiculites and mica are preferred. When a compound having a radius of 20 angstroms or more and a pore volume of less than 0.1 cc / g measured by a mercury intrusion method is used as component B, a high polymerization activity tends to be difficult to obtain. / G or more,
In particular, those having 0.3 to 5 cc / g are preferable. Component B can be used as it is without any particular treatment, but it is also preferable to subject component B to a chemical treatment. Here, the chemical treatment can be any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the structure of the clay.

Specific examples include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment increases the surface area by removing impurities on the surface and eluting cations such as Al, Fe, and Mg in the crystal structure.
Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In salt treatment and organic matter treatment,
An ion complex, a molecular complex, an organic derivative, or the like can be formed to change a surface area or an interlayer distance. By utilizing the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, it is also possible to obtain a layered material in which the layers are expanded. That is, the bulky ions play a pillar-like role to support the layered structure, and are called pillars. Introducing another substance between layered substance layers is called intercalation.

As the guest compound to be intercalated, cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ ,
Metal alcoholates such as B (OR) ₃ [R is alkyl, aryl, etc.], [Al ₁₃ O ₄ (OH) ₂₄ ] ₇₊ , [Zr ₄ (O
H) ₁₄ ] ₂₊ , and metal hydroxide ions such as [Fe ₃ O (OCOCH ₃ ) ₆ ] ₊ . These compounds may be used alone or in combination of two or more.
When intercalating these compounds, Si
A polymer obtained by hydrolyzing a metal alcoholate such as (OR) ₄ , Al (OR) ₃ , Ge (OR) _{4, and} a colloidal inorganic compound such as SiO ₂ can also be present. Examples of pillars include oxides formed by intercalating the hydroxide ions between layers and then heating and dehydrating. Component B may be used as it is, or may be used after heat dehydration treatment. Further, they may be used alone or as a mixture of two or more of the above solids.

As the ion-exchange layered silicate, at least 40%, preferably 6%, of the exchangeable Group 1 metal cations contained in the ion-exchange layered silicate before being treated with salts.
0% or more of a cation dissociated from the following salts,
Preferably, ion exchange is performed. The salt used in the salt treatment for the purpose of ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of Group 2 to 14 atoms,
A compound comprising a cation containing at least one atom selected from the group consisting of Group 14 atoms and at least one anion selected from the group consisting of halogen atoms, inorganic acids and organic acids, more preferably , A cation containing at least one atom selected from the group consisting of Group 2-14 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO
₃ , CO ₃ , C ₂ O ₄ , OCOCH ₃ , CH ₃ COCHCOC
H ₃ , OCl ₃ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (S
O ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OCOH, OCOC
It is a compound comprising at least one anion selected from the group consisting of H ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ .

Specifically, CaCl_Two, CaSO_Four, Ca
C_TwoO_Four, Ca (NO_Three)_Two, Ca_Three(C₆H_FiveO₇)_Two, Mg
Cl_Two, Sc (OCOCH_Three)_Two, ScF_Three, ScBr_Three,
Y (OCOCH_Three)_Three, LaPO_Four, La_Two(SO_Four)_Three, S
m (OCOCH_Three)_Three, SmCl_Three, Yb (NO_Three)_Three, Y
b (ClO_Four)_Three, Ti (OCOCH_Three)_Four, Ti (C
O_Three)_Two, Ti (SO_Four)_Two, TiF_Four, TiCl_Four, Zr
(OCOCH_Three)_Four, Zr (CO_Three)_Two, Zr (NO_Three)_Four,
ZrOCl_Two, Hf (SO_Four)_Two, HfBr_Four, HfI_Four,
V (CH_ThreeCOCHCOCH_Three)_Three, VOSO_Four, VC
l_Four, VBr_Three, Nb (CH _ThreeCOCHCOCH_Three)_Five, N
b_Two(CO_Three)_Five, Ta_Two(CO_Three)_Five, Ta (NO)_Five, T
aCl_Five, Cr (OOCH_Three)_TwoOH, Cr (NO_Three)_Three,
Cr (ClO_Four)_Three, MoOCl_Four, MoCl_Three, MoCl
_Four, MoCl_Five, MoF₆, WCl_Four, WBr_Five, Mn (C
H_ThreeCOCHCOCH_Three)_Two, Mn (NO_Three)_Two, Fe (O
COCH_Three)_Two, Fe (NO_Three)_Three, FeSO_Four, Co (O
COCH_Three)_Two, Co_Three(PO_Four)_Two, CoBr_Two, NiCO
_Three, NiC_TwoO_Four, Pb (OCOCH_Three)_Four, Pb (OOC
H_Three)_Two, PbCO_Three, Pb (NO_Three)_Two, CuI_Two, CuB
r_Two, CuC_TwoO_Four, Zn (OOCH_Three)_Two, Zn (CH_ThreeC
OCHCOCH_Three)_Two, Cd (OCOCH_TwoCH_Three)_Two, C
dF_Two,, AlCl_Three, Al_Two(C_TwoO_Four)_Three, Al (CH_Three
COCHCOCH_Three)_Three, GeCl_Four, GeBr_Four, Sn
(OCOCH_Three)_Four, Sn (SO_Four)_TwoAnd the like.

In addition to removing impurities on the surface, the acid treatment can elute a part or all of cations such as Al, Fe and Mg having a crystal structure. The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, phosphoric acid and acetic acid. The salt and the acid used for the treatment may be two or more. When combining the salt treatment and the acid treatment, after performing the salt treatment, a method of performing an acid treatment,
There is a method of performing a salt treatment after performing the acid treatment, and a method of simultaneously performing the salt treatment and the acid treatment.

The treatment conditions with salts and acids are not particularly limited, but usually, the concentration of salts and acids is 0.1 to 3
0% by weight, treatment temperature from room temperature to boiling point, treatment time from 5 minutes to
It is preferable to select the condition for 24 hours and to elute at least a part of at least one compound contained in the ion-exchange layered silicate. Further, salts and acids are generally used in an aqueous solution.

In the salt treatment and / or the acid treatment, the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, a chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination. These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water to use as component B.

Here, the adsorbed water is water adsorbed on the surface of the compound particles of the ion-exchangeable layered silicate or on the crystal fracture surface, and the interlayer water is water existing between the layers of the crystal. In the present invention, these adsorbed water and / or interlayer water can be removed by heat treatment before use. The method for heat treatment of the adsorbed water and interlayer water of the ion-exchanged layered silicate is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. Can be The temperature at the time of heating cannot be specified unconditionally because it depends on the types of ion-exchanged layered silicate and interlayer ions. However, the temperature is 100 ° C. or higher, preferably 150 ° C. or higher, so that interlayer water does not remain. Is not preferable (for example, 800 ° C. or higher, depending on the heating time). Further, a heat dehydration method for forming a crosslinked structure such as heating under air flow is not preferable because the polymerization activity of the catalyst is reduced. The heating time is at least 0.5 hour, preferably at least 1 hour. At this time, component B after removal
Is preferably 3% by weight or less, more preferably 1% by weight or less, assuming that the moisture content when dehydrated for 2 hours at a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight.

As the component B, it is preferable to use spherical particles having an average particle diameter of 5 μm or more. More preferably, spherical particles having an average particle size of 10 μm or more are used. More preferably, spherical particles having an average particle diameter of 10 μm or more and 100 μm or less are used. The average particle size here is represented by a number average particle size calculated by performing image processing on an optical microscope photograph (100 times magnification) of the particles. Component B may be a natural product or a commercially available product as long as the shape of the particles is spherical.
Particles in which the shape and particle size of the particles are controlled by a particle diameter, a separation, or the like may be used.

The granulation methods used here include, for example, stirring granulation, spray granulation, tumbling granulation, briquetting, compacting, extrusion granulation, fluidized bed granulation, and emulsion granulation. , A submerged granulation method, a compression molding granulation method and the like, but are not particularly limited as long as the component B can be granulated. The granulation method is preferably a stirring granulation method, a spray granulation method, a tumbling granulation method, or a fluidized bed granulation method, and particularly preferably a stirring granulation method or a spray granulation method. When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, or xylene is used as a dispersion medium for the raw material slurry. Preferably, water is used as the dispersion medium. The concentration of the component B in the raw slurry liquid for spray granulation to obtain spherical particles is 0.1 to 70%, preferably 1 to 50%.
%, Particularly preferably 5 to 30%. The temperature of the inlet of the hot air of the spray granulation from which the spherical particles are obtained varies depending on the dispersion medium.
Perform at 00-220 ° C.

At the time of granulation, an organic substance, an inorganic solvent, an inorganic salt, and various binders may be used. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcellulose, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein,
Latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel,
Gum arabic, sodium alginate and the like can be mentioned.

The spherical particles obtained as described above preferably have a compressive breaking strength of 0.2 MPa or more in order to suppress crushing and fine powder in the polymerization step. In the case of such a particle strength, the effect of improving the particle properties is effectively exhibited, particularly when prepolymerization is performed.

As the organoaluminum compound (component C) used as an optional component in addition to the components A and B, a compound represented by the following general formula (3) is suitable. The ^{_{(AlR 3 n X 3-n}} ) m (3) in the present invention compound represented by the formula alone, can be used in or in combination as a mixture of two or more. Also,
This use is possible not only at the time of catalyst preparation but also at the time of prepolymerization or polymerization. In this formula, R ³ has 1 to 20 carbon atoms.
X represents a halogen, hydrogen, an alkoxy group, or an amino group. n is an integer of 1-3 and m is an integer of 1-2. R ³ is preferably an alkyl group.
Is preferably chlorine when it is halogen, alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and amino group having 1 to 8 carbon atoms when it is an amino group. Therefore, specific examples of preferred compounds include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum,
Triisobutyl aluminum, tri normal hexyl aluminum, tri normal octyl aluminum, tri normal decyl aluminum, diethyl aluminum chloride, diethyl aluminum sesquichloride, diethyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum dimethyl amide, diisobutyl aluminum hydride, diisobutyl aluminum chloride, etc. Is mentioned. Of these, preferred are m = 1, n = 3 trialkylaluminum and dialkylaluminum hydride. More preferably, R ³ is a trialkyl aluminum having 1 to 8 carbon atoms.

As another example of the metallocene catalyst used in the present invention, the metallocene transition metal compound (component A)
Is combined with an aluminum oxy compound (component D). Also in this case, an organic aluminum compound (component C) can be used in combination as an optional component. Specific examples of the aluminum oxy compound (component D) include compounds represented by the following general formulas (4), (5) and (6).

[0044]

Embedded image

In the above formulas, R ⁴ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, more preferably a hydrocarbon residue having 1 to 6 carbon atoms. In addition, a plurality of R ⁴
May be the same or different. Also, p is 0
And an integer of 2 to 30, preferably 2 to 30.

The compounds represented by the general formulas (4) and (5) are also called alumoxanes and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water. Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane obtained from one type of trialkylaluminum and water, (b) two types of trialkylaluminum and Examples thereof include methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane obtained from water. Of these, methylalumoxane or methylisobutylalumoxane is preferred.

The compound represented by the general formula (6) can be prepared by mixing one kind of trialkylaluminum or two or more kinds of trialkylaluminums with an alkylboronic acid represented by the following general formula (7): It can be obtained by a 1: 1 (molar ratio) reaction. In the general formula (7), R ⁵ represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms or a halogenated hydrocarbon group. R ⁵ B (OH) ₂ (7) Specifically, the following reaction products can be exemplified. (A) Trimethylaluminum and methylboronic acid 2:
(B) 2: 1 reaction product of triisobutylaluminum and methylboronic acid (c) 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid (d) 2: 2 reaction of trimethylaluminum and methylboronic acid
1 Reactant (e) Triethylaluminum and butylboronic acid 2:
1 reactant

As another example of the metallocene catalyst used in the present invention, a specific compound (such as a metallocene-based transition metal compound (component A), which reacts with the component A to form a stable ion). Catalysts in combination with component E) are mentioned. Also in this case, an organic aluminum compound (component C) can be used in combination as an optional component.

The specific compound (E) is an ionic compound formed from an ion pair of a cation and an anion, or an electrophilic compound, and reacts with a metallocene compound to form a stable ion to form a polymerization active species. To form. Among them, the ionic compound is represented by the general formula (8). [Q '] ^{m +} [Y] ^m- (M is an integer of 1 or more) (8) In the formula, Q ′ is a cation component of an ionic compound, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation.
Metal cations and organic metal cations which are themselves easily reduced can also be mentioned. These cations
Not only a cation capable of giving a proton as disclosed in Japanese Patent Publication No.
A cation that does not give a proton may be used. Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, NNdimethylammonium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, Trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, palladium ion, mercury ion, ferro A cerium ion and the like.

Y is an anionic component of an ionic compound, which is a component which reacts with a metallocene compound to form a stable anion, such as an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, and an organic phosphorus compound. Anions, organic arsenic compound anions, organic antimony compound anions and the like can be mentioned. Specifically, tetraphenylboron, tetrakis (3,
4,5-trifluorophenyl) boron, tetrakis (3,5-di (trifluoromethyl) phenyl) boron, tetrakis (3,5- (t-butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron,
Tetraphenylaluminum, tetrakis (3,4,5
-Trifluorophenyl) aluminum, tetrakis (3,5-di (trifluoromethyl) phenyl) aluminum, tetrakis (3,5-di (t-butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, tetraphenylgallium , Tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis (3,5-di (trifluoromethyl) phenyl) gallium, tetrakis (3,5-di (t-butyl)
Phenyl) gallium, tetrakis (pentafluorophenyl) gallium, tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic, tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, decaborate, Undecaborate, carbado decaborate, decachloro decaborate and the like can be mentioned.

As the electrophilic compound, among compounds known as Lewis acid compounds, those which react with a metallocene compound to form stable ions to form polymerization active species, and include various metal halides Examples include compounds and metal oxides known as solid acids. Specific examples include magnesium halides and Lewis acidic inorganic compounds. These catalyst components can be used by being appropriately supported on an inorganic solid carrier, an organic solid carrier, or the like.
Examples of the loading include the methods described in JP-A-61-296008, JP-A-1-101315, JP-A-5-301917, and the like.

<Formation of Catalyst> The metallocene catalyst comprising the components A and B and the component C used if necessary is prepared in the polymerization vessel or outside the polymerization vessel in the presence or absence of the monomer to be polymerized. It can be adjusted by contact. Component A and component D or component E
The same applies to the case of combining. In addition, the catalyst,
Prepolymerization may be performed in the presence of an olefin. As the olefin used for the prepolymerization, propylene, ethylene, 1-butene, 3-methylbutene-
1, styrene, divinylbenzene and the like are used.

<Polymerization> The polymerization of the propylene polymer used in the present invention is carried out by mixing and contacting a metallocene catalyst and a required monomer. The amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio, and to change the mixing ratio of the supplied monomers over time. Is also possible. Further, any of the monomers can be dividedly added in consideration of the copolymerization reaction ratio.

As the polymerization mode, any method can be adopted as long as the catalyst component and each monomer are efficiently contacted. Specifically, a slurry method using an inert solvent, a bulk method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a method in which each monomer is substantially gaseous without substantially using a liquid solvent Can be employed. Further, the present invention is also applied to continuous polymerization and batch polymerization. In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene can be used as a polymerization solvent.

The polymerization conditions are such that the polymerization temperature is from -78 to
The temperature is 160 ° C., preferably 0 to 150 ° C., and hydrogen can be used as a molecular weight regulator at that time. The polymerization pressure is 0 to 90 kg / cm ² · G, preferably 0 to 60 kg / cm ² · G, particularly preferably 1 to 60 kg / cm ² · G.
50 kg / cm ² · G is appropriate.

In the resin material forming the surface layer, other additional components can be further compounded, if necessary, in addition to the propylene-based polymer as long as the effects of the present invention are not significantly impaired. Such additional optional ingredients include antioxidants, light stabilizers used for normal polyolefins,
UV absorbers, lubricants, antistatic agents, anti-fogging agents, crystal nucleating agents, neutralizing agents, metal deactivators, coloring agents, dispersants, peroxides, fillers, optical brighteners, and the above propylene-based Resins other than polymers, elastomers and the like can be mentioned.

(2) Internal Layer In the present invention, the resin material constituting the internal layer is not particularly limited, and any of the materials used in ordinary polyolefin sheet materials can be used.
In order to obtain the above-mentioned desired flexibility and transparency, it is preferable to use a polymer mainly composed of an ethylene-α-olefin random copolymer.

Here, the α-olefin which is a comonomer of the ethylene-α-olefin random copolymer preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and particularly preferably 6 to 6 carbon atoms. 10 things. Specifically, propylene, butene-1, pentene-
1, hexene-1, octene-1, heptene-2, 4-
Methyl-pentene-1, 4-methyl-hexene-1,
4,4-dimethylpentene-1 and the like can be mentioned.

In the ethylene-α-olefin random copolymer, a preferable ratio of a structural unit derived from ethylene (hereinafter referred to as “ethylene unit”) is 5% of all the structural units.
0-98% by weight, more preferably 60-95% by weight, particularly preferably 70-90% by weight, and the preferred proportion of comonomer units derived from α-olefin is 2-5%.
0% by weight, more preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight.

The above ethylene-α-olefin random copolymer
The polymer is measured according to JIS-K7112 (23 ° C).
The specified density is preferably 0.860 to 0.910 g /
cm ^Three, More preferably 0.870 to 0.908 g / c.
m^Three, More preferably 0.875 to 0.906 g / c.
m^ThreeIt is. Insufficient flexibility when density exceeds the above range
However, if the density falls below the above range, bleeding of low crystalline components will occur.
It is not preferable because it easily occurs.

The ethylene-α-olefin random copolymer is JIS-K7210 (190 ° C., 2.
MFR measured in conformity with 16 kg load) is 1 to 5
0 g / 10 min, preferably 1.5 to 40 g / 10 min, more preferably 2 to 35 g / 10 min. If the MFR exceeds the above range, the viscosity becomes low, drawdown tends to occur during the formation of the laminated sheet, and the stability is insufficient.
On the other hand, if the MFR is lower than the above range, poor flow will occur at the time of forming the laminated sheet, and the thickness will fluctuate.

Such ethylene-α- used in the present invention
The olefin random copolymer can be produced using a known catalyst such as a Ziegler catalyst, a chromium-based catalyst, or a metallocene-based catalyst. Among them, those obtained by copolymerizing ethylene as a main component and α-olefin as a subcomponent using a metallocene catalyst as in the case of the propylene polymer in the surface layer are particularly preferable. When both the surface layer and the inner layer are produced using a metallocene compound, it is estimated that the Q values of the produced polymers are close to each other, so that the adhesiveness and the moldability are improved.

Examples of the method of copolymerization using these catalysts include a gas phase method, a slurry method, a high pressure ionic polymerization method, a solution method and the like, and the ethylene-α-olefin random copolymer of the present invention can be used. In order to obtain the density range described above, a high-pressure ion polymerization method or a solution method is suitable.

The adhesion between the surface layer and the inner layer of the polyolefin-based laminated soft sheet of the present invention is not particularly problematic when the sheet is used as it is, but when the sheets are adhered to each other by heat sealing or the like, stronger adhesion is obtained. Adhesion between layers is required. In order to improve such interlayer adhesion,
As the resin material constituting the inner layer, it is preferable to use a resin composition comprising the following components (A) and (A).

(A) Ethylene-α-olefin random copolymer having MFR of 1 to 10 g / 10 min, preferably 1.5 to 8 g / 10 min: 100 parts by weight (a) MFR of 11 to 50 g / 10 min , Preferably 12
４０40 g / 10 min ethylene-α-olefin random copolymer: 10 to 200 parts by weight

Here, if the MFR of the component (A) exceeds the above range, the viscosity becomes low and drawdown tends to occur during the formation of a laminated sheet, resulting in insufficient stability. On the other hand, M
When the FR is less than the above range, the thickness of the laminated sheet is fluctuated due to poor flow during molding. Also, the MFR of the component (a)
Exceeds the above range, the amount of low-viscosity components increases, causing bleeding problems. If the MFR is below the above range, improvement in adhesion between the surface layer and the inner layer cannot be achieved.

The mixing ratio of each component of the resin composition is as follows:
(A) is 10 to 200 with respect to 100 parts by weight of (A) component.
Parts by weight. If the amount of (a) exceeds the above range,
The viscosity becomes low, drawdown during molding of the laminated sheet is apt to occur, and the stability is insufficient. On the other hand, if it is less than the above range, improvement in the adhesion between the surface layer and the inner layer cannot be achieved.

The resin material for forming the internal layer may contain ethylene-α as long as the effects of the present invention are not significantly impaired.
-In addition to the olefin random copolymer, other additional components can be further compounded as required. Such additional optional components include antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, antifogging agents, crystal nucleating agents, neutralizing agents, metal salts used for ordinary polyolefins. Activators, colorants, dispersants, peroxides, fillers, optical brighteners,
And resins and elastomers other than the propylene-based polymer.

(3) Laminated Structure The laminated polyolefin flexible sheet of the present invention has, as essential layers, an inner layer made of the above resin material and a total of two surface layers provided on both surface sides of the inner layer. It is a laminate.

Regarding the preferable thickness of the sheet, the total sheet thickness is 0.1 to 3 mm, more preferably 0.1 to 3 mm.
2 mm, and the total thickness of the two surface layers on both surface sides is preferably 2 to 40%, more preferably 3 to 35%, based on the total sheet thickness. If the total thickness of the surface layer exceeds the above range, the flexibility is insufficient, and if the total thickness is below the above range, it becomes difficult to control the thickness during sheet molding, which is not preferable. The scale of flexibility can be expressed by a tensile modulus in accordance with JIS-K7127. In the sheet of the present invention, the tensile modulus in the machine direction (MD) and the transverse direction (TD) is 200MPa or less, preferably 150M
Pa or less.

In the polyolefin laminated soft sheet of the present invention, the melt viscosity ratio of the resin material forming the inner layer to the resin material forming the surface layer is preferably 1 or more, more preferably 1.5 or more. Here, the melt viscosity ratio is a value represented by the following equation.

Melt viscosity ratio = V2 / V1 V1: Melt viscosity of resin material forming surface layer V2: Melt viscosity of resin material forming inner layer

The term “melt viscosity” as used in the present invention refers to
It is a melt viscosity (poise) measured using a Toyo Seiki Seisakusho Capillograph 1B at a temperature of 230 ° C., a capillary L / D of 10 mm / 1 mm, and a piston extrusion speed of 10 mm / min.

When the melt viscosity ratio (V2 / V1) falls below the above range, the surface of the laminated sheet becomes rough, resulting in poor appearance and impaired value as a product. The difference (absolute value) between the Q value of the propylene-based polymer constituting the surface layer and the Q value of the ethylene / α-olefin copolymer constituting the inner layer may be selected to be 1.5 or less. preferable. The method for producing the polyolefin-based laminated soft sheet of the present invention is not particularly limited, and a normal processing method can be employed. For example, T-die method, inflation method,
A co-extrusion molding machine such as a calender roll method can be used.

A more specific example will be described with a co-extrusion T-die molding machine. The resin material of the present invention is charged into the extruder of each layer, and heated and melted and kneaded at a temperature of 190 to 270 ° C. Laminated with a road adjuster, extruded in the form of a film from the die lip of the T die, air knife method, air chamber method, polishing roll method, swing roll method,
A desired laminated sheet can be manufactured by squeezing and cooling the laminated molten film sheet by a belt casting method, a water cooling method, or the like, and then taking it by a take-off machine.

In the polyolefin-based laminated soft sheet of the present invention, as a layer constitution, other layers besides the above-mentioned essential layers can be added if necessary within a range not to impair the effects of the present invention. Other layers that can be added include a layer made of a recycled resin, a gas barrier resin, an adhesive resin, and the like.

In the polyolefin-based laminated soft sheet of the present invention, various additives and resins can be applied to the surface of the surface layer. Examples of the material to be applied include an antistatic agent, a lubricant, an antifogging agent, and various urethane-based resins. Thus, the tensile modulus is 200MP
a, the haze per 100 μm thickness is 1.5% or less, the surface roughness is 25 nm or less, and the surface gloss is preferably 1 or less.
A polyolefin-based laminated soft sheet of 15% or more can be obtained.

[0078]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention.

Example 1 Propylene-ethylene-random copolymer having a content of ethylene units of 2.4% by weight, a density of 0.900 g / cm ³ and an MFR of 6 g / 10 minutes polymerized using a metallocene catalyst was used. The polymer was used as the resin material for the surface layer. Various physical properties of this resin material were as follows. Melt viscosity: 5277 poise, Durometer hardness: 64 Weight average molecular weight Mw: 232,000, Number average molecular weight M
n: 83,700, Q value: 2.78

Further, the density obtained by polymerization using the metallocene catalyst is 0.898 g / cm ³ , and the MFR is 2.2 g / l.
An ethylene-hexene-1 random copolymer (Kernel-KF260, manufactured by Nippon Polychem Co., Ltd.) having a hexene content of 18.5% by weight for 0 minutes was used as the resin material for the inner layer. Various physical properties of this resin material were as follows. Melt viscosity: 12,750 poise, durometer hardness:
40 weight average molecular weight Mw: 80,300, number average molecular weight M
n: 35,500, Q value: 2.26

Then, the resin material for the inner layer was put into both surface layer sides of a feed block having two and three layers composed of an extruder having a screw diameter of 45 mm heated to 230 ° C. Screw diameter 65mm
From the extruder to the inner layer side of the feed block. These are extruded into a sheet shape by a T-die having a width of 500 mm heated to 230 ° C., and sandwiched between two mirror-finished rolls (hard chrome plated) having cooling water at 20 ° C. circulating therein, and cooled and solidified. Then, the sheet was taken out to obtain a laminated sheet. The thickness of the laminated sheet was 50 μm for both surface layers and 500 μm for the inner layer, and the total sheet thickness was 600 μm in total.

The external appearance of this sheet was visually observed, and the surface roughness (center line average roughness Ra) according to JIS-B0601, the tensile modulus according to JIS-K7127, and the tensile modulus according to JIS-K7105. Haze, JIS-K
The surface gloss was measured in accordance with 7105. Further, two sheets of this sheet are stacked, and the seal width is 5 mm, the temperature is 190 ° C., the time is 2 seconds, the pressure is 2 kg / c by a heat sealer.
Adhesion was performed under the conditions of m ² , and the state of peeling off by hand was evaluated as interlayer adhesion according to the following criteria. Table 1 shows the results.

(Interlayer adhesion) X: easily peeled off. ：: There is considerable resistance for peeling. A: The base material is cut without peeling.

Example 2 Example 1 was repeated except that the resin materials shown in Table 1 were used for the surface layer and the inner layer.
A sheet was manufactured and evaluated in the same manner as described above. Table 1 shows the results.

Comparative Examples 1 and 2 Sheets were produced and evaluated in the same manner as in Example 1 except that the resin materials shown in Table 2 were used for the surface layer and the inner layer. Table 2 shows the results.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

The polyolefin laminated soft sheet of the present invention is a soft sheet having good surface appearance and high flexibility, transparency and surface hardness, and a soft sheet having all of these physical properties has been achieved conventionally. It was not possible. Further, by selecting a resin material, the interlayer adhesion of each layer can be remarkably improved.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AK01C AK07A AK07B AK62C AK66A AK66B BA03 BA06 BA10A BA10B BA25 EH232 GB15 JA06A JA06B JA06C JA13A JA13B JA13C JK07 JK12A JK12B JK15 JN01 YNYY00Y00

Claims (12)

[Claims] 1. A laminated sheet having at least an inner layer as a constituent layer and a surface layer provided on both surface sides of the inner layer, wherein the surface layer is produced using a metallocene catalyst and has a Q value. 1.5-3.5, Durometer hardness is 60
A polyolefin-based laminated soft sheet formed of the above propylene-based polymer and having a tensile modulus of 200 MPa or less, a haze per 100 μm thickness of 1.5% or less, and a surface roughness of 25 nm or less. 2. The propylene polymer constituting the surface layer,
MFR of 1 at a density of 0.880 to 0.905 g / cm ³
2. The polyolefin-based laminated soft sheet according to claim 1, wherein the weight is from 50 g / 10 min. 3. The propylene polymer constituting the surface layer,
The polyolefin laminate soft sheet according to claim 1 or 2, wherein the melt viscosity is from 4,500 to 8,000 poise. 4. The propylene polymer constituting the surface layer,
A propylene / α-olefin copolymer.
3. The polyolefin-based laminated soft sheet according to any one of 3. 5. The sheet has a haze of 1.2% or less per 100 μm thickness and a surface roughness of 20 nm or less.
5. The polyolefin-based laminated soft sheet according to any one of items 4 to 4. 6. The polyolefin according to claim 1, wherein the inner layer is produced using a metallocene catalyst and is an ethylene / α-olefin copolymer having a Q value of 1.5 to 3.5. Series laminated soft sheet. 7. Density of ethylene / α-olefin copolymer
Is 0.860 to 0.910 g / cm ^ThreeMFR is 1-5
The pouring amount according to any one of claims 1 to 6, which is 0 g / 10 minutes.
Reolefin-based laminated soft sheet. 8. The Q of the propylene polymer constituting the surface layer
The difference (absolute value) between the value and the Q value of the ethylene / α-olefin copolymer constituting the inner layer is 1.5 or less.
7. The laminated polyolefin-based flexible sheet according to any one of 7. 9. The thickness of all sheets is 0.1 to 3 mm,
The polyolefin laminate soft sheet according to any one of claims 1 to 8, wherein the total thickness of the surface layers provided on both surface sides is 2 to 40% with respect to the total sheet thickness. 10. The polyolefin laminated soft sheet according to claim 1, wherein the sheet has a surface gloss of 115% or more. 11. The melt viscosity V of a resin material forming an inner layer.
The polyolefin laminate soft sheet according to any one of claims 1 to 10, wherein a ratio (V2 / V1) of 2 to a melt viscosity V1 of the resin material forming the surface layer is 1 or more. 12. A laminated sheet having at least an inner layer as a constituent layer and surface layers provided on both surface sides of the inner layer, wherein the surface layer is produced using a metallocene catalyst and has a Q value of at least one. 1.5-3.5, durometer hardness is 6
0 or more propylene-based polymer, the inner layer is manufactured using a metallocene catalyst, and has a Q value of 1.5
-3.5-3.5 ethylene-α-olefin copolymer, the sheet has a tensile modulus of 200 MPa or less,
A polyolefin-based laminated soft sheet having a haze per 100 μm thickness of 1.5% or less, a surface roughness of 25 nm or less, and a surface gloss of 115% or more.