JPH10286918A - Laminate sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a composition having excellent moldability such as thermal molding, vacuum molding or pressure molding and high melting tension by laminating a layer made of specific amount of polypropylene composition made of specific olefin (co)polymer and polypropylene, a print layer and polypropylene layer thereon. SOLUTION: The laminate sheet is obtained by adhering a layer made of polypropylene composition made of 0.01 to 5 pts.wt. of olefin(co)polymer having intrinsic viscosity [ηE] of 15 to 100 dl/g measured in tetraphosphorus at 135 deg.C and 100 pts.wt. of polypropylene, a print layer executed on the layer and a layer made of polypropylene indicated next. Here, the polypropylene is made of propylene-olefin copolymer containing 50 wt.% or more of propylene sole polymer or propylene polymer unit with 0.2 to 10 dl/g of intrinsic viscosity [ηP] measured in tetraphosphorus at 135 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated sheet excellent in formability such as thermoforming, vacuum forming, pressure forming and the like.

[0002]

2. Description of the Related Art Polypropylene is widely used in various molding fields because it has excellent mechanical properties, chemical resistance and the like, and is extremely useful in balance with economic efficiency. As a method for increasing the melt tension of polypropylene, a method in which a polypropylene is reacted with an organic peroxide and a crosslinking aid in a molten state (JP-A-59-93711, JP-A-59-93711).
JP-A 1-152754), a method of reacting a semi-crystalline polypropylene with a peroxide having a low decomposition temperature in the absence of oxygen to obtain a gel-free polypropylene having free-end long-chain branches (Japanese Unexamined Patent Publication No. 298536) and the like.

As other methods for improving the melt viscoelasticity such as the melt tension, there have been proposed a composition containing polyethylene or polypropylene having different intrinsic viscosities or molecular weights, and a method for producing such a composition by multi-stage polymerization. Have been.

For example, ultra high molecular weight polypropylene 2
A method in which 30 parts by weight is added to 100 parts by weight of ordinary polypropylene and extruded in a temperature range from the melting point to 210 ° C. (Japanese Patent Publication No. 61-28694), wherein the intrinsic viscosity ratio obtained by the multistage polymerization method is 2 or more. Extruded sheet made of two-component polypropylene with different
No. 70), polyethylene having a high viscosity average molecular weight of 1 to
A method in which a polyethylene composition containing 10% by weight and comprising three kinds of polyethylenes having different viscosity average molecular weights is produced by a melt-kneading method or a multi-stage polymerization method (Japanese Patent Publication No. Sho 62-118).
JP-A-61057), using a highly active titanium-vanadium solid catalyst component and a limiting viscosity of 20 d by a multistage polymerization method.
1 / g or more of ultra-high molecular weight polyethylene to polymerize 0.05 to less than 1% by weight of polyethylene (Japanese Patent Publication No. 5-79683), 1-butene and 4-methyl-
Using a highly active titanium catalyst component prepolymerized with 1-pentene, a multistage polymerization method using a specially arranged polymerization reactor is used to convert ultrahigh molecular weight polyethylene having an intrinsic viscosity of 15 dl / g or more to 0.1 to 5% by weight. A polymerization method of polyethylene to be polymerized (Japanese Patent Publication No. 7-8890) and the like are disclosed.

Further, by polymerizing propylene using a prepolymerized catalyst in which ethylene and a polyene compound are prepolymerized to a supported titanium-containing solid catalyst component and an organoaluminum compound catalyst component, a polypropylene having a high melt tension is produced. (Japanese Unexamined Patent Publication No. 5-22212)
No. 2) and a prepolymerization using ethylene alone using the same catalyst component and an ethylene / α-olefin copolymer having a high melt tension using an ethylene-containing prepolymerization catalyst containing a polyethylene having an intrinsic viscosity of 20 dl / g or more. A method for manufacturing a united product (Japanese Patent Laid-Open No. 5-5410) is disclosed.

[0006]

In the above-mentioned various compositions and their production methods, although the melt tension of the polyolefin is improved to some extent,
The temperature dependency of the melt tension is large, and when heated to a temperature equal to or higher than the melting point, the melt viscosity is rapidly reduced and the melt tension is also significantly reduced, so that the formability of a sheet using this composition is reduced.

In a multi-stage polymerization method in which a process for producing a high-molecular-weight polyolefin is incorporated into a usual propylene (co) polymerization process in the main polymerization, an olefin (co-) is used to form a trace amount of the high-molecular-weight polyolefin.
It is difficult to control the amount of polymerization very small, and sometimes a low polymerization temperature is required to produce a polyolefin having a sufficiently large molecular weight.
Furthermore, the productivity of the final polypropylene composition is reduced.

In the method of prepolymerizing a polyene compound, it is necessary to separately prepare a polyene compound,
Further, when propylene is polymerized based on a document that discloses a method of prepolymerizing polyethylene, the dispersibility of the prepolymerized polyethylene in the finally obtained polypropylene composition is non-uniform, and the stability of the polypropylene composition is Further improvement is required in terms of aspects. This document also states that
Although the polymerization of 1-butene is specifically described, the (co) polymerization of propylene is not specifically described. As mentioned above, in the prior art, polypropylene is insufficient in improving its melt tension,
In addition, when producing such polypropylene, it is required to improve the productivity. TECHNICAL FIELD The present invention relates to a laminated sheet using a polypropylene composition having a high melt tension and excellent in moldability such as thermoforming, vacuum forming, and pressure forming.

[0009]

Means for Solving the Problems The present invention provides the following (1) to
It has the configuration of (4). (1) The present invention relates to the following olefin (co) polymer (a)
0.01 to 5 parts by weight, and polypropylene (b) 10
A laminated sheet comprising a layer composed of 0 parts by weight of a polypropylene composition (x), a printed layer formed on the layer, and a layer composed of the following polypropylene (b) laminated and bonded. (A) Intrinsic viscosity [η measured in tetralin at 135 ° C.
_[E ] is 15 to 100 dl / g. (B) a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units, having an intrinsic viscosity [η _P ] of 0.2 to 10 dl / g measured in tetralin at 135 ° C. Some polypropylene.

(2) The polypropylene composition (x) has a log (MS)> 4 between the melt tension (MS) at 230 ° C. and the intrinsic viscosity [η _T ] measured in tetralin at 135 ° C. The laminated sheet according to the above (1), having a relationship represented by 24 × log [η _T ] −1.05.

(3) The olefin (co) polymer (a) is
The laminated sheet according to the above (1), which is an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymerized units.

(4) Polypropylene (b) has a melting point of 16
0 ° C to 125 ° C, α-olefin content is 2 to 8% by weight
The laminated sheet according to the above (1), which is a propylene-α-olefin copolymer contained.

As used herein, the term "olefin (co) polymer" refers to a homopolymer of an olefin having 2 to 12 carbon atoms and an olefin in which the polymerization unit of one of these olefins is 50% by weight or more. Meaning a random copolymer, the term "polypropylene" means a propylene homopolymer and a propylene-olefin random copolymer and a propylene-olefin block copolymer containing 50% by weight or more of propylene polymer units,
The term "polyethylene" refers to an ethylene homopolymer and an ethylene-containing polymer containing at least 50% by weight of ethylene polymerized units.
It means an olefin random copolymer and an ethylene-olefin block copolymer.

The olefin (co) polymer constituting the component (a) of the polypropylene composition (x) of the present invention is 13
The intrinsic viscosity [η _E ] measured in tetralin at 5 ° C. is 15 to
An olefin (co) polymer of 100 dl / g may be used.
Ethylene-olefin random copolymer containing at least 70% by weight of ethylene-olefin random copolymer, preferably ethylene homopolymer or ethylene-polymerized random copolymer containing ethylene polymer unit content of at least 70% by weight, particularly preferably ethylene homopolymer or ethylene polymer. Suitable are ethylene-olefin random copolymers containing at least 90% by weight of units, and these (co) polymers may be used alone or in admixture of two or more.

If the intrinsic viscosity [η _E ] of the olefin (co) polymer of the component (a) is less than 15 dl / g, the resulting polypropylene composition will have insufficient melt tension and crystallization temperature. The upper limit of the intrinsic viscosity [η _E ] is not particularly limited, but if the intrinsic viscosity [η _P ] difference from the polypropylene of the component (b) is large, the component (b) may be added to the polypropylene in the composition. Dispersion of the olefin (co) polymer of the component (a) becomes poor, and as a result, the melt tension does not increase. Furthermore, the upper limit is 10 in terms of manufacturing efficiency.
It is good to be about 0 dl / g. The intrinsic viscosity [η _E ] of the olefin (co) polymer of the component (a) measured in tetralin at 135 ° C. is 15 to 100 dl / g, preferably 17 to 100 dl / g.
dl / g to 50 dl / g. In addition, the olefin (co) polymer of the component (a) needs to have a high intrinsic molecular weight [η _E ] measured in tetralin at 135 ° C. of up to 15 dl / g. It is preferable that the ethylene polymerization unit is 50% by weight or more.

The olefin constituting the olefin (co) polymer of the component (a) is not particularly limited, but an olefin having 2 to 12 carbon atoms is preferably used. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, and the like. The olefin may be not only one kind but also two or more kinds.

The density of the olefin (co) polymer of the component (a) is not particularly limited.
g / l to 980 g / l are preferred.

The polypropylene (b), which is another component of the polypropylene composition (x) used in the present invention, has an intrinsic viscosity [η] measured in tetralin at 135 ° C.
_P ] is 0.2 to 10 dl / g of a crystalline polypropylene, a propylene homopolymer or a propylene-olefin random copolymer or a propylene-olefin block copolymer containing 50% by weight or more of propylene polymer units. Preferably, it is a propylene homopolymer, a propylene-olefin random copolymer having a propylene polymer unit content of 90% by weight or more, or an ethylene-olefin block copolymer having a propylene polymer unit content of 70% by weight or more. These (co) polymers may be not only one kind but also a mixture of two or more kinds.

The intrinsic viscosity [η _P ] of the polypropylene (b) is 0.2 to 10 dl / g, preferably 0.5 dl / g.
/ G to 8 dl / g. When the intrinsic viscosity [η _P ] of the polypropylene as the component (b) is less than 0.2 dl / g, the moldability of the obtained sheet is deteriorated, and 10 dl.
/ G also deteriorates the moldability of the obtained sheet.

The olefin other than propylene copolymerized with propylene constituting the polypropylene of the component (b) is not particularly limited, but an olefin having 2 to 12 carbon atoms is preferably used. Specifically, ethylene, 1
-Butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, and the like. It may be the above.

The stereoregularity of the component (b) polypropylene is not particularly limited, and any polypropylene that achieves the object of the present invention may be used as long as it is a crystalline polypropylene. Specifically, the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR (nuclear magnetic resonance spectrum) is preferably 0.80 to 0.99, more preferably 0.85 to 0.99, and particularly preferably 0.85 to 0.99. Preferably 0.
90 to 0.99 are used.

Isotactic pentad fraction (mmm
m) refers to ¹³ C-NMR proposed by A. Zambelli et al. (Macromolecules 6, 925 (1973)).
Is the isotactic fraction in pentad units in the polypropylene molecular chain, as determined by the following method.
(A. Zambelli) et al. (Macromolecules 8, 687
(1975)). In particular,
Using a mixed solution of o-dichlorobenzene / bromide benzene = 8/2 weight ratio with a polymer concentration of 20% by weight, 67.20.
It is determined by measuring at 130 MHz. As a measuring device, for example, JEOL-GX270
An NMR measurement device (manufactured by JEOL Ltd.) is used.

The polypropylene composition (x) used in the present invention is used in an amount of 0.01 to 5 parts by weight, preferably 0.02 to 5 parts by weight, of the olefin (co) polymer of the component (a).
2 parts by weight, particularly preferably 0.05 to 1 part by weight,
And 100 parts by weight of the component (b) polypropylene. When the amount of the olefin (co) polymer of the component (a) is 0.0
If the amount is less than 1 part by weight, the effect of improving the melt tension of the obtained polypropylene composition is small, and if it exceeds 5 parts by weight, the effect is saturated and the homogeneity of the obtained polypropylene composition may be impaired. Not preferred.

The melt tension of the polypropylene composition (x) used in the present invention is 230 ° C. (M)
S) and intrinsic viscosity [η] measured in tetralin at 135 ° C.
_T ] and log (MS)> 4.24 × log [η _T ] −1.05. The upper limit is not particularly limited, but if the melt tension is too high, the fluidity of the composition deteriorates. Therefore, preferably, 4.24 × log [η _T ] +0.50> log (MS)> 4.24 × log [η _T ]
−1.05, more preferably 4.24 × log [η _T ] +0.24> log (MS)> 4.24 × log [η _T ]
−1.05, most preferably 4.24 × log [η _T ] +0.24> log (MS)> 4.24 × log [η _T ]
Satisfies the relationship shown by −0.93.

Here, the melt tension at 230 ° C. (M
S), using a melt tension tester type 2 (manufactured by Toyo Seiki Seisaku-sho, Ltd.), the polypropylene composition was heated to 230 ° C. in the apparatus, and the molten polypropylene composition was heated from a 2.095 mm diameter nozzle to 20 mm / 2 at the speed of a minute
It is a value (unit: cN) obtained by measuring the tension of the filamentous polypropylene composition when the strand is extruded into the air at 3 ° C. to form a strand and the strand is taken off at a speed of 3.14 m / min.

As a method for producing the polypropylene composition (x) used in the present invention, any production method may be adopted as long as the melt tension of the composition falls within the above range. An example is a method in which propylene or propylene and other olefins are subjected to main (co) polymerization in the presence of a catalyst which has been preactivated by an olefin.

The term “method” refers to a transition metal compound catalyst component containing at least a titanium compound, and a periodic table of elements of 0.01 to 1,000 mol per mol of transition metal atom (1991).
Year edition) 0 to 500 based on 1 mole of an organometallic compound (AL1) and a transition metal atom of a metal selected from the group consisting of metals belonging to Group 1, Group 2, Group 12 and Group 13.
A catalyst for producing a polyolefin comprising a combination of a molar electron donor (E1), and 0.01 to 100 g of 13 per 1 g of a transition metal compound component supported on the catalyst.
The intrinsic viscosity [η _B ] measured in tetralin at 5 ° C. is 15d
1 / g of polypropylene (B) for the purpose of main (co) polymerization and 0.0 g / g of the catalyst component of the transition metal compound
Propylene alone or propylene in the presence of a preactivated catalyst consisting of polyethylene (A) having an intrinsic viscosity [η _A ] of 15 dl / g to 100 dl / g measured in tetralin at 135 ° C. of 1 to 5,000 g. And carbon number 2-1
(2) main (co) polymerization of the olefin (2).

As used herein, the term "pre-activation" refers to the activity of the polyolefin-producing catalyst for increasing the molecular weight of propylene or the (co)
This means that the olefin is pre-activated before the polymerization is carried out, and the olefin is preactivated (co) polymerized in the presence of a catalyst for producing a polyolefin and supported on the catalyst.

The preactivated catalyst used in the method is a catalyst component of a transition metal compound containing at least a titanium compound, and 0.01 to 1,000 mol of the periodic table (1991 edition) of 1 to 1 mol per mol of transition metal atom. Organometallic compound (AL1) of a metal selected from the group consisting of metals belonging to Group 2, Group 12, Group 12 and Group 13, and 0 to 500 moles of an electron donor (E1 ), A catalyst for producing polyolefin comprising a combination of
0.0 g / g of the transition metallization synthesis component supported on this catalyst
1 to 100 g of polypropylene (B) for intrinsic (co) polymerization having intrinsic viscosity [η _B ] of less than 15 dl / g measured in tetralin at 135 ° C., and about 0.01 to 5000 g per 1 g of transition metal compound catalyst component Has an intrinsic viscosity [η _A ] of 15 to 100 d measured in tetralin at 135 ° C.
1 / g of polyethylene (A).

In the preactivated catalyst, as the transition metal compound catalyst component, any known catalyst component mainly composed of a transition metal compound catalyst component containing at least a titanium compound proposed for producing a polyolefin is used. Among them, a titanium-containing solid catalyst component is preferably used for industrial production.

As the titanium-containing solid catalyst component, a titanium-containing solid catalyst component containing a titanium trichloride composition as a main component (JP-B-56-3356, JP-B-59-2857)
No. 3, JP-B-63-66323, and the like, and a titanium-containing supported catalyst component in which titanium tetrachloride is supported on a magnesium compound and titanium, magnesium, halogen, and an electron donor are essential components (Japanese Patent Application Laid-Open No. Sho 62-63). -10481
0, Japanese Patent Application Laid-Open No. 62-104811, Japanese Patent Application Laid-Open
JP-A-2-104812, JP-A-57-63310, JP-A-57-63311, JP-A-58-83
006, JP-A-58-138712, etc.), and any of these can be used.

As the organometallic compound (AL1), an organic group of a metal selected from the group consisting of metals belonging to Groups 1, 2, 12, and 13 of the Periodic Table of the Elements (1991). Compounds having, for example, an organic lithium compound, an organic sodium compound, an organic magnesium compound, an organic zinc compound, an organic aluminum compound,
The transition metal compound can be used in combination with the catalyst component.

In particular, the general formula is AlR ¹ _p R ² _q X _{3- (p + q)}
(Wherein R ¹ and R ² are an alkyl group, a cycloalkyl group,
X represents a halogen atom, and p and q each represent a positive number of 0 <p + q ≦ 3. )) Can be suitably used.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-i-aluminum. Hexyl aluminum, trialkyl aluminum such as tri-n-octyl aluminum, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-i
-Dialkylaluminum monohalides such as butylaluminum chloride, diethylaluminum bromide and diethylaluminum iodide; dialkylaluminum hydrides such as diethylaluminum hydride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; monoalkylaluminum dihalides such as ethylaluminum dichloride. Other examples include alkoxyalkylaluminums such as diethoxymonoethylaluminum. Preferably, trialkylaluminum and dialkylaluminum monohalide are used. These organoaluminum compounds can be used alone or in combination of two or more.

In the production of the polypropylene composition (x) used in the present invention, the electron donor (E1) is used as needed for the purpose of controlling the production rate and / or stereoregularity of the polyolefin. Examples of the electron donor (E1) include ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates, and azo compounds. , Phosphines, phosphites, phosphinites, hydrogen sulfide and thioethers, organic compounds having any atom of oxygen, nitrogen, sulfur, phosphorus in the molecule such as neoalcohols and silanols and Si- An organic silicon compound having an OC bond is exemplified.

As ethers, dimethyl ether,
Diethyl ether, di-n-propyl ether, di-n
-Butyl ether, di-i-amyl ether, di-n-
Pentyl ether, di-n-hexyl ether, di-i
-Hexyl ether, di-n-octyl ether, di-i
-Octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like, alcohols such as methanol,
Ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, etc., and phenols such as phenol, cresol, xylenol, ethyl phenol, naphthol, etc. . Esters include methyl methacrylate, methyl formate, methyl acetate,
Methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate, i-propyl acetate, butyl formate, amyl acetate,
N-butyl acetate, octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate,
2-ethylhexyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate,
Monocarboxylic esters such as methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate, diethyl succinate, diethyl methylmalonate, diethyl butylmalonate, maleic acid Dibutyl, aliphatic polycarboxylic acid esters such as diethyl butyl maleate,
Monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-n-phthalate
Butyl, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, -di-ethyl phthalate,- dipropyl i-phthalate, dibutyl i-phthalate, di-2-ethylhexyl i-phthalate, diethyl terephthalate, dipropyl terephthalate,
Dibutyl terephthalate, di-i-naphthalenedicarboxylic acid
And aromatic polycarboxylic esters such as -butyl. Aldehydes include acetaldehyde, propionaldehyde, benzaldehyde, etc. as carboxylic acids, monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, benzoic acid, and anhydride. Acid anhydrides such as benzoic acid, phthalic anhydride and tetrahydrophthalic anhydride are used as ketones such as acetone, methyl ethyl ketone, methyl-
Examples thereof include i-butyl ketone and benzophenone.

Examples of the nitrogen-containing compound include nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, , 4,6-trimethylpyridine, 2,2,5,6-tetramethylpiperidine,
2,2,5,5, tetramethylpyrrolidine, N, N, N
^{', N'} - tetramethylethylenediamine, aniline,
Amines such as dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ^' , N ^' , N ^" -
Pentamethyl -N ^{'-.beta.-dimethylaminomethyl} phosphoric acid triamide, amides such as octamethyl pyro ^{phosphoramide, N, N, N',} N '- ureas such as tetramethylurea, phenyl isocyanate, toluyl isocyanate or the like Examples include azo compounds such as isocyanates and azobenzene.

Examples of the phosphorus-containing compound include phosphines such as ethyl phosphine, triethyl phosphine, tri-n-octyl phosphine, triphenyl phosphine, and triphenyl phosphine oxide; dimethyl phosphite;
Phosphines such as di-n-octyl phosphine, triphenyl phosphine and triphenyl phosphine oxide, dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite and triphenyl phosphite; Phosphites are exemplified.

Examples of the sulfur-containing compound include thioethers such as diethylthioether, diphenylthioether and methylphenylthioether, ethylthioalcohol,
thioalcohols such as n-propylthioalcohol and thiophenol; and further, as an organosilicon compound, trimethylsilanol, triethylsilanol,
Silanols such as triphenylsilanol, trimethylmethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, diisopropyl Dimethoxysilane, diisobutyldimethoxysilane, diphenyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, vinyltriacetoxysilane, cyclopentylmethyl Dimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane Emissions, cyclohexylmethyl dimethoxysilane, cyclohexyl trimethoxysilane, dicyclohexyl dimethoxysilane, organic silicon compounds having Si-O-C bonds, such as 2-norbornyl methyl dimethoxysilane and the like. These electron donors can be used alone or in combination of two or more.

In the preactivated catalyst, the polyethylene (A) has an intrinsic viscosity [η _A ] of 15 to 100 dl / g, preferably 17 to 50, measured in tetralin at 135 ° C.
dl / g of ethylene homopolymer or ethylene polymerized unit is 50% by weight or more, preferably 70% by weight or more,
More preferably, it is a copolymer of 90% by weight or more of ethylene and an olefin having 3 to 12 carbon atoms, and finally constitutes the polyethylene as the component (a) of the polypropylene composition (x) of the first invention. . Therefore, the intrinsic viscosity [η _E ] of the polyethylene (a) and the intrinsic viscosity [η _A ] of the polyethylene (A) have a relationship of [η _E ] = [η _A ].

The supported amount of polyethylene (A) per g of the transition metal compound catalyst component is 0.01 to 5,000 g, preferably 0.05 to 2,000 g, and more preferably 0.1 to 1,000 g. If the amount supported per 1 g of the transition metal compound catalyst component is less than 0.01 g, the effect of improving the melt tension of the polypropylene composition finally obtained by the present (co) polymerization is insufficient, and if it exceeds 5,000 g. However, not only the improvement of these effects is not remarkable, but also the homogeneity of the finally obtained polypropylene composition may be deteriorated.

On the other hand, polypropylene (B) has a temperature of 135 ° C.
Has an intrinsic viscosity [η _B ] of 15 dl /
It is a polypropylene having the same composition as the polypropylene of the component (b) for the purpose of main (co) polymerization smaller than g, and is finally incorporated as a part of the polypropylene of the component (b) of the polypropylene composition of the first invention. The polyolefin (B) is a component that imparts dispersibility to the finally obtained polypropylene composition of the polyethylene (A),
In this sense, the intrinsic viscosity [η _B ] is preferably smaller than the intrinsic viscosity [η _A ] of the polyethylene (A) and larger than the intrinsic viscosity [η _T ] of the finally obtained polypropylene composition.

On the other hand, the amount of the polypropylene (B) supported per gram of the transition metal compound catalyst component is 0.01 to 100.
g, in other words, the range of 0.001 to 1% by weight based on the finally obtained polypropylene composition (x) is suitable. If the supported amount of the polypropylene (B) is small, the dispersibility of the polyethylene (A) in the target polypropylene composition becomes insufficient, and if too large, the dispersibility of the polyethylene (A) in the polypropylene composition becomes saturated. In addition, the production efficiency of the preactivated catalyst is reduced.

In the present invention, the preactivated catalyst is a polyolefin production catalyst comprising a combination of the above-mentioned transition metal compound catalyst component containing at least a titanium compound, an organometallic compound (AL1) and an electron donor (E1) used as desired. In the presence of a catalyst for use, the polypropylene for the purpose of (co) polymerization or preliminary (co) polymerization of propylene and other olefins to produce polypropylene (B),
Then, ethylene or ethylene and other olefins are preactivated (co) polymerized to produce polyethylene (A), which is then subjected to a preactivation treatment for supporting polypropylene (B) and polyethylene (A) on the transition metal compound catalyst component. Manufactured.

In this preactivation treatment, a transition metal compound catalyst component containing a titanium compound, and 0.01 to 1,000 mol, preferably 0.05 to 500 mol of an organic metal, per 1 mol of the transition metal in the catalyst component. It is used as a catalyst for producing a polyolefin comprising a combination of the compound (AL1) and the electron donor (E1) in an amount of 0 to 500 mol, preferably 0 to 100 mol, per 1 mol of the transition metal in the catalyst component.

The polyolefin production catalyst is used in an amount of 0.001 to 5,000 mmol, preferably 0.1 to 0.005 mmol, in terms of transition metal atoms in the catalyst component per liter of the (co) polymerization volume of ethylene or ethylene and other olefins.
Propylene or a mixture of propylene and propylene with another olefin for the purpose of (co) polymerization in the presence of from 0.01 to 1,000 mmol and in the absence of a solvent or in a solvent up to 100 liters per gram of the transition metal compound catalyst component.
The catalyst is supplied to the reaction vessel in an amount of from 0.01 to 500 g to be preliminarily (co) polymerized to produce 0.01 to 100 g of polypropylene (B) per 1 g of the transition metal compound catalyst component, and then ethylene or a mixture of ethylene and other olefins of 0.01 g. ~ 1
000 g is supplied and pre-activated (co) polymerized, and 0.01 to 5,000 per 1 g of the transition metal compound catalyst component.
By producing g of polyethylene (A), the transition metal compound catalyst component is coated with and supported by polypropylene (B) and polyethylene (A).

In the present specification, the term “polymerization volume” refers to the volume of the liquid phase portion in the polymerization vessel in the case of liquid phase polymerization.
In the case of gas phase polymerization, it means the volume of the gas phase portion in the polymerization vessel. The amount of the transition metal compound catalyst component used is preferably in the above range in order to maintain an efficient and controlled (co) polymerization reaction rate of propylene. On the other hand, if the amount of the organometallic compound (AL1) is too small, the (co) polymerization reaction rate becomes too slow, and even if it is too large, a corresponding increase in the (co) polymerization reaction rate cannot be expected. It is not preferable because the residue of the organometallic compound (AL1) increases in the obtained polypropylene composition. Furthermore, if the amount of the electron donor (E1) is too large,
The (co) polymerization reaction rate decreases. If the amount of the solvent used is too large, not only a large reaction vessel is required, but also it is difficult to efficiently control and maintain the (co) polymerization reaction rate.

The pre-activation treatment includes, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, -i-octane, decane and dodecane; and alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane. Can be carried out in a liquid phase using olefin itself as a solvent, an inert hydrocarbon such as aromatic hydrocarbons such as toluene, xylene and ethylbenzene, a gasoline fraction or a hydrogenated diesel oil fraction, and the like. It is also possible to carry out in the gas phase without.

The preactivation treatment may be carried out in the presence of hydrogen, but the intrinsic viscosity [η _A ] is 15 to 100 dl.
/ G of high molecular weight polyethylene (A) is preferably not used with hydrogen. In the pre-activation treatment, the conditions for the preliminary (co) polymerization of propylene or a mixture of propylene and another olefin for the purpose of the (co) polymerization are as follows: polypropylene (B) is produced in an amount of 0.01 g to 100 g per 1 g of the transition metal compound catalyst component. Under normal conditions, usually at a temperature of -40 ° C to 100 ° C and 0.1 to 5
It is performed under a pressure of MPa for 1 minute to 24 hours. The pre-activation (co) polymerization conditions for ethylene or a mixture of ethylene and another olefin are as follows: polyethylene (A) is used in an amount of 0.01 g to 5,000 g per transition metal compound catalyst component.
0 g, preferably 0.05 to 2,000 g, more preferably 0.1 to 1,000 g, is not particularly limited as long as it is produced in an amount of usually -40 to 40 ° C, preferably -40 to 30 ° C. More preferably, at a relatively low temperature of about -40 to 20 ° C, 0.1 to 5 MPa, preferably 0.2
The pressure is from 1 minute to 24 hours, preferably from 5 minutes to 18 hours, more preferably from 10 minutes to 12 hours under a pressure of from 5 to 5 MPa, more preferably from 0.3 to 5 MPa.

Further, after the preactivation treatment, propylene or a mixture of propylene and other olefins for the purpose of main (co) polymerization is used for the purpose of suppressing a decrease in main (co) polymerization activity due to the preactivation process. By addition of from 0.01 to 10 per gram of the transition metal compound catalyst component.
The reaction may be performed with a reaction amount of 0 g of polypropylene (D).
In this case, the organometallic compound (AL1) and the electron donor (E
1), the solvent, and the amount of propylene or a mixture of propylene and other olefins can be used in the same range as the preactivated polymerization using ethylene or a mixture of ethylene and other olefin olefins,
It is preferable to carry out the reaction in the presence of 0.005 to 10 mol, preferably 0.01 to 5 mol of the electron donor per mol of the transition metal atom. The reaction conditions are -40C to 10C.
1 minute to 2 minutes at a temperature of 0 ° C. and a pressure of 0.1 to 5 MPa.
Run for 4 hours.

The organometallic compound (A) used for the addition polymerization
L1), the electron donor (E1), and the type of the solvent,
The same ones as those used in the preactivated polymerization using ethylene or a mixture of ethylene and other olefins can be used, and the mixture with propylene or other olefins has the same composition as that of the present (co) polymerization. The intrinsic viscosity [η _d ] of the polypropylene produced by the addition polymerization is in a range smaller than the intrinsic viscosity [η _A ] of the polyethylene (A), and finally, the polypropylene of the component (b) after the main (co) polymerization. Incorporated as part.

The preactivated catalyst can be used as such or with an additional organometallic compound (AL2) and an electron donor (E2).
Can further be used in the main (co) polymerization of an olefin having 2 to 12 carbon atoms to obtain the desired polypropylene composition (x).

The olefin main (co) polymerization catalyst may be any one of the preactivated catalyst and the transition metal atom 1 in the preactivated catalyst.
The total amount of the organometallic compound (AL2) and the organometallic compound (AL1) in the activation catalyst (AL1 + AL
2) in 0.05 to 3000 mol, preferably 0.1 to
The electron donor (E2) is added in a total amount (E1 + E2) of 0 to 5,000 with respect to 1,000 mol and 1 mol of the transition metal atom in the activation catalyst in combination with the electron donor (E1) in the preactivation catalyst.
It consists of 0 mol, preferably 0-3,000 mol.

Content of organometallic compound (AL1 + AL
If (2) is too small, the (co) polymerization reaction rate in the main (co) polymerization of propylene or other olefins is too slow, while if it is too large, the (co) polymerization reaction rate increases as expected. Not only is it inefficient and is not recognized, but also undesirably, the organometallic compound residue remaining in the finally obtained polypropylene composition increases.
Further, when the content of the electron donor (E1 + E2) becomes excessive, the (co) polymerization reaction rate is remarkably reduced.

The types of the organometallic compound (AL2) and the electron donor (E2) which are additionally used as necessary for the olefin main (co) polymerization catalyst are as described above for the organometallic compound (AL1) and the electron donor (E1). The same ones as in E1) can be used. They may also be used alone or in combination.
A mixture of more than one species may be used. Further, they may be the same or different from those used in the pre-activation treatment.

The olefin main (co) polymerization catalyst is obtained by filtering or decanting a solvent, an unreacted olefin, an organometallic compound (AL1), an electron donor (E1) and the like present in the preactivated catalyst. Or a suspension obtained by adding a solvent to the granules obtained by removing the particles, and an additional organometallic compound (AL2) and, if desired, an electron donor (E2). The solvent and the unreacted olefin present are removed by distillation under reduced pressure or by an inert gas stream or the like, or the granules obtained by adding a solvent to the granules or, if desired, an organometallic compound (AL2 ) And the electron donor (E2).

In the above method, the amount of the preactivated catalyst or the catalyst for the main (co) polymerization of olefin is 0.001 to 0.001 per liter of polymerization volume, in terms of transition metal atoms in the preactivated catalyst. 1,000 mmol, preferably 0.005-500 mmol, is used. By setting the amount of the transition metal compound catalyst component in the above range, it is possible to maintain an efficient and controlled (co) polymerization reaction rate of propylene or a mixture of propylene and a composition olefin.

For the main (co) polymerization of propylene or a mixture of propylene and another olefin in the present invention, a known olefin (co) polymerization process can be used as the polymerization process. Specifically, propane, butane, pentane, hexane, heptane, octane, -i
-Aliphatic hydrocarbons such as octane, decane and dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; gasoline fractions and hydrogenated diesel oil Olefin (co) in an inert solvent such as a distillate
A slurry polymerization method for carrying out polymerization, a bulk polymerization method using olefin itself as a solvent, a gas phase polymerization method for carrying out (co) polymerization of olefin in a gas phase, and a polyolefin produced by (co) polymerization in a liquid state Solution polymerization or a polymerization process combining two or more of these processes can be used.

In the case of using any of the above polymerization processes, the polymerization conditions include a polymerization temperature of 20 to 120 ° C., preferably 30 to 100 ° C., and particularly preferably 40 to 100 ° C.
° C, the polymerization pressure is 0.1 to 5 MPa, preferably in the range of 0.3 to 5 MPa, continuous, semi-continuous,
Alternatively, the polymerization is carried out batchwise in a range of about 5 minutes to 24 hours. By adopting the above polymerization conditions, the polypropylene as the component (b) can be produced with high efficiency and a controlled reaction rate.

After completion of the (co) polymerization, if necessary, a post-treatment step such as a known catalyst deactivation treatment step, catalyst residue removal step and drying step is carried out, and the desired polypropylene composition having a high melt tension is obtained. (X) is obtained.

In a more preferred embodiment of the method for producing the polypropylene composition (x) used in the present invention, the polypropylene of the component (b) produced in the (co) polymerization and the finally obtained polypropylene composition (x)
Has an intrinsic viscosity [η _T ] of 0.2 to 10 dl / g, preferably 0.7 to 5 dl / g, and polyethylene (A) derived from the preactivated catalyst used in the obtained polypropylene composition. Is in the range of 0.01 to 5% by weight. In addition, similarly to the known olefin polymerization method, the molecular weight of the (co) polymer obtained by using hydrogen during the polymerization can be adjusted.

The polypropylene composition (x) according to the present invention
In the method for producing a high molecular weight polyethylene (A)
Is produced by the pre-activation step and is uniformly dispersed in the finally obtained polypropylene composition (x), so that the required amount of the pre-activation catalyst can be prepared at once, In propylene or other olefin main (co) polymerization, ordinary olefin (co) polymerization may be carried out using an existing process, so that productivity equivalent to that of normal polyolefin production can be maintained.

The polypropylene composition (x) used in the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an antiblocking agent, a coloring agent, an inorganic or After blending various additives such as organic fillers and various synthetic resins, the mixture is heated and melt-kneaded as required, and further provided in the form of pellets cut into granules for production of various molded products.

Examples of the method for producing the sheet of the present invention include a method for producing a sheet by a known molding method (extrusion molding, calender molding, compression molding, cast molding, etc.) using the polypropylene composition (x).

The thickness of the sheet forming the layer produced from the polypropylene composition (x) of the present invention is from 50 μm to 2 μm.
A range of 50μ, preferably 60μ to 150μ is good.

The thickness of the sheet forming the layer produced from the polypropylene (b) of the present invention is from 50 μm to 250 μm.
μ, preferably in the range of 60μ to 150μ.

The printing on the sheet forming the layer composed of the polypropylene composition (x) is usually carried out by a gravure method, but is not particularly limited thereto, and a valley printing method or a rotary screen printing method is also possible.

In the above-mentioned lamination of the two-layer sheet made of the polypropylene composition (x) and the sheet made of the polypropylene (b), the adhesive is coated on a required surface of the sheet made of the polypropylene composition (x), and the heat lamination is performed. It is adhered by processing by. As the adhesive, biurethane vinegar is usually used, but is not limited thereto.

[0069]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The definitions of the terms used in the examples and comparative examples and the measuring method are as follows.

MFR: Measured according to JIS K7210, condition 14 in Table 1. (Unit: g / 10min)

Intrinsic viscosity [η]: A value obtained by measuring the intrinsic viscosity in tetralin at 135 ° C. using an Ostwald viscometer (manufactured by Mitsui Toatsu Chemicals, Inc.). (Unit: dl / g)

Melt tension (MS): A value measured by a melt tension tester type 2 (manufactured by Toyo Seiki Seisaku-sho, Ltd.). (Unit: cN)

Extrudability: Composition or resin 100 to be evaluated
The tetrakis [methylene-3- (3′-
5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and 0.1 part by weight of calcium stearate to obtain a composition,
The composition was melt-kneaded and granulated at 230 ° C. using a 65 mmφ extrusion granulator to obtain a pellet-shaped composition. 65m
Using a mΦ extruder and a molding machine having a T-die, the obtained composition is supplied to the raw material supply port of the extruder, and the screw rotation speed and load are adjusted so that the discharge rate is 60 kg / hr at a resin temperature of 230 ° C from the T-die. The current value (I) was set, and this set value was measured.

Formability: A sheet having a thickness of 0.4 mm is used as a sample sheet. This sample sheet is opened at 300 × 300.
The sample sheet is fixed to a frame having a size of mm, and the fixed sample sheet is horizontally held in a heating furnace maintained at 180 ° C. for a certain time. The following phenomena generally occur in a sheet using polypropylene and its composition when the above evaluation is performed. First, the central portion of the sheet hangs down due to the heating. Next, a part of the sag returns, and the returned state continues for a certain period of time. Finally, there is no sagging again and then no return. As described above, the initially sagged amount is referred to as the “sag amount” (m
m). The amount returned in a state where a part of the droop has returned is referred to as a “return amount” (mm),
The time during which this state continued was defined as "holding time" (seconds). The “return rate” (%) was determined from the following equation.

Return rate = Return amount / Drop amount × 100%

The smaller the amount of droop, the greater the return rate and the longer the holding time, the better the vacuum formability of the sheet.

Example 1 (1) Preparation of transition metal compound catalyst component Decane 0,1 in a stainless steel reactor equipped with a stirrer.
3 liters, 48 g of anhydrous magnesium chloride, 170 g of n-butyl orthotitanate and 195 g of 2-ethyl-1-hexanol were mixed, and the mixture was heated to 130 ° C. while stirring.
The mixture was heated for a period of time to dissolve to form a uniform solution. This homogeneous solution was heated to 70 ° C., 18 g of di-i-butyl phthalate was added with stirring, and after 1 hour, 520 g of silicon tetrachloride was added over 2.5 hours to precipitate a solid.
For one hour. The solid was separated from the solution and washed with hexane to give a solid product.

The total amount of the solid product was mixed with 1.5 liters of titanium tetrachloride dissolved in 1.5 liters of 1,2-dichloroethane and then di-i-butyl phthalate 36
g, and reacted at 100 ° C. for 2 hours with stirring.
At the same temperature, the liquid phase was removed by decantation,
Again, 1.5 liters of 1,2-dichloroethane and 1.5 liters of titanium tetrachloride were added, the mixture was stirred at 100 ° C. for 2 hours, washed with hexane and dried, and the titanium-containing carrier containing 2.8% by weight of titanium was added. A catalyst component (transition metal compound catalyst component) was obtained.

(2) Preparation of Pre-Activated Catalyst After replacing a stainless steel reactor having an inner volume of 5 liters with inclined blades with nitrogen gas, 2.8 liters of n-hexane was added.
Triethyl aluminum (organic metal compound (AL1))
After adding 4 mmol and 9.0 g (5.26 mmol in terms of titanium atom) of the titanium-containing supported catalyst component prepared in the preceding section, 20 g of propylene was supplied, and prepolymerization was performed at -2 ° C for 10 minutes.

Separately, when the polymer formed after the prepolymerization conducted under the same conditions was analyzed, 2 g of propylene was converted to polypropylene (B) per 1 g of the titanium-containing supported catalyst component, and the polypropylene (B) was dissolved in tetralin at 135 ° C. The measured intrinsic viscosity [η _B ] was 2.8 dl / g. After completion of the reaction time, unreacted propylene is discharged outside the reactor, and the gas phase of the reactor is replaced with nitrogen once,
While maintaining the temperature in the reactor at -1 ° C, ethylene was continuously supplied to the reactor for 2 hours so that the pressure in the pressure reactor was maintained at 0.59 MPa, thereby performing preactivated polymerization.

Separately, as a result of analyzing the polymer formed after the prepolymerization performed under the same conditions, 24 g of the polymer was present per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity of the polymer measured in tetralin at 135 ° C. [ η _T2 ]
Was 31.4 dl / g.

The amount (W ₂ ) of polyethylene (A) per 1 g of the titanium-containing supported catalyst component produced by the preactivation polymerization with ethylene is the amount of the polymer produced per 1 g of the titanium-containing supported catalyst component after the preactivation treatment. The difference between (W _T2 ) and the amount of produced polypropylene (B) per 1 g of the titanium-containing supported catalyst component after prepolymerization (W ₁ ) is determined by the following equation. W ₂ = W _T2 −W ₁

The intrinsic viscosity [η _A ] of the polyethylene (A) produced by the pre-activation with ethylene was determined by the intrinsic viscosity [η _B ] of the polypropylene (B) produced by the pre-polymerization and the pre-activation treatment. Intrinsic viscosity of polymer [η _T2 ]
From the following equation. [Η _A ] = ([η _T2 ] × W _T2 − [η _B ] × W ₁ ) / (W _T2 −W
₁ ) = [η _E ]

The amount of polyethylene (A) produced by preactivation polymerization with ethylene according to the above formula was 22 g per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η _E ] was 3
It was 4.0 dl / g.

After the completion of the reaction time, unreacted ethylene was discharged to the outside of the reactor, and the gas phase of the reactor was replaced with nitrogen once, and then di-i-propyldimethoxysilane (electron donor) was introduced into the reactor. (E1)) After 1.6 mmol was added, 20 g of propylene was supplied, and the mixture was kept at 1 ° C. for 10 minutes to perform addition polymerization after the preactivation treatment.

Separately, the analysis results of the polymer formed by the addition polymerization performed under the same conditions show that the intrinsic viscosity of 26 g of the polymer per 1 g of the titanium-containing supported catalyst component was measured and the polymer was measured in tetralin at 135 ° C. [Η _T3 ] is 29.2 dl / g, and the amount of polypropylene produced by addition polymerization (W ₃ ) calculated in the same manner as above
Was 2 g per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η _d ] was 2.8 dl / g. After the reaction time, unreacted propylene was discharged outside the reactor, and the gas phase of the reactor was replaced with nitrogen once to obtain a preactivated catalyst slurry for main polymerization.

(3) Production of Polypropylene Composition (Main (Co) polymerization of Propylene) After replacing a stainless steel polymerization vessel equipped with a stirrer with an internal volume of 500 liters with nitrogen, at 20 ° C. n-hexane 24
0 liters, 780 mmol of triethylaluminum (organic metal compound (AL2)), 78 mmol of di-i-propyldimethoxysilane (electron donor (E2)), and を of the preactivated catalyst slurry obtained above It was charged into the polymerization vessel. Subsequently, 55 liters of hydrogen were introduced into the polymerization vessel, and the temperature was raised to 70 ° C.
Under the conditions described above, propylene was continuously supplied into the polymerization vessel for 2 hours while maintaining the gas phase pressure in the polymerization vessel at 0.79 MPa, to thereby perform main polymerization of propylene.

After the polymerization time had elapsed, 1 liter of methanol was introduced into the polymerization vessel, and the catalyst was deactivated at 70 ° C. for 15 minutes. Then, after discharging the unreacted gas, solvent separation,
After drying the polymer, the intrinsic viscosity [η _r ] is 1.97 dl /
g of polymer, 40.1 kg. The obtained polymer is a polypropylene composition having a polyethylene (A) content of 0.25% by weight corresponding to the preactivated polymerization corresponding to the component (a), and the intrinsic viscosity [η _P ] of the polypropylene of the component (b) is It was 1.97 dl / g. The resulting polypropylene composition has a melt tension (MS) of 4.9 cN, MF
R was

To 100 parts by weight of this polypropylene composition, 2,6-di-tert-butyl-p-cresol was added in an amount of 0.1%.
One part by weight and 0.1 part by weight of calcium stearate were mixed, and then a pellet-shaped composition was formed using an extrusion granulator having a cylinder set temperature of 230 ° C. and a screw diameter of 40 mm. Using this composition, a T
Using a die sheet molding machine, the resin temperature is 230 ° C, the cooling roll temperature is 60 ° C, the take-up speed is 10m / min, and the sheet thickness is
mm sheet was prepared. Printed on this sheet (by gravure method) and coated with a biurethane vinegar adhesive, a density of 0.90, a crystal melting point of 160 ° C., an isotactic pentad fraction of 95%, and a homopolypropylene having an intrinsic viscosity [η] of 2.8. A laminated sheet was prepared by heat lamination with a 0.15 mm sheet obtained in the same manner as in the composition (x). Table 1 shows the moldability of this sheet.

Example 2 A polypropylene composition was produced under the same conditions as in Example 1. To 100 parts by weight of this polypropylene composition, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 0.1 part by weight of calcium stearate were mixed. The composition was pelletized using a 40 mm extrusion granulator. Using this composition, a T-die sheet molding machine having a screw diameter of 65 mm, a resin temperature of 230 ° C., a cooling roll temperature of 60 ° C., a take-up speed of 10 m / min, and a sheet thickness of 0.1 mm
Created a sheet. Printed on this sheet (by gravure method) and coated with a biurethane vinegar adhesive, a density of 0.90, a crystal melting point of 160 ° C., an isotactic pentad fraction of 95%, and a homopolypropylene having an intrinsic viscosity [η] of 2.8. 0.1 obtained by the same method as in the composition (x).
Laminated sheets were made with 1 mm sheets and hot lamination. Table 1 shows the moldability of this sheet.

COMPARATIVE EXAMPLE 1 2,6-di-tert-butyl butylamine was used for 100 parts by weight of homopolypropylene having a density of 0.90, a crystal melting point of 160 ° C., an isotactic pentad fraction of 95% and an intrinsic viscosity [η] of 2.8. 0.1 part by weight of p-cresol and 0.1 part by weight of calcium stearate were mixed, and then a pellet-shaped composition was obtained using an extrusion granulator having a cylinder set temperature of 230 ° C. and a screw diameter of 40 mm. Using this composition, in a T-die sheet molding machine having a screw diameter of 65 mm, a resin temperature of 230 ° C., a cooling roll temperature of 60 ° C., and a take-up speed of 10 m / m
A sheet having a sheet thickness of 0.15 mm was prepared in minutes. This sheet was printed (by gravure method), coated with a biurethane vinegar adhesive, and a 0.15 mm sheet obtained from the same homopolypropylene by the same method as described above and a laminated sheet was formed by thermal lamination. Table 1 shows the moldability of this sheet.

COMPARATIVE EXAMPLE 2 2,6-Di-tert-butyl-butyl was added to 100 parts by weight of homopolypropylene having a density of 0.90, a crystal melting point of 160 ° C., an isotactic pendat fraction of 95% and an intrinsic viscosity [η] of 2.8. 0.1 part by weight of p-cresol and 0.1 part by weight of calcium stearate were mixed, and then a pellet-shaped composition was obtained using an extrusion granulator having a cylinder setting temperature of 230 ° C. and a screw diameter of 40 mm. Using this composition, in a T-die sheet molding machine having a screw diameter of 65 mm, a resin temperature of 230 ° C., a cooling roll temperature of 60 ° C., and a take-up speed of 10 m / m
A sheet having a sheet thickness of 0.1 mm was prepared in minutes. This sheet was printed (by gravure method), coated with a biurethane vinegar adhesive, and a 0.1 mm sheet obtained from the same homopolypropylene as described above in the same manner as above and a laminated sheet made by thermal lamination. Is shown in Table 1.

[0093]

[Table 1]

[0094]

As is clear from the above-described embodiment,
The sheet of the present invention is a laminated sheet having excellent moldability.
Due to the excellent moldability, the sheet of the present invention having a large thickness and a wide width is useful for forming a large vacuum molded product, a large compressed air molded product, a large press molded product, and the like.

Claims (4)

[Claims] 1. An olefin (co) polymer (a)
A layer composed of the polypropylene composition (x) consisting of 01 to 5 parts by weight and 100 parts by weight of the polypropylene (b), a printed layer provided on the layer and a layer composed of the following polypropylene (b) are laminated and bonded. A laminated sheet, comprising: (A) Intrinsic viscosity [η measured in tetralin at 135 ° C.
_[E ] is 15 to 100 dl / g. (B) a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene polymerized units, having an intrinsic viscosity [η _P ] of 0.2 to 10 dl / g measured in tetralin at 135 ° C. Some polypropylene. 2. A polypropylene composition (x) comprising:
The difference between the melt tension (MS) at 30 ° C. and the intrinsic viscosity [η _T ] measured in tetralin at 135 ° C. is expressed as log (MS)> 4.24 × log [η _T ] −1.05. The laminated sheet according to claim 1 having a relationship. 3. The laminated sheet according to claim 1, wherein the olefin (co) polymer (a) is an ethylene homopolymer or an ethylene-olefin copolymer containing 50% by weight or more of ethylene polymerized units. 4. Polypropylene (b) has a melting point of 160 ° C.
The laminated sheet according to claim 1, which is a propylene-α-olefin copolymer having an α-olefin content of 2 to 8% by weight at 125 ° C.