JP2534370B2 - Laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate suitable for exterior and interior materials of various products, agricultural films, steel material coating materials and the like.

[Prior Art] Conventionally, various types of homo-type and block-type polypropylene resins (PP) are known.
Sheet materials, packaging materials and the like, which are obtained by combining and other materials, are used in various fields.

[Problems to be solved by the invention] However, conventional polypropylene resins generally have a high welding temperature of 160 ° C or higher and a bending elastic modulus of 9000k.
It had a hard property at g / cm ² or more. Therefore, a sheet material, a packaging material, or the like formed of a conventional laminated body containing a polypropylene resin has poor heat sealability and lacks flexibility, and therefore, it is not always easy to handle depending on the intended use. Conventionally, linear low density polyethylene (LLDP
E) was used, but the heat resistance temperature is low at 115-125 ℃,
Therefore, the use target was limited.

Therefore, an object of the present invention is to provide a laminate having good low-temperature heat sealability, rich flexibility, and excellent heat resistance.

[Means for Solving the Problems] In the present invention, as a result of intensive studies for achieving the above-mentioned object, it is possible to lower the welding temperature by forming a laminate using a specific polypropylene resin. The inventors have found that the above problems can be solved with appropriate flexibility and excellent heat resistance, and have completed the present invention based on this finding.

That is, according to the present invention, it is composed of a plurality of material layers,
In a laminate in which at least one material layer is formed mainly of soft polypropylene, the soft polypropylene is a polypropylene-based polymer (a) shown in (A) below,
Alternatively, a propylene-based composition (b) containing the polymer (a) shown in (B) below is provided.

(A) (i) Boiling heptane soluble polypropylene 10-90
% Of boiling heptane-insoluble polypropylene of 90 to 10% by weight, (ii) rrrr / (1-mmmm) is 20% or more in pentad fraction by ¹³ C-NMR, and (iii) differential calorimetric analyzer ( Melting peak temperature (T
m) is 150 ° C. or higher and (iV) the enthalpy of fusion (ΔH) measured by DSC is 100 J / g or less (a) (B) (i) The polypropylene polymer (A) 10 to 95
% By weight, and (ii) an ethylene-propylene copolymer (c) having an ethylene unit content of 10 to 60 mol% and an intrinsic viscosity of 0.5 to 7.0 dl / g and / or an ethylene unit content of 10 to 60.
Polypropylene composition comprising 90 to 5% by weight of ethylene-propyllene-polyene copolymer (c ') having a polyene unit content of 1 to 10% by mole and an intrinsic viscosity of 0.5 to 7.0 dl / g. (B) Further, as an embodiment of the present invention, it may include a material layer made of at least one of a thermoplastic resin and a thermosetting resin. Alternatively, it may include at least a material layer made of metal, rubber, cloth, paper, wood, cellophane, or leather.

Here, of the materials of the laminate of the present invention, soft polypropylene which is the main component will be described.

In the present specification, the "soft polypropylene" means a polypropylene polymer (a) shown in (A) above or a propylene composition (b) containing the polymer (a) shown in (B) above. It means a soft polypropylene film characterized by comprising a certain soft polypropylene.

The polypropylene-based polymer (a) preferably has a property of observing a domain structure when observed with a transmission electron microscope.

Among the soft polypropylenes used in the present invention, the polypropylene-based polymer (a) can be prepared, for example, by either the gas-phase one-step polymerization method or the slurry one-step polymerization method described below. Hereinafter, their preparation methods will be described in order.

Gas-Phase One-Step Polymerization Method The catalyst system used in the gas-phase one-step polymerization method is, for example, (I) (i) a crystalline poiolefin and (ii) a solid catalyst component composed of magnesium, titanium, a halogen atom and an electron-donating compound. And (II) an organoaluminum compound, (III) an alkoxy group-containing aromatic compound, and (IV) an electron-donating compound.

The above solid component (I) is 0.005-3 parts by weight of the solid catalyst component (ii) in 1 part by weight of the crystalline polyolefin (i).
It is contained in a proportion of 0 parts by weight (preferably 0.02 to 10 parts by weight).

The solid component (I) is, for example, a solid catalyst component (i
It can be prepared by a method of prepolymerizing an olefin in the presence of i), an organoaluminum compound and optionally an electron donating compound (preliminary polymerization method).

Here, the solid catalyst component (ii) contains magnesium, titanium, a halogen atom and an electron donating compound as essential components, and is prepared by contacting a magnesium compound, a titanium compound and an electron donating compound. can do.

As the magnesium compound, for example, magnesium dihalide such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite, carboxylic acid salt of magnesium, alicoxy magnesium such as diethoxy magnesium, aryloxy magnesium,
Alkoxy magnesium halides, allyloxy magnesium halides, alkyl magnesiums such as ethylbutyl magnesium, alkyl magnesium halides, or reaction products of organomagnesium compounds with electron donors, halosilanes, alkoxysilanes, silanols, aluminum compounds and the like. However, among these, magnesium halide, alkoxy magnesium, alkyl magnesium, and alkyl magnesium halide are preferable. These magnesium compounds may be used alone or in combination of two or more.

Examples of the titanium compound include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, and tetra-n-.
Tetraalkoxytitanium such as butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium and tetraphenoxytitanium, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other tetrahalogenated titanium, methoxytitanium trichloride, ethoxytitanium trioxide. Chloride, propoxytitanium trichloride, n-
Trihalogenated alkoxytitanium such as butoxytitanium trichloride, ethoxytitanium tribromide,
Dihalogenated dialkoxytitanium such as dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, Examples of the mono-hagogenized trialkoxy titanium such as tri-n-butoxytitanium chloride include
Among these, high halogen content titanium compounds, particularly titanium tetrachloride, are preferable. These titanium compounds may be used alone or in combination of two or more.

The electron-donating compound is an organic compound containing oxygen, nitrogen, phosphorus, sulfur, silicon and the like, and can basically improve the regularity in the polymerization of propylene.

Examples of such an electron-donating compound include esters, thioesters, amines, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides, aldehydes, Examples thereof include organic acids. Furthermore, for example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxylane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane,
Organosilicon compounds such as methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane and benzyltrimethoxysilane, aromatic dicarboxylic acid esters such as n-butyl phthalate and diisobutyl phthalate, benzoic acid , P-
Alkyl ester having 1 to 4 carbon atoms of aromatic monocarboxylic acid such as methoxybenzoic acid, p-ethoxybenzoic acid and toluic acid, isopropyl methyl ether, isopropyl ethyl ether, t-butyl methyl ether, t-butyl ethyl ether, t Asymmetric ethers such as -butyl-n-propyl ether, t-butyl-n-butyl ether, t-amyl methyl ether and t-amyl ethyl ether, 2,2'-azobis (2-ethylpropane), 2,2
-Azobis (2-ethylpropane), 2,2'-azobis (2-methylpetane), aa'-azobisisobutyronitrile, 1,1'-azobis (1-cyclohexanecarboxylic acid), (1- Examples include azo compounds such as phenylmethyl) -azodiphenylmethane, 2-phenylazo-2,4-dimethyl-4-trixypentanenitrile, etc., in which a sterically hindering substituent is bonded to an azo bond, and these are used alone. Alternatively, two or more kinds may be used in combination.

Specifically, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate,
Methyl ethyl phthalate, methyl propyl phthalate,
Methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl propyl terephthalate, methyl isobutyl terephthalate, ethyl propyl terephthalate, ethyl isobutyl terephthalate, propyl Isobutyl terephthalate,
Aroma such as dimethylisophthalate, diethylisophthalate, dipropylisophthalate, diisobutyleisophthalate, methylethylisophthalate, methylpropylisophthalate, methylisobutylisophthalate, ethylpropylisophthalate, ethylisobutylisophthalate and propylisobutylisophthalate Group dicarboxylic acid diester, methyl formate, ethyl acetate,
Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl acetate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate,
Dimethyl maleate, ethyl cyclofuxanecarboxylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl toluate,
Monoesters such as amyl triylate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethyl naphthoate,
γ-valerolactone, coumarin, phthalide, esters of C2-18 such as ethylene carbonate, benzoic acid, organic acids such as p-oxybenzoic acid, succinic anhydride, benzoic anhydride, p-toluic anhydride, etc. C3 to C15 ketones such as acid anhydrides, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone, and C2 to C15 aldehydes such as acetaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthylaldehyde C2 to C15 acid halides such as compounds, acetyl chloride, benzyl chloride, toluic acid chloride, anisic acid chloride, methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole , Ethers having 2 to 20 carbon atoms such as diphenyl ether and ethylene glycol butyl ether, acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide, tributylamine, N, N′-dimethylpiperazine, trindylamine, aniline, Examples thereof include amines such as pyridine, picoline and tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile and tolunitrile.

Among these, esters, ethers, ketones and acid anhydrides are preferable, and in particular, aromatic dicarboxylic acid diesters such as di-n-butyl phthalate and diisobutyl phthalate, benzoic acid, p-methoxybenzoic acid, Preferable are alkyl esters having 1 to 4 carbon atoms of aromatic monocarboxylic acids such as p-ethoxybenzoic acid and toluic acid.
Aromatic dicarboxylic acid diesters are particularly preferred because they improve catalyst activity and activity persistence.

The above-mentioned solid catalyst component (ii) can be prepared by known methods (JP-A-53-43094, JP-A-55-135102, JP-A-55-135103, JP-A-56-18606). (Publication). For example, (1) a method in which a magnesium compound or a complex compound of a magnesium compound and an electron donor is pulverized in the presence of an electron donor and a pulverization auxiliary optionally used, and then reacted with a titanium compound,
(2) A method of reacting a liquid material of a magnesium compound having no reducing ability with a liquid titanium compound in the presence of an electron donor to deposit a titanium complex on a solid,
(3) A method of reacting a titanium compound with the product obtained in (1) or (2) above, and (4) an electron donor and a titanium compound further added to the product obtained in (1) or (2) above. Method of reacting, (5) pulverizing a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence of an electron donor, a titanium compound, and a pulverization auxiliary optionally used, and then halogen or It can be prepared by a method of treating with a halogen compound, (6) a method of treating the compound obtained in the above (1) to (4) with halogen or a halogen compound, and the like.

Furthermore, methods other than these methods (Japanese Patent Application Laid-Open No. 56-166205)
JP-A-57-63309, JP-A-57-190004, JP-A-57-300407 and JP-A-58-47003), the solid catalyst component (ii) is It can be prepared.

Further, oxides of elements belonging to groups II to IV of the periodic table, for example, composite oxides containing at least one oxide of elements belonging to groups II to IV of the periodic table, such as oxides of silicon oxide, magnesium oxide, and amminium oxide. Substance, for example, a solid substance in which the magnesium compound is supported on silica alumina, an electron donor and a titanium compound, in a solvent,
Depending on the temperature in the range of 0 ° C, preferably 10 to 150 ° C, 2 minutes to
The solid catalyst component (ii) can be prepared by contacting for 24 hours.

In preparing the solid catalyst component (ii), an organic solvent which is inert to the magnesium compound, the electron donor and the titanium compound as a solvent, for example, an aliphatic hydrocarbon such as hexane or heptane, or an aromatic solvent such as benzene or toluene. Group hydrocarbons or halogenated hydrocarbons such as mono- or polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms can be used.

The composition of the solid catalyst component (ii) thus prepared is usually in the range of magnesium / titanium atomic ratio of 2 to 100, halogen / titanium atomic ratio of 5 to 200, and electron donor / titanium molar ratio of 0.1 to 10. It is in.

The solid component (I) can be prepared by prepolymerizing an olefin in the presence of the thus obtained solid catalyst component (ii), an organoaluminum compound and optionally an electron donating compound.

As the organoaluminum compound used herein, the general formula _{^{A1R 3 pX 3 -p (1)}} (R 3 in the formula is an alkyl group having 1 to 10 carbon atoms, X is chlorine, a halogen atom such as bromine, p is 1 A number represented by 3). Examples of such an aluminum compound include, for example, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, and trioctyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, dioctyl aluminum. Dialkylaluminum monohalides such as monochloride and alkylaluminum sesquihalides such as ethylaluminum sesquichloride can be preferably used. These aluminum compounds may be used alone or in combination of two or more.

Further, as the electron-donating compound that can be optionally present, the compounds described in connection with the solid catalyst component (ii) can be used. In the method for preparing the solid component (I), examples of olefins include ethylene, propylene, butene-1,4-methylpentene-1.
Such as C2-C10 α-olefin, usually 30 ~
Prepolymerization is carried out at a temperature of 80 ° C., preferably in the range of 55 to 70 ° C., to form a crystalline polyolefin having a melting point of 100 ° C. or higher. At this time, the aluminum / titanium atomic ratio of the catalyst system is usually 0.1 to 100, preferably 0.5 to 5
And the electron donating compound / titanium molar ratio is 0 to 50, preferably 0.1 to 2.

The solid component (I) comprises crystalline powder such as crystalline polypropylene or polyethylene having a uniform particle size, the solid catalyst component (ii), an organoaluminum compound, an electron donating compound (having a melting point of 100 ° C. or higher). Can also be prepared by a method of dispersing (dispersion method).

Furthermore, the solid component (I) can be prepared by combining the above-mentioned prepolymerization method and dispersion method.

As described above, the catalyst system used in the gas-phase one-step polymerization method is the solid component (I), the organoaluminum compound (II), the alkoxy group-containing aromatic compound (III), and the electron-donating compound (I).
The organic aluminum compound (II) and the electron donating compound (IV) may be the compounds described above, respectively.

In addition, the alkoxy group-containing aromatic compound (III) can be represented by the general formula [In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is 1 carbon atom
To a hydrocarbon group, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is an integer of 0 to (6-m)], and specifically, for example, m- Methoxytoluene, o-methoxyphenol, m-methoxyphenol, 2-methoxy-4-methylphenol, vinylanisole, p- (1-propenyl) anisole,
p-allylanisole, 1,3-bis (p-methoxyphenyl) -1-pentene, 5-allyl-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4-hydroxy-3-methoxybenzyl alcohol, Monoalkoxy compounds such as methoxybenzyl alcohol, nitroanisole and nitrophenetol, o-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3,4-dimethoxytoluene, 2,6-dimethoxyphenol, 1-allyl-3 Dialkoxy compounds such as 1,4-dimethoxybenzene and 1,3,5-trimethoxybenzene, 5-allyl-1,2,3-trimethoxybenzene, 5-
Allyl-1,2,4-trimethoxybenzene, 1,2,3-trimethoxy-5- (1-propenyl) benzene, 1,2,4-trimethoxy-5- (1-propenyl) benzene, 1,2, 3
Examples thereof include trialkoxy compounds such as -trimethoxybenzene and 1,2,4-trimethoxybenzene, and among these, dialkoxy compounds and trialkoxy compounds are preferable. These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more.

In the above catalyst system, the solid component (I) is used in an amount of 0.0005 to 1 mol per liter of reaction volume in terms of titanium atom. The amount of the alkoxy group-containing aromatic compound (III) used is 0.01 to 500 mol, preferably 1 to 300 mol, based on 1 mol of the titanium atom in the solid component (I). If the amount used is less than 0.01 mol, the physical properties of the produced polymer deteriorate, and if it exceeds 500 mol, the catalyst activity decreases, which is not preferable. In this catalyst system, the atomic ratio of aluminum to titanium is 1: 1 to 3000 (preferably Is 1:40 to 800). If the atomic ratio is out of this range, sufficient catalytic activity cannot be obtained. Furthermore, an alkoxy group-containing aromatic compound (III)
And the electron donating compound (IV) have a molar ratio of 1: 1.01 to 100.
(Preferably 1: 0.2 to 100).

In the gas-phase one-step polymerization method, the above polypropylene-based polymer (a) is obtained by homopolymerizing propylene, and the above random copolymer is obtained by copolymerizing propylene and an α-olefin having 4 to 30 carbon atoms. A polymer (b) is obtained. The molecular weight can be adjusted by known means (for example, adjustment of hydrogen concentration). The polymerization temperature is generally 40 to 90 ° C (preferably 60 to 75 ° C), and the polymerization pressure is 10 to 45 kg / cm.
² (preferably 20 to 30 kg / cm ² ), and the polymerization time is 5 minutes to 10 hours.

Thriller One-Step Polymerization Method In the thriller one-step polymerization method, for example, either of the following two types of catalyst systems can be used. That is, (1) a catalyst comprising a combination of (a) magnesium, titanium, a halogen atom and a solid component containing an electron donating property as essential components, (b) an alkoxy group-containing aromatic compound, and (c) an organoaluminum compound. System, or (2) (A) a solid catalyst obtained by reacting the above (a) solid component and (b) an alkoxy group-containing aromatic compound in the presence or absence of (c) an organoaluminum compound A catalyst system comprising a combination of components and (B) an organic amminium compound.

First, the catalyst system of (1) above will be explained. The solid component (a) contains magnesium, titanium, a halogen atom and an electron donor as essential components, and the magnesium compound, the titanium compound and the electron donor are used as catalysts. Can be prepared.

In preparing the solid component (a), an organic solvent inert to the magnesium compound, the electron donor and the titanium compound as a solvent, such as an aliphatic hydrocarbon (hexane, heptane, etc.), an aromatic hydrocarbon ( Benzene, toluene, etc.) or halogenated hydrocarbons (mono or polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms) alone or in combination of two or more. Can be used in combination.

The magnesium compound, titanium compound and electron donating compound used in preparing the solid component (a) of the catalyst system (1) are each compound described in relation to the catalyst system of the gas phase one-step polymerization method described above. Can be the same. From these compounds, the solid component (a) can be prepared by a known method (for example, the method described in the gas-phase one-step polymerization method).

As the alkoxy group-containing aromatic compound (b) and the organoaluminum compound (c) which are brought into contact with the solid component (a) thus obtained, the compounds described in connection with the catalyst system of the gas phase one-step polymerization method can be used. Can be used.

Regarding the amount of each component constituting the catalyst system (1),
The solid component (a) is usually the reaction volume converted to titanium atoms.
It is used in an amount of 0.0005 to 1 mol per liter, and the alkoxy group-containing aromatic compound (b) has a molar ratio of the solid component (a) to the titanium atom of usually 0.01 to 500 (preferably 1 to 300).
It is used at a rate of. If this molar ratio is less than 0.01, the physical properties of the polymer produced will deteriorate, and if it exceeds 500, the catalyst activity will decrease, which is not preferable. The organoaluminum compound (c) is used in an amount such that the aluminum / titanium atomic ratio is usually 1 to 3000 (preferably 40 to 800). If this amount deviates from the above range, the catalytic activity will be insufficient.

Next, the catalyst system (2) will be described. The solid catalyst component (A) in the catalyst system (2) includes the solid component (a) of the catalyst system (1) and the alkoxy group-containing aromatic compound (ro). ) And the above organoaluminum compound (C)
It can be prepared by reacting in the presence or absence of. For this preparation, a hydrocarbon solvent (for example, a hydrocarbon solvent used for preparing the catalyst system (1)) is generally used.

Reaction temperature is usually 0 to 150 ° C (preferably 10 to 50 ° C)
When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature exceeds 150 ° C., a side reaction occurs and the activity decreases.

The reaction time varies depending on the reaction temperature, but is usually 1
Minutes to 20 hours, preferably 10 to 60 minutes.

When the solid catalyst component (A) is prepared in the presence of the organoaluminum compound (C), the concentration of the aluminum compound (C) is usually 0.05 to 100 mmol / 1 (preferably 1 to 10 mmol / 1). is there. This concentration is 0.05 mmol
If it is less than / 1, the effect of carrying out the reaction in the presence of the organoaluminum compound (c) is not sufficiently obtained, and if it exceeds 100 mmol / 1, the reduction of titanium in the solid component (a) proceeds and the catalyst The activity decreases.

On the other hand, in the absence of the organoaluminum compound (C),
Solid component (a) and alkoxy group-containing aromatic compound (b)
When the solid catalyst component (A) is prepared by reacting with,
The alkoxy group-containing compound (ii) is used in such a proportion that the molar ratio to the titanium atom in the solid component (ii) is usually 0.1 to 200 (preferably 1 to 50). The concentration of) is usually selected in the range of 0.01 to 10 mmol / 1 (preferably 0.1 to 2 mmol / 1). If the molar ratio to the titanium atom is out of the above range, it is difficult to obtain a catalyst having a desired activity. The concentration is 0.01 mmol
If it is less than / 1, the volumetric efficiency is low and not practical, and if it exceeds 10 mmol / 1, overreaction is likely to occur and the catalytic activity is lowered.

Organoaluminum compound (B) in catalyst system (2)
As the above, the organoaluminum compounds exemplified for the catalyst of the vapor phase one-step method can be used.

Regarding the amount of each component used in the catalyst system (2), the solid catalyst component (A) is converted into titanium atoms, and the reaction volume
It is usually used in an amount of 0.0005 to 1 mmol / l, and the organoaluminum compound (B) is
The aluminum / titanium atomic ratio is usually used in an amount of 1 to 3000 (preferably 40 to 800). If this atomic ratio deviates from the above range, the catalytic activity will be insufficient.

In the slurry one-stage polymerization method of the present invention, homopolymerization of propylene can give the above-mentioned polypropylene polymer (a), and propylene and α having 4 to 30 carbon atoms can be obtained.
The above random copolymer (b) can be obtained by copolymerization with an olefin.

In the case of slurry one-stage polymerization, the polymerization temperature is usually 0 to 200 ° C.
(Preferably 60 to 100 ° C.), and the propylene pressure is usually selected in the range of 1 to 50 kg / cm ² . Polymerization time is 5
Minutes to 10 hours is sufficient, and the molecular weight of the polymer can be controlled by known means, for example, adjusting the hydrogen concentration in the polymerization vessel.

Next, among the soft polypropylenes used in the present invention, a propylene composition (b) {the above polypropylene polymer (a) and an ethylene-propylene copolymer (c) or an ethylene-propylene-polyene copolymer (c '). ) And a polypropylene-based composition} are, for example, the following vapor phase multi-stage method,
It can be prepared by either a slurry multi-stage method or a blending method.

Gas phase multi-stage polymerization method The catalyst used in the gas phase multi-stage polymerization method is the same as the catalyst used in the gas phase one-stage polymerization method.

In the gas phase multi-stage polymerization method, the first polymerization (first stage polymerization) is the same as the above-mentioned gas phase one stage polymerization. Therefore, the molecular weight can be adjusted by known means (for example, adjustment of hydrogen concentration). The polymerization temperature is generally 40 to 90 ° C (preferably 60 ° C).
~ 75 ° C) and the polymerization pressure is 10-45 kg / cm ² (preferably
20 to 30 kg / cm ² ) and the polymerization time is 5 minutes to 10 hours.

The second to final polymerization (nth stage polymerization) is ethylene-propylene copolymer or ethylene-propylene-polyene copolymer.

Examples of the non-conjugated polyene that can be used in the copolymer include dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene,
5-isopropenyl-2-norbornene, 5- (1-butenin) -2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatriene,
6-methyl-4,7,8,9-tetrahydroindene, 2-
2'-dicyclopentenyl, trans-1,2-divinylcyclobutane, 1,4-hexadiene, 4-methyl-1,4-
Hexadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, Examples include 1,4,7-octatriene, 5-methyl-1,8-nonadiene, norbornadiene, vinylnorbornene and the like. Of these non-conjugated polyenes,
Particularly, dicyclopentadiene, 5-ethylidene-2-norbornene and 1,7-octadiene are preferable.

In each polymerization step, the molecular weight can be adjusted by a known means (for example, adjustment of hydrogen concentration). In the case of an ethyne-propylene copolymer, the ethylene unit content can be adjusted by adjusting the composition of the charged gas. Also in the case of an ethylene-propylene-polyene copolymer, the polyene unit content can be adjusted by adjusting the charged amount of the polyene compound. Polymerization temperature is 20 ~
90 ℃ (preferably 40 to 50 ℃), the polymerization pressure is 5 to 30
kg / cm ² (preferably 10~20kg / cm ^2), and the polymerization time is 5 minutes to 10 hours.

Slurry multi-stage polymerization method In the slurry multi-stage polymerization method, either the catalyst system (1) or (2) used in the above-mentioned slurry one-stage polymerization method can be used.

The polymerization order and the number of polymerization stages in the slurry multi-stage polymerization method are not particularly limited and can be arbitrarily selected. For example,
Propylene homopolymerization or copolymerization of propylene with an α-olefin having 4 to 30 carbon atoms is performed in the first and third stages of polymerization, and ethylene-propylene copolymerization or ethylene-in the second and fourth stages of polymerization. Propylene-polyene polymerization can be carried out. As for the number of polymerization stages (the number of n), the optimum number of stages may be selected in order to obtain a desired product, as in the case of the gas-phase multi-stage method. As the polymerization mode, either a continuous polymerization method or a discontinuous polymerization method is used. be able to.

In the case of propylene homopolymerization or copolymerization of propylene and an α-olefin having 4 to 30 carbon atoms, the polymerization temperature is usually 0 to
The range of 200 ° C. (preferably 60 to 100 ° C.), and the propylene pressure are usually selected in the range of 1 to 50 kg / cm ² . In the case of ethylene-propylene copolymer or ethylene-propylene-polyene copolymer, the polymerization temperature is usually 0 to 200.
Range ° C. (preferably 40 to 80 ° C.), and the olefin pressure is selected in the range of usually 1 to 50 kg / cm ^2.

In any of the above-mentioned polymerizations, a reaction time of about 5 minutes to 10 hours is sufficient, and the molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel.

The ethylene unit content in the case of ethylene-propylene copolymer can be adjusted by adjusting the composition of the charged gas,
In the case of ethylene-propylene-polyene copolymer, the polyene unit content can be adjusted by adjusting the charged amount. As the polyene monomer, the polyene monomer described in the vapor phase multi-stage method can be used.

Blending Method As the mixture (propylene composition) (b), a polypropylene polymer (a) and an ethylene-propylene copolymer (c) or an ethylene-propylene-polyene copolymer (c ') are known. It can be prepared by blending by the method (for example, dry blending or kneading). The polypropylene-based polymer (a) can be obtained by the gas-phase one-step polymerization method or the slurry one-step polymerization method, and the ethylene-propylene copolymer (c) or the ethylene-propylene-polyene copolymer can be obtained. Each of (c ') can be obtained by a known method.

The post-treatment after the polymerization can be performed by a conventional method. That is, in the gas-phase one-stage polymerization method or the gas-phase multi-stage polymerization method, after polymerization, the polymer powder discharged from the polymerization vessel is passed through a nitrogen stream or the like in order to remove unreacted olefins and the like contained therein. You may let me. If desired, pelletization may be carried out by an extruder, and in that case, a small amount of water, alcohol, etc. may be added in order to completely deactivate the catalyst. Further, in the slurry one-stage polymerization method or the slurry multi-stage polymerization method, after the polymerization, the monomer can be completely separated from the polymer discharged from the polymerization vessel, and then pelletized.

The laminate of the present invention contains the above-mentioned soft polypropylene in at least one material layer. Further, the other material layer preferably includes at least one of a thermoplastic resin layer and a thermosetting resin layer. On the other hand, the other material layer may be formed of at least one of metal, rubber, cloth, paper, wood, cellophane, or leather. Which of these materials is used for the "other material layer" may be appropriately selected according to the application of the laminate.

The thermoplastic resin forming the "other material layer" may be appropriately selected depending on the application of the laminate to be manufactured, and is not particularly limited. For example, polystyrene having an atactic structure, polystyrene having an isotactic structure, polystyrene having a syndiotactic structure, styrene polymers such as AS resin and ABS resin, and polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) Examples of the resin include polycarbonate resin, polyphenylene sulfide resin (PPS), and polyamide resin. In addition, polyether resins such as polyphenylene oxide, polysulfone, and polyether sulfone, acrylic resins such as polyacrylic acid, polyacrylic acid ester, and polymethylmethacrylate, polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, ethylene -Propylene copolymer, ethylene-propylene-butene-1, which ethylene-α olefin copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl alcohol copolymer, ethylene-
Polyolefin resins such as vinyl acetate copolymers, halogen-containing vinyl compound polymers such as polyvinyl chloride, polyvinylidene chloride and polyvinylidene fluoride, polyoxymethylene, polyvinyl alcohol resins and their derivatives, ethylene-carboxylic anhydride Examples thereof include ionomers which are metal chloride compounds of copolymers.

Among these, when high mechanical strength is required for the obtained resin laminate, polyester resin, polyamide resin, polycarbonate resin, polyolefin resin or halogen-containing vinyl compound polymer is selected as the thermoplastic resin. If importance is attached to the gas barrier property, polyester resin such as PET, polyamide resin, PPS, polyvinyl alcohol resin and its derivatives, ethylene vinyl acetate, polyvinylidene chloride, etc. should be selected. By selecting a thermoplastic resin having a melting point, a laminate having good heat-sealing property can be obtained. Especially when low temperature heat sealability is important, polypropylene (PP), PET, PBT, etc. should be selected. From the viewpoint of maintaining sufficient flexibility, polyamide,
It is preferable to select ethylene-vinyl acetate copolymer (EVA), polyethylene (PE), polyvinyl chloride (PVC), or the like.

The thermosetting resin that constitutes the "other material layer" may be polyurethane, unsaturated polyester, epoxy, silicon, phenol, or the like.

Aluminum (Al) and iron (Fe) can be used as the metal forming the “other material layer”, and woven fabric, knitted fabric, non-woven fabric, etc. can be used as the fabric. From the viewpoint of placing importance on heat sealability, aluminum, cloth, and paper are preferable, and when placing importance on flexibility, rubber is preferable.

1 (a), (b), and (c) are cross-sectional views showing an example of the structure of the laminated body of the present invention. FIG. 3A shows an example in which the soft polypropylene layer 100 and the other material layer 200 are two layers.
As an application example of this, another material layer 200 may be overlaid with another material layer. FIG. 2B shows a structure in which the soft polypropylene layer 10 is superposed on both surfaces of another material layer 200. As an application example of this, another material layer may be provided between the two soft polypropylene layers in a plurality of stages. FIG. 3C shows a structure in which the other material layers 200 and 300 are superposed on both surfaces of the soft polypropylene layer 100. As an application example of this, it is also possible to adopt a configuration in which a plurality of layers of other materials are superposed on both surfaces of the soft polypropylene layer 100. Furthermore, one or two or more of the above configuration examples may be combined.

The thickness of the laminate is not particularly limited, but is preferably 10 to 2000 μm in order to maintain flexibility.

Also, the thickness of the soft polypropylene layer is not particularly limited, but in order to sufficiently draw out the material of the layer, it is 5 to 1,000.
It is preferable to set in the range of μm.

By the way, in manufacturing the laminate of the present invention,
Although various means can be considered depending on the form and use of the laminate, ordinary methods may be appropriately combined depending on the situation. Specifically, the following manufacturing method can be mentioned.

That is, the following method can be mentioned as a method for producing a laminate comprising a soft polypropylene layer and a thermoplastic resin layer.

The first method is a method in which soft polypropylene (soft PP) and a thermoplastic resin are multilayer coextruded from a molding machine having a multilayer die to form a multilayer cast molding film, or multilayer inflation molding is performed. At this time, in order to increase the adhesive force between layers, soft as the third component
An adhesive layer having an affinity for each of the PP and the thermoplastic resin layers may be provided, or an adhesive material may be preliminarily blended with either or both of the soft PP and the thermoplastic resin. When producing a multilayer cast film, the T-die temperature is set to 190 to 320 ° C., preferably 200 to 280 ° C., the cooling roll temperature is set to 90 ° C. or lower, and the take-up speed is 5 to 130 m / min, preferably 30. It is preferable to set in the range of up to 130 m / min. Especially chill roll temperature 90 ℃
If set to the following, an amorphous film can be obtained, and if the take-up speed and the extrusion speed ratio, that is, the draft ratio is 4 or less, a non-oriented raw sheet (film) can be obtained,
It is suitable for stretching.

In this way, or if necessary, a stretching treatment is then carried out to obtain the desired resin laminate. When a stretched multilayer film is produced by stretching here, as the stretching method, a method such as uniaxial stretching, tubular biaxial stretching, sequential biaxial stretching or simultaneous biaxial stretching may be appropriately selected and used. The conditions for this stretching process vary depending on the situation and are not uniquely defined, but usually the temperature is 80 ° C.
As described above, the melting point may be set to be equal to or lower than the melting point, and the draw ratio may be set to at least one of 3 times or more. Further, this stretched multilayer film is preferably subjected to a heat treatment as a post-treatment because sufficient dimensional stability can be obtained. The heat treatment temperature at this time varies depending on the melting point and glass transition temperature of the film used, but it is usually set to 80 to 160 ° C., and the treatment time is about 2 seconds to 20 minutes.

The second method is a method in which a soft PP film (stretched or unstretched) and a thermoplastic resin film (stretched or unstretched) are separately prepared in advance, and these are laminated. In this lamination, each film surface may be treated by corona treatment or ozone treatment, and an interlayer adhesive (for example, a dry laminating adhesive such as a curable urethane adhesive) should be used. You can also In addition, the press roll temperature at the time of lamination is about 40 to 100 ° C., and the processing speed is suitably 50 to 150 m / min.

The first and second methods can also be applied as a method for producing a laminate including a soft polypropylene layer which is a material layer other than the thermoplastic resin layer. Then, which manufacturing method is suitable for any configuration will be individually described with an example. First, the co-extrusion method that does not use adhesive is
And PP, ethylene-propylene copolymer, polybutene-1,
Suitable for lamination with ethylene vinyl acetate copolymer etc.
The co-extrusion method using an adhesive (carboxylic acid modified polypropylene, etc.) is suitable for laminating soft PP and PE, polystyrene (PS), etc. In the case of a laminate made of these materials, a method of laminating a film or sheet made of soft PP with another material layer coated with an adhesive is also suitable. In this case, a urethane adhesive is used as the adhesive. Soft
The method of laminating another material layer after co-extruding PP and an adhesive is suitable when a thermosetting resin, metal, paper, cloth, cellophane, rubber, wood, or the like is used as the other material layer. In the above production method, the extrusion temperature is not uniquely determined by the type of the material layer, but is usually set to 170 to 320 ° C, preferably 200 to 280 ° C.

The above-described laminate of the present invention has a low temperature heat-sealing property because the soft polypropylene layer has a welding temperature of about 143 ° C., a flexural modulus of about 3000 kg / cm ² , and a heat resistant temperature of 140 to 165 ° C. because of good characteristics. It has good properties, excellent flexibility, and excellent heat resistance. Therefore, for example, it is suitable for the following applications.

That is, if the present laminate is used as an outer layer or an intermediate layer of a packaging material used for general packaging, packaging of root vegetables, etc.,
It is possible to provide a packaging material having excellent earthquake resistance (particularly for blocks), flexibility and heat resistance. Specifically, a laminate having a constitution of homopolypropylene (HPP) / soft PP / random polypropylene (RPP) or EVA and a laminate having a constitution of RPP / soft PP / RPP are suitable for this packaging material. Further, when used as an inner layer of a packaging material, it is possible to provide a packaging material excellent in low temperature heat sealability and heat resistance. Specifically, a laminated body composed of nylon (NY) / soft PP, ethylene-
A laminate having a constitution of vinyl alcohol modified polymer (EVOH) / soft PP is suitable for this packaging material, and in particular, they can be used as a wrap film or a stretch film. In addition, it can be used for coating steel plates or steel pipes and automobile interiors with a laminate of metal and soft PP.
A book cover etc. that is flexible and excellent in texture can be manufactured by a laminate with PP, and a bag etc. can be manufactured by a laminate with leather and soft PP.

[Example] Example 1 A laminate was manufactured using homotype soft PP (soft homo PP) manufactured by the following method.

(A) a glass three-neck flask having an inner volume of 500ml was prepared thoroughly purged with nitrogen in Production Example (1) fixed catalyst component of the soft Moho polypropylene, purified heptane 20 ml, Mg (OEt) ₂ 4g and phthalate -n- butyl Add 1.2 g, keep the system temperature at 90 ° C, add ₄ ml of TiCl ₄ while stirring, and then add 111 ml of TiCl ₄
Was additionally charged and the temperature was raised to 110 ° C. After reacting for 2 hours at 110 ° C., it was washed with purified heptane at 80 ° C. 115 ml of TiCl ₄ was added to the obtained solid phase portion, and the mixture was further reacted at 110 ° C. for 2 hours. After completion of the reaction, the product was washed several times with 100 ml of purified heptane to give a solid catalyst component [corresponding to the solid catalyst component (ii) in the gas phase method].

(2) Preparation of solid component In a glass pressure-resistant _three- necked flask with an internal volume of 2.5 l that had been sufficiently replaced with nitrogen, 1.7 l of purified heptane, 0.07 mol of AlEt ₃ , 0.05 mmol of diphenyldimethoxysilane (DPDMS) and 120 g of the catalyst component of (1) above Was added. Keep the system at 30 ℃,
Propylene was continuously supplied with stirring, and the internal pressure was 0.5k.
It was kept at g / cm ² . This reaction was continued for 1 hour and then washed 5 times with 1 liter of purified heptane to obtain a solid component [corresponding to solid component (I) in the gas phase method].

(3) Gas-phase first-stage polymerization AlEt ₃ 3 mmol, 1-allyl-
0.15 mmol of 3,4-dimethoxybenzene (ADMB), 0.23 mmol of diphenyldimethoxysilane (DPDMS) and 100 mg of the solid component (I) of the above (2) (converted to Ti atom)
20 ml of a heptane solution containing 0.06 mmol) was added. After 5 minutes the exhaust the inside of the system, hydrogen gas was introduced up to 0.7 Kg / cm ^2, while supplying propylene gas until the total pressure is 28 kg / cm ²
Gas phase polymerization was carried out at 70 ° C. for 1.7 hours. 640 g of soft polypropylene having a melt index (MI) of 10 g / 10 min was obtained.
The boiling heptane-soluble matter (HSP) of this soft polypropylene
Min) was 46.8% by weight and the intrinsic viscosity was 1.13 dl / g. In addition, boiling heptane insoluble matter (HIP content) is 53.2% by weight.
And the intrinsic viscosity was 1.74 dl / g. Further ¹³ C-NMR
Rrrr / 1-mmmm is 34.5%, and melting peak temperature (Tm) measured by DSC is 158 ℃.
The melting enthalpy (ΔH) measured by DSC was 58.2 J / g, and the domain structure was observed in the observation with a transmission electron microscope.

(B) Manufacturing conditions The manufacturing conditions for the laminate are as follows. Homo PP (F-700N (trade name) manufactured by Idemitsu Petrochemical Co., Ltd.) was used for the other material layers.

・ Layer composition: soft homo PP / homo PP / soft homo PP (thickness ratio 1/8/1) ・ Film thickness: 30μm / 240μm / 30μm ・ Co-extrusion method ・ Molding machine used For soft homo PP: screw diameter 20mm Extruder Homo PP: Screw diameter 30mm Extruder Multi-manifold used ・ Molding condition: Resin temperature 250 ℃ ・ Extrusion amount Soft Homo PP: 1.1-1.2kg / Hr Moho PP: 9.5-9.5kg / Hr ・ Others: Chill roll temperature 35 C., air knife used, take-up speed 5 to 5.5 m / min. The produced laminate had a heat-sealing temperature of 143 ° C. and a heat-resistant temperature of 145 ° C. or higher, and exhibited excellent properties at low temperature heat-sealing property and heat resistance.

Example 2 Instead of the soft homo PP of Example 1, a block type soft PP (soft block PP) produced by the following method was used, and a laminate was produced under the same conditions as in Example 1.

Production Example of Soft Block Polypropylene Similar to the above-mentioned soft moho polypropylene, after the solid catalyst component and the solid component A were prepared, the procedure was as follows.

(1) First-stage gas phase polymerization In a 5 liter stainless steel pressure autoclave containing 20 g of polypropylene powder, AlEt ₃ 3 mmol, 1-allyl-
0.15 mmol of 3,4-dimethoxybenzene (ADMB), 0.23 mmol of diphenyldimethoxysilane (DPDMS), and 100 mg of the solid component (I) prepared in the above Production Example 1 (1) and (2) (0.06 in terms of Ti atom). 20 ml of a heptane solution containing (mmol) was added. After the inside of the system 5 minutes the exhaust, introducing hydrogen gas until 0.7 Kg / cm ^2, further total pressure was carried out for 1.7 hours gas phase polymerization at 70 ° C. while supplying propylene gas until 28Kg / cm ^2.

(2) Gas-Phase Second Stage Polymerization After the reaction of (1) above was completed, the system was depressurized and evacuated, then hydrogen gas 0.5 kg / cm ² , ethylene-propylene mixed gas (molar ratio 1/4) Is supplied up to 10 kg / cm ² and 1.4 at 50 ° C.
The gas phase polymerization was carried out for a time.

810 g of soft polypropylene with a melt index (MI) of 4.4 g / 10 min was obtained. This soft propylene is composed of 81% by weight of polypropylene homopolymer and 19% by weight of ethylene-propylene copolymer, and the homopolymer has a boiling heptane-soluble content (HSP content) of 46.8% by weight with an intrinsic viscosity of 1.13 dl / g. %
And boiling heptane insoluble matter (HIP content) with an intrinsic viscosity of 1.74 dl / g 5
3.2 wt%, the rrrr / 1-mmmm was 34.5% in the pentad fraction by ¹³ C-NMR, the melting peak temperature (Tm) measured by DSC was 158 ° C., the enthalpy of fusion measured by DSC (ΔH ) Was 58.2 J / g, and a domain structure was observed in a transmission electron microscope. On the other hand, the ethylene unit content of the copolymer was 39 mol% and the intrinsic viscosity was 1.77 dl / g.

As a result of the above example, a laminate having a heat sealing temperature of 143 ° C. and a heat resistant temperature of 145 ° C. or higher could be obtained as in Example 1.

Example 3 A laminate was manufactured by laminating a soft homo PP (same as in Example 1) layer and a nylon layer using an adhesive.

Layer composition is soft homo PP / adhesive / nylon / adhesive /
Soft homo PP (thickness ratio 1 / 0.5 / 8 / 0.5 / 1). In addition, as the nylon, ηr (relative accuracy) = 3.75 6-nylon (manufactured by Ube Industries, Ltd.) was used, and as the adhesive, carboxylic acid-modified polypropylene was used.

The molding machine used was the same as in Example 1 except that an extruder for adhesives was attached, and a feed block and a multi-manifold were used. Molding temperature is 250 ℃, nylon extrusion rate is 11.5-1
1.8Kg / Hr, carboxylic acid modified polypropylene extrusion rate is 0.6K
It was set to g / Hr.

Film thickness 30μm / 15μm / 240μm / 30μm with the above molding machine
The laminated film of
The film was stretched to 3 to give a film thickness of 3 μm / 1.5 μm / 27 μm / 1.5 μm / 3 μm.

This laminated film also has excellent heat resistance and oxygen impermeability,
It showed suitable properties as a wrap film.

Example 4 A laminate was manufactured by laminating a soft homo PP (same as in Example 1) layer and an EVOH layer using an adhesive.

The layer structure is soft homo PP / adhesive / EVOH / adhesive / soft homo PP. EVOH has an ethylene content of 32 mol% EP
-F (manufactured by Kuraray Co., Ltd.) was used, and the other conditions were the same as in Example 3.

The stretched film has excellent oxygen impermeability and heat resistance,
It showed suitable properties as a wrap film.

Example 5 A laminate was produced by laminating a soft homo PP (the same as in Example 1) layer and an aluminum layer using an adhesive. The layer structure is soft homo PP / adhesive / aluminum. In the production, an extruder for adhesive was attached to the soft PP extruder used in Example 1, co-extrusion of soft pp / adhesive = 30 μm / 15 μm was performed, and an aluminum foil having a thickness of 15 μm was laminated on it.

A bag was formed by heat-sealing the inner layer of the obtained film as soft PP, the heat-sealing temperature at this time was 143 ° C, the heat-resistant temperature was 145 ° C or higher, and the low-temperature heat-sealing property and heat resistance were excellent. , For example, showed suitable properties for retort pouches.

[Effects of the Invention] As described above, the laminate of the present invention can have a lower welding temperature than before, for example, 15 ° C by mainly using soft polypropylene, and further has flexibility and heat resistance. As a result, there is an effect that it can be used as a packaging material for various uses, a film material, a sheet material, etc., and its commercial value can be improved.

[Brief description of drawings]

1 (a), (b), and (c) are cross-sectional views showing a configuration example of the laminated body of the present invention. 100: Soft polypropylene layer 200: Other material layer

Claims (3)

(57) [Claims] 1. A laminate comprising a plurality of material layers, wherein at least one material layer is formed mainly of soft polypropylene, wherein the soft polypropylene is a polypropylene-based polymer (a) shown below (A), or (B)
A propylene-based composition (b) containing the polymer (a) shown in FIG. (A) (i) Boiling heptane soluble polypropylene 10-90
Wt% and boiling heptane-insoluble polypropylene 90 to 10 wt%, (ii) rrrr / (1-mmmm) is 20% or more in pentad fraction by ¹³ C-NMR, and (iii) differential calorimetric analyzer ( Melting peak temperature (T
m) is 150 ° C. or higher, and (iV) the enthalpy of fusion (ΔH) measured by DSC is 100 J / g or less (a) (B) (i) The polypropylene polymer (A) 10 to 95
% By weight, and (ii) an ethylene-propylene copolymer (c) having an ethylene unit content of 10 to 60 mol% and an intrinsic viscosity of 0.5 to 7.0 dl / g and / or an ethylene unit content of 10 to 60.
Polypropylene composition comprising 90 to 5% by weight of ethylene-propylene-polyene copolymer (c ') having a polyene unit content of 1 to 10% by mole and an intrinsic viscosity of 0.5 to 7.0 dl / g. (B) 2. The laminated body according to claim 1, comprising a material layer made of at least one of a thermoplastic resin and a thermosetting resin. 3. The laminate according to claim 1, wherein
A laminate, comprising at least a material layer made of metal, rubber, cloth, paper, wood, cellophane, or leather.