JP2987792B2 - Polyolefin-based multilayer sheet or film and applications - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer sheet or film in which polyolefin sheets or films are laminated, and more particularly to a polyolefin multilayer sheet or film suitable as a molding material for packaging.

[0002]

2. Description of the Related Art Packaging materials such as daily necessities, miscellaneous goods, food, tablets and the like are required to have many functions such as transparency, moisture proof, heat sealability, vacuum or pressure forming, and hand twisting. For this reason, these functions cannot be sufficiently satisfied with only one kind of resin, and a multilayer sheet or film obtained by laminating a sheet or film made of one resin and a sheet or film made of another resin is often used. .

[0003] On the other hand, in view of the problems during recycling and incineration, polyolefin resins tend to be preferred as materials. Cyclic olefin resins are excellent in transparency, moisture resistance, vacuum or pressure forming, dead hold, etc.
Because it is an amorphous resin, it softens rapidly near the glass transition temperature, and its elastic modulus, strength, and the like decrease. For this reason, there is a problem that a range of molding conditions in heat sealing, inflation molding, vacuum or pressure molding is narrow.

[0004] Such problems can be solved by laminating a sheet or film made of a cyclic olefin-based resin and a sheet or film made of a polypropylene resin which is a crystalline resin to form a multilayer. And polypropylene resin have low affinity, so that when molded by a co-extrusion molding method, a new problem arises in that the interface is hardly adhered and easily peeled.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems by providing interlayer adhesion, moldability, moisture resistance,
An object of the present invention is to provide a polyolefin-based multilayer sheet or film excellent in transparency, heat sealing property and dead hold property, and also excellent in vacuum or pressure forming property, and a sheet or film for packaging.

[0006]

SUMMARY OF THE INVENTION The present invention provides the following polyolefin-based multilayer sheet or film, and a packaging sheet or film comprising the same. (1) (A) (a) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 10 dl / g, and the softening temperature (T
(B) 135, a copolymer of ethylene and a cyclic olefin represented by the following general formula [1], wherein MA) is 50 ° C. or higher:
° C. intrinsic viscosity [η] measured in decalin is 0.01 to
A ring-opening (co) polymer of a cyclic olefin represented by the following general formula [1] or a hydrogenated product thereof, which has a softening temperature (TMA) of 50 deg.
The ethylene / cyclic olefin random copolymer (a)
Alternatively, at least one sheet or film composed of a cyclic olefin resin as a ring-opened (co) polymer of a cyclic olefin or a hydrogenated product thereof (b), and (B) a polypropylene resin, and having a density of 0.93
A polyolefin-based multilayer sheet or film, wherein at least one sheet or film made of a polypropylene resin composition comprising 0 g / cm ³ or more of a polyethylene resin is laminated.

Embedded image (In the formula [1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R
¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. You may. Here, when q is 0, the respective bonds are combined to form a 5-membered ring. (2) The polyolefin-based multilayer sheet or film according to the above (1), wherein the cyclic olefin-based resin (A) is an ethylene / cyclic olefin random copolymer (a). (3) A packaging sheet or film comprising the polyolefin-based multilayer sheet or film according to (1) or (2).

Hereinafter, the resin used as the material of the multilayer sheet or film of the present invention will be described. (A) Cyclic olefin-based resin First, (A) the cyclic olefin-based resin which is a material of the film of one layer of the multilayer sheet or film of the present invention will be described. Examples of the cyclic olefin resin used in the present invention include (a) a random copolymer of ethylene and the cyclic olefin represented by the above formula [1], and (b) opening of a cyclic olefin represented by the formula [1]. A ring (co) polymer or a hydride thereof, or (c) a graft-modified product of the above (a) or (b) can be mentioned.

[0008] The cyclic olefin resin used in the present invention has a softening temperature (TMA) of 50 ° C or higher, preferably 60 ° C, as measured by a thermal mechanical analyzer.
To 180 ° C, more preferably 70 to 180 ° C.

The cyclic olefin resin has an intrinsic viscosity [η] of 0.01 to 10 as measured in decalin at 135 ° C.
dl / g, preferably 0.05 to 2.0 dl / g.
g, more preferably 0.4 to 1.2 dl / g.

The cyclic olefin resin has a glass transition point (Tg) of usually 30 ° C. or higher, preferably 40 ° C. or higher.
To 170 ° C., and the degree of crystallinity measured by X-ray diffraction is usually 0 to 20%, preferably 0 to 2%.

First, the cyclic olefin represented by the general formula [1] used for forming the above-mentioned cyclic olefin resin will be described. In the above formula [1], R ^{1 to} R ¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.

Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Moreover, as a hydrocarbon group, each independently usually has 1 to 1 carbon atoms.
Examples thereof include an alkyl group having 20 atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. And a group in which at least a part of the hydrogen atoms forming the above-mentioned alkyl group is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Further, in the above formula [1], R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ represent R
R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ are bonded to each other (together with each other) to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring thus formed may have a double bond. Specific examples of the monocyclic or polycyclic ring formed here include the following.

[0014]

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In the above examples, the carbon atoms numbered 1 or 2 represent R in formula [1]
Represents a carbon atom to which ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded. Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

Further, as the cyclic olefin represented by the above formula [1], a compound represented by the following general formula [2] can be exemplified.

Embedded image (In the formula [2], h is 0 or a positive integer, j
And k are 0, 1 or 2. m, R ^{7 to} R ¹⁵ and R ^{17 to} R ¹⁸ represent the same as those in the formula [1]. R ¹⁹ ~R ²⁷
Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and an alkoxy group. )

Here, the halogen atom is the same as the halogen atom in the formula [1]. Further, R ^19-
As the hydrocarbon group for R ²⁷ , each is usually an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic group. And a hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. ,
Examples thereof include groups in which at least a part of the hydrogen atoms forming the above-mentioned alkyl group has been substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specific examples include a phenyl group, a tolyl group, a naphthyl group, and a benzyl group. And a phenylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. Where R ¹⁷
And the carbon atom to which R ¹⁸ is bonded and the carbon atom to which R ²¹ is bonded or the carbon atom to which R ¹⁹ is bonded are bonded directly or via an alkylene group having 1 to 3 carbon atoms. You may. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ¹⁷ and R ²¹ or the groups represented by R ¹⁸ and R ¹⁹ cooperate with each other. Te, a methylene group (-CH ₂ -), ethylene group (-CH ₂ CH ₂ -) or propylene group (-C
H ₂ CH ₂ CH ₂ —) to form any alkylene group.

Further, when j = k = 0, R ²³ and R ²⁰ or R ²³ and R ²⁷ may combine with each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include R ²³ and R ²³ when j = k = 0.
^The following groups and the like in which ²⁰ further forms an aromatic ring can be mentioned.

[0021]

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In the above example, h represents the same as h in the formula [2]. Specific examples of the cyclic olefin represented by the above formula [1] or [2] include bicyclo [2.2.1] hept-2-ene derivatives and tetracyclo [4.4.0.1]. ^2,5 . 1 ^7,10 ] -3-dodecene derivative,
Hexacyclo [6.6.1 1.1 ^3,6. 1 ^{10 and 13.} 0 ^2,7. 0 ^9,14]
4-heptadecene derivative, octacyclo [8.8.0.
1 ^2,9. 1 ^4,7. 1 ^{11, 18.} 1 ^13,16. 0 ^3,8. 0 ^12,17] -5-docosene derivatives, pentacyclo [6.6.1 1.1 ^3,6. 0 ^2,7.0
9,14] -4-hexadecene derivative, heptacyclo-5-eicosene derivatives, heptacyclo-5-heneicosene derivatives,
Tricyclo [4.3.1 0.1 ^2,5] -3-decene derivatives, tricyclo [4.4.1 0.1 ^2,5] -3-undecene derivatives, pentacyclo [6.5.1 1.1 ^3,6 . 0 ^2,7. 0 ^9,13] -4-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [7.4.1 .1 ^2,5. 1 ^9,12. 0 ^8,13] -3- pentadecene derivatives, heptacyclo [8. 7. 0.1 ^3,6. 1 ^{10, 17.} 1
^{12 and 15.} 0 ^2,7. 0 ^11,16] -4-eicosene derivatives, Nonashikuro [10. 9.1.4 1 ^4,7. 1 ^{13, 20.} 1 ^{15, 18.} 0 ^3,8. 0 ^{2 ,} 10.0
^{12 and 21.} 0 ^{14,1 9]} -5-pentacosene derivatives, pentacyclo [8.4.1 .1 ^2,5. 1 ^9,12. 0 ^8,13] -3-hexadecene derivative, heptacyclo [8.8 . 0. 1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0
^3,8. 0 ^12,17] -5-heneicosene derivatives, Nonashikuro [10. 10. 1.1 ^5,8. 1 ^{14, 21.} 1 ^{16, 19.} 0 ^2,11. 0 ^4,9. 0
. ^{13, 22} 0 ^{15, 20]} -5-hexacosenoic derivatives, 1,4-methano -
1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano
-1,4,4a, 5,10,10a-hexahydroanthracene derivative,
And cyclopentadiene-acenaphthylene adduct.

The following formula (1) or (2)
A more specific example of the cyclic olefin represented by is shown below.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The cyclic olefin represented by the above general formula [1] or [2] can be produced by subjecting cyclopentadiene to an olefin having a corresponding structure by a Diels-Alder reaction.

These cyclic olefins can be used alone or in combination of two or more. The cyclic olefin resin (A) used in the present invention can be prepared by using the cyclic olefin represented by the formula [1] or [2] as described above, for example, in JP-A-60-168708 and JP-A-61-1986. JP-A-120816, JP-A-61-115912
JP, JP-A-61-115916, JP-A-61-161916
JP-A-271308, JP-A-61-272216, JP-A-62-252406, and JP-A-62-2
In accordance with the method proposed by the present applicant in Japanese Patent No. 52407 and the like, it can be produced by appropriately selecting conditions.

(A) Ethylene / cyclic olefin random copolymer (a) The (a) ethylene / cyclic olefin random copolymer used as (A) the cyclic olefin resin in the present invention is:
Usually, 52 to 90 mol%, preferably 55 to 80 mol% of the structural unit derived from ethylene and 10 to 48 mol%, preferably 20 to 45 mol% of the structural unit derived from the cyclic olefin are used. It is contained in the amount. The ethylene composition and the cyclic olefin composition are measured by ¹³ C-NMR.

In the ethylene / cyclic olefin random copolymer (a), the structural units derived from ethylene and the structural units derived from the cyclic olefin are randomly arranged and bonded, and Has a linear structure. The fact that this copolymer is substantially linear and has substantially no gel-like cross-linked structure should be confirmed by dissolving this copolymer in an organic solvent and containing no insoluble matter. Can be. For example, when the intrinsic viscosity [η] is measured as described later, the copolymer has a temperature of 135 ° C.
It can be confirmed by completely dissolving in decalin.

In the ethylene / cyclic olefin random copolymer (a) used in the present invention, at least a part of the structural units derived from the cyclic olefin represented by the above formula [1] or [2] has the following structure. The structural formula [1-
a] or [2-a].

[0050]

Embedded image (In the formula [1-a], n, m, q, R ^{1 to} R ¹⁸ and R ^a and R ^b represent the same as in the formula [1].
In a), m, h, j, k, R ^{7 to} R ¹⁵ and R ¹⁷
To R ²⁷ represent the same as those in the formula [2]. )

Further, the (a) ethylene
The cyclic olefin random copolymer may contain a structural unit derived from another copolymerizable monomer, if necessary, as long as the object of the present invention is not impaired.

Examples of such other monomers include olefins other than the above-described ethylene or cyclic olefin, norbornenes, non-conjugated dienes, and the like. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-
Methyl-1-pentene, 3-ethyl-1-pentene, 4
-Methyl-1-pentene, 4-methyl-1-hexene,
4,4-dimethyl-1-hexene, 4,4-dimethyl-
Carbon such as 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene Equations 3 to 20
Olefin, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2 (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano- Cycloolefins such as 1H-indene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene, 5-n-butyl-2-norbornene, 5-isobutyl- 2-norbornene, 5,
Norbornenes such as 6-dimethyl-2-norbornene, 5-chloro-2-norbornene, 5-fluoro-2-norbornene, 1,4-hexadiene, 4-methyl-
1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene,
Non-conjugated dienes such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.

These other monomers can be used alone or in combination of two or more. (A) In the ethylene / cyclic olefin random copolymer, the constituent units derived from the other monomers as described above may be contained in an amount of usually 20 mol% or less, preferably 10 mol% or less.

The ethylene / cyclic olefin random copolymer (a) used in the present invention is prepared by using ethylene and the cyclic olefin represented by the formula [1] or [2] as disclosed in the above publication. Can be manufactured. Among these, this copolymerization is carried out in a hydrocarbon solvent, and using a catalyst formed from a vanadium compound and an organoaluminum compound soluble in this hydrocarbon solvent as a catalyst, (a) an ethylene / cyclic olefin random copolymer It is preferred to produce

(B) Ring-Opening Polymer or Copolymer of Cyclic Olefin The (b) ring-opening polymer or ring-opening copolymer of cyclic olefin used in the present invention is represented by the above formula [1] or [2]. It comprises a structural unit derived from the cyclic olefin represented, and at least a part of this structural unit has the following formula [1-
b] or [2-b].

[0056]

Embedded image (In the formula [1-b], n, m, q, R ^{1 to} R ¹⁸ and R ^a and R ^b represent the same as in the formula [1].
b), m, h, j, k, R ^{7 to} R ¹⁵ and R ¹⁷
To R ²⁷ represent the same as those in the formula [2]. )

Such a ring-opening polymer or ring-opening copolymer can be produced by the production method disclosed in the above-mentioned publication. Specifically, it can be produced by polymerizing or copolymerizing the cyclic olefin represented by the formula [1] or [2] in the presence of a ring-opening polymerization catalyst.
As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide selected from ruthenium, rhodium, palladium, osmium, indium or platinum, a nitrate or an acetylacetone compound, and a reducing agent, or titanium, palladium, zirconium Alternatively, a catalyst comprising a metal halide or acetylacetone compound selected from molybdenum and the like and an organoaluminum compound can be used.

The hydride of the ring-opening polymer or copolymer (b) used in the present invention can be obtained by converting the ring-opening polymer or copolymer obtained as described above into a conventionally known hydrogenation catalyst. Obtained by hydrogenation in the presence of

In this (b) hydride of the ring-opened polymer or copolymer, at least a part of the structural units derived from the cyclic olefin represented by the formula [1] or [2] has the following formula [ 1-c] or [2-c].

[0060]

Embedded image (In the formula [1-c], n, m, q, R ^{1 to} R ¹⁸ and R ^a and R ^b represent the same as in the formula [1].
c), m, h, j, k, R ^{7 to} R ¹⁵ and R ¹⁷
To R ²⁷ represent the same as those in the formula [2]. )

(C) Graft Modified Product The graft modified product of the (c) cyclic olefin resin used in the present invention can be obtained by using the above (a) ethylene / cyclic olefin random copolymer or (b) cyclic olefin It is obtained by graft-modifying a part of a ring-opening (co) polymer or a hydride thereof with a modifying agent.

Examples of the modifying agent include unsaturated carboxylic acids such as maleic anhydride, and derivatives thereof such as acid anhydrides and alkyl esters of unsaturated carboxylic acids.
In the graft modified product of the cyclic olefin resin used in the present invention, the content of the structural unit derived from the modifier is usually 10 mol% or less.

Such a graft modified product of a cyclic olefin resin can be produced by blending a modifier with the cyclic olefin resin so as to obtain a desired modification ratio and graft-polymerizing the same. It can also be produced by preparing a modified product and then mixing the modified product with an unmodified cyclic olefin resin.

The (A) cyclic olefin resin used in the present invention is selected from the group consisting of (a), (b) and (c) as described above, and is a combination of two or more of these. Is also good. In the present invention, (a) an ethylene / cyclic olefin random copolymer is preferably used as the (A) cyclic olefin-based resin.

The (A) cyclic olefin-based resin used in the present invention may contain a rubber component for improving impact strength as another component, or other resin as long as the object of the present invention is not impaired. Ingredients, heat stabilizers, weather stabilizers, light stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, nucleating agents, lubricants, dyes that absorb only light of a specific wavelength, pigments, natural oils, synthetic Oils, waxes or translucent fillers can be incorporated.

For example, as a stabilizer blended as an optional component, specifically, tetrakis [methylene-3 (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-tert-butyl-4-)
(Hydroxyphenyl) propionic acid alkyl ester,
2,2'-oxamidobis [ethyl-3 (3,5-di-
phenolic antioxidants such as t-butyl-4-hydroxyphenyl) propionate]; zinc stearate;
Fatty acid metal salts such as fatty acid calcium such as calcium stearate and calcium 12-hydroxystearate; fatty acid esters of polyhydric alcohols; and the like.

These may be blended alone, for example, tetrakis [methylene-3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate] methane and a combination of zinc stearate and glycerin monostearate. In the present invention,
It is preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol. As such a fatty acid ester of the polyhydric alcohol, a part of the alcoholic hydroxyl group of the trihydric or higher polyhydric alcohol is esterified. And polyhydric alcohol fatty acid esters.

Examples of such fatty acid esters of polyhydric alcohols include glycerin monostearate,
Glycerin fatty acid esters such as glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin dilaurate; pentaerythritol monostearate (p
entaerythritol mono star
ate), fatty acid esters of pentaerythritol such as pentaerythritol monolaurate, pentaerythritol distearate and pentaerythritol tristearate. These may be used alone or in combination with each other.

The phenolic antioxidant is used in an amount of less than 10 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the essential components.
It is desirable to use less than 2 parts by weight, more preferably less than 2 parts by weight. The fatty acid ester of the polyhydric alcohol is desirably used in a proportion of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the total of essential components.

(B) Polypropylene Resin Composition Next, the polypropylene resin composition which is the material of the film of the other layer of the multilayer sheet or film of the present invention will be described. The polypropylene resin used in the present invention is a homopolymer of propylene or a copolymer of propylene having a propylene content of 90 mol% or more, preferably 94 mol% or more and another α-olefin,
The melt flow rate at 230 ° C is 0.05 to 100 g /
10 min, preferably 0.5 to 50 g / 10 min,
The density is 0.89 to 0.93 g / cm ³ , preferably 0.1 to 0.93 g / cm ³ .
90 to 0.92 g / cm ³ , 4.6 kg / cm ² heat deformation temperature under load of 90 to 140 ° C., preferably 100 to 130 ° C.
It is desirable to use one in the range of ° C.

Other α-olefins copolymerized with propylene include ethylene, 1-butene, 1-pentene,
-Hexene, 3-methyl-1-butene, 3-methyl-1
-Pentene, 3-ethyl-1-pentene, 4-methyl-
1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1- Octene, 1-decene, 1-dodecene, 1-
Examples thereof include ethylene such as tetradecene and those having 4 to 14, preferably 4 to 10 carbon atoms.

As the polyethylene resin used in the present invention, an ethylene homopolymer or an ethylene content of 9
0 mol% or more, preferably 95 mol% or more of a copolymer of ethylene and another α-olefin, having a density of 0.1 mol% or more.
930 g / cm ³ or more, preferably 0.940 to 0.9
80 g / cm ³ is used. As other physical properties,
The melt flow rate at 190 ° C is 0.01 to 100 g /
10 min, preferably 0.03 to 50 g / 10 mi
n, Vicat softening point is 110-140 ° C, preferably 1
It is desirable to use one in the range of 15 to 130 ° C.

Other α-olefins copolymerized with ethylene include propylene, 1-butene, 1-pentene,
-Hexene, 3-methyl-1-butene, 3-methyl-1
-Pentene, 3-ethyl-1-pentene, 4-methyl-
1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1- Octene, 1-decene, 1-dodecene, 1-
3-14 carbon atoms such as tetradecene, preferably 3-1
0 is given.

The mixing ratio of the polypropylene resin and the polyethylene resin is 90 to 40:10 to 60, preferably 85 to 5 in terms of the weight ratio of the polypropylene resin to the polyethylene resin.
0: 15-50 is desirable.

In the polypropylene resin composition, in addition to the polypropylene resin and the polyethylene resin, a rubber component for improving impact strength may be blended as another component within a range not impairing the object of the present invention. Ingredients, heat stabilizer, weather stabilizer, light stabilizer, antistatic agent, slip agent, antiblocking agent, antifogging agent, nucleating agent, lubricant,
Dyes, pigments, natural oils, synthetic oils, waxes, translucent fillers, and the like that absorb only light of a specific wavelength can be added.

Known methods can be used for producing the polypropylene resin composition.
Examples thereof include a method of mixing with a blender, a ribbon blender, a tumbler blender and the like, a method of mixing and kneading with a single-screw extruder, a twin-screw extruder, a kneader or the like, followed by granulation or pulverization.

The polyolefin-based multi-layer sheet or film of the present invention comprises: (A) a sheet or film comprising a composition of a cyclic olefin-based resin or other components optionally blended therewith; ) Laminated, that is, a laminate of a polypropylene resin composition or a sheet or film composed of the composition with another component blended as required. As the form of lamination, a layer of the polypropylene resin composition (B) /
Cyclic olefin resin (A) layer / polypropylene resin composition (B) layer, cyclic olefin resin (A) layer / polypropylene resin composition (B) layer / cyclic olefin resin (A) layer, polypropylene resin composition ( Any form such as B) layer / cyclic olefin-based resin (A) layer may be used.

In order to form a polyolefin-based multilayer sheet or film, a general multilayer sheet or film forming method such as a co-extrusion method such as a multilayer-die method and a multilayer inflation method can be employed. The molded polyolefin-based multilayer sheet or film can be used as it is without stretching, or after uniaxial or biaxial stretching. Further, in order to provide other functions, it can be used by further laminating it with a coat such as vinylidene chloride or another resin film.

The polyolefin-based multi-layer sheet or film of the present invention is excellent in interlayer adhesion, moisture resistance, transparency and dead-holding property, and also excellent in vacuum or pressure forming properties, so that it can be used for packaging medicines, foods and tobacco. Demonstrates sufficient performance as a material for Therefore, the polyolefin-based multilayer sheet or film of the present invention can be suitably used as a packaging sheet or film.

Examples of the packaged items include drugs, foods, daily necessities,
Arbitrary items such as miscellaneous goods can be given. In particular, when used for packaging medicines such as tablets and capsules, foods such as rice crackers, snacks and cookies, and hygroscopic articles such as tobacco and tea bags, moistureproofness and transparency are guaranteed. Packaging forms include bags, packs, PTP (press thro
high pack), blister packs, hand twists, wrappings, shrings, easy peels and other films.

[0081]

As described above, according to the present invention, a sheet or film composed of a specific cyclic olefin resin and a sheet or film composed of a polypropylene resin composition having good adhesion to the sheet or film are provided. Because it is laminated, it is excellent in interlayer adhesion, moldability, moisture proof, transparency, heat sealability and dead hold property, and also very good polyolefin-based multilayer as packaging material with excellent vacuum or air pressure moldability. A sheet or film is obtained.

Further, according to the present invention, the polyolefin-based multilayer sheet or film is excellent in interlayer adhesion, moldability, moisture proofing, transparency, heat sealability and dead holdability, and has vacuum or air pressure moldability. Also, an excellent packaging sheet or film can be obtained.

[0083]

Next, an embodiment of the present invention will be described. As Example 1 cycloolefin resin (A), the ethylene and 8-ethyl tetracyclo [4.4. 0.1 ^2,5. 1 ^7,10] -3-dodecene (the formula [1], n = 0, m = 1, R ⁷ ~
A random copolymer of R ¹⁴ and R ^{16 to} R ¹⁸ with a hydrogen atom and a cyclic olefin in which R ¹⁵ is an ethyl group (hereinafter abbreviated as ETCD-3), having an intrinsic viscosity [η] of 0.67.
dl / g and a softening temperature (TMA) of 90 ° C. were used.

As the polypropylene resin composition (B),
230 ° C melt flow rate (measurement method: ASTM D
1238) is 7.2 g / 10 min, density (measurement method: A
STM D1505) is 0.91 g / cm ³ , the crystallinity by X-ray diffraction is 58%, the heat distortion temperature under a load of 4.6 kg / cm ² (measurement method: ASTM D648) is 112 ° C. polypropylene and 190 ° C. Melt flow rate is 5.5 g / 10 min, density is 0.968 g / cm ³ ,
Vicat softening point (measurement method: ASTM D1525) is 1
A composition obtained by melt blending polyethylene at 25 ° C. with an extruder at a weight ratio of polypropylene: polyethylene of 6: 4 was used.

These raw materials were used under the following conditions under the following conditions: polypropylene resin composition (B) layer / cyclic olefin resin (A) layer /
Two- and three-layer extruded sheets having the structure of the polypropylene resin composition (B) layer were prepared, and sheet physical properties, moldability, and interlayer adhesion between the polypropylene resin composition layer and the cyclic olefin resin layer were evaluated by the following methods. Table 1 shows the results.

(Molding conditions) Molding machine: Two-type three-layer extruder Screw: Cyclic olefin resin (A) layer; diameter 30 mm, L / D
= 24, mild compression full flight type polypropylene resin composition (B) layer; diameter 40 mm, L
/ D = 28, slow compression full flight type Cylinder temperature: Cyclic olefin resin (A) layer; 200 ° C Polypropylene resin composition (B) layer; 200 ° C Dice: T-die Black box type

(Evaluation Method) Thickness of each layer: Cut the formed sheet in the thickness direction,
The cross section was observed with a microscope and measured. 2. Light transmittance: performed according to ASTM D1003. 3. Moisture permeability coefficient: Performed according to ASTM F1249.
3. 40 ° C., 90% relative humidity Interlaminar adhesiveness: To remove the edges of two- and three-layer sheets,
Those that peeled off had poor interlayer adhesion. 5. Continuous vacuum pressure forming: width 10 mm, length 150 mm
A two-layer, three-layer sheet cut into strips of
After holding for 1 minute, the sample was pulled under a load of 1 kg / cm ² , and a sample having an elongation of 1% or less was accepted.

Example 2 Polypropylene resin composition used in Example 1
Instead of (B), the melt flow rate at 230 ° C is 1
1.5g / 10min, density 0.91g / cm ^Three, X
Crystallinity by line diffraction is 59%, 4.6 kg / cm^Twoload
Heavy polypropylene having a heat distortion temperature of 110 ° C .;
Melt flow rate at 6.1 ° C is 6.1 g / 10 min, density
Is 0.957 g / cm^ThreeWith a Vicat softening point of 115 ° C
Polyethylene and polypropylene: polyethylene heavy
Performed in the same manner as in Example 1 except that the quantitative ratio was 6: 4.
Was. Table 1 shows the results.

Comparative Example 1 Instead of the polypropylene resin composition (B) used in Example 1, no polyethylene was blended.
The procedure was performed in the same manner as in Example 1 except that polypropylene was used alone. Table 1 shows the results.

[0090]

[Table 1]

From the results shown in Table 1, it can be seen that the sheets of Examples have improved interlayer adhesiveness without lowering the light transmittance, moisture permeability coefficient, and continuous vacuum pressure-air moldability.

Claims (3)

(57) [Claims] (A) (a) An intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 10 dl / g and a softening temperature (TMA) of 50 ° C. or more are represented by the following general formula [1]: ]
An ethylene / cyclic olefin random copolymer comprising a copolymer of a cyclic olefin and ethylene represented by
(B) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.01 to 10 dl / g and the softening temperature (TMA) is 50
C. or higher, a ring-opened (co) polymer of a cyclic olefin represented by the following general formula [1] or a hydrogenated product thereof, or (c) the ethylene / cyclic olefin random copolymer (a) or a cyclic olefin At least one sheet or film comprising a cyclic olefin-based resin as a ring-opened (co) polymer or a hydrogenated product thereof (b), and (B) a polypropylene resin, and having a density of 0.930 g.
A polyolefin-based multilayer sheet or film, wherein at least one sheet or film made of a polypropylene resin composition made of a polyethylene resin of at least / cm ³ is laminated. Embedded image (In the formula [1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R
¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. You may. Here, when q is 0, the respective bonds are combined to form a 5-membered ring. ) 2. The polyolefin multilayer sheet or film according to claim 1, wherein the cyclic olefin resin (A) is an ethylene / cyclic olefin random copolymer (a). 3. A packaging sheet or film comprising the polyolefin-based multilayer sheet or film according to claim 1.