JPH06226935A - Multilayer polyolefin sheet or film and intended use thereof - Google Patents

Abstract

(57) [Summary] [Purpose] To obtain a very good multilayer film as a packaging material excellent in interlayer adhesion, moldability, moisture resistance, transparency, heat sealability, and dead hold. [Constitution] A) 70 to 99% by weight of crystalline polyolefin
And a film comprising a crystalline polyolefin resin composition comprising 1 to 30% by weight of a hydrogenated alicyclic petroleum resin,
B) The intrinsic viscosity measured in decalin at 135 ° C is 0.01.
-10 dl / g, softening temperature of 50 ℃ or more, a polyolefin-based multi-layer film laminated with a film made of an ethylene / cyclic olefin random copolymer in which a cyclic olefin represented by the following formula and ethylene are copolymerized . [Chemical 1] (N and q are 0 or 1, m is 0 or a positive integer, R ^{1 to} R
¹⁸ , R ^a and R ^b represent H, halogen or a hydrocarbon group. R
^{15 to} R ¹⁸ may combine with each other to form a ring, and the ring may have a double bond. Also with R ¹⁵ and R ¹⁶ , or
R ¹⁷ and R ¹⁸ may form an alkylidene group. )

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, sundries, foods, tablets and chemicals are required to have many functions such as transparency, moisture resistance, heat sealability, vacuum or pressure molding and hand twist molding. Therefore, these functions cannot be sufficiently satisfied with only one type of resin, and a multilayer sheet or film in which a sheet or film made of one resin and a sheet or film made of another resin are superposed is often used. .

On the other hand, in consideration of problems at the time of recycling and incineration, there is a tendency that a polyolefin resin is preferred as a material. Cyclic olefin resins are excellent in transparency, moisture resistance, vacuum or pressure molding, dead hold, etc.
Since it is an amorphous resin, it softens rapidly near the glass transition temperature, and the elastic modulus, strength, etc. decrease. For this reason, there is a problem that the molding condition width in heat sealing, inflation molding, vacuum or pressure molding is narrow.

Such problems can be solved by stacking a sheet or film made of a cyclic olefin resin and a sheet or film made of a polypropylene resin which is a crystalline resin to form a multilayer structure. Since polypropylene resin and polypropylene resin have a low affinity, when they are molded by a co-extrusion molding method, there arises a new problem that the interface is difficult to adhere and peels off easily.

[0005]

DISCLOSURE OF THE INVENTION It is an object of the present invention to solve the above problems by providing interlayer adhesion, moldability, moisture resistance,
(EN) It is intended 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 air moldability, and a packaging sheet or film.

[0006]

The present invention is the following polyolefin-based multilayer sheet or film, and a packaging sheet or film comprising them. (1) (A) 70 to 99% by weight of crystalline polyolefin,
And at least one sheet or film of a crystalline polyolefin resin composition comprising 1 to 30% by weight of a hydrogenated alicyclic petroleum resin, and (B) (a) an intrinsic viscosity [η measured in decalin at 135 ° C. ] Is 0.01 to 10d
An ethylene / cyclic olefin random copolymer comprising a copolymer of a cyclic olefin represented by the following general formula [1] and ethylene, having a ratio of 1 / g and a softening temperature (TMA) of 50 ° C. or higher, (b) 135. Intrinsic viscosity [η] measured in decalin at 0.01 to 0.01 dl / g, softening temperature (TM
The ring-opening (co) polymer of a cyclic olefin represented by the following general formula [1] or a hydrogenated product thereof having A) of 50 ° C. or higher, or (c) the ethylene / cyclic olefin random copolymer (a). ) Or a ring-opened (co) polymer of a cyclic olefin or a graft-modified product of a hydrogenated product (b) thereof, and at least one sheet or film made of a cyclic olefin resin, which are laminated. Sheet or film.

[Chemical 2] (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 ^1
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. May be. Here, when q is 0, the respective bonds bond to each other to form a 5-membered ring. (2) The crystalline polyolefin is polypropylene having a crystallinity of more than 30% (1).
The polyolefin-based multilayer sheet or film described. (3) The polyolefin-based multilayer sheet or film as described in (1) or (2) above, wherein the cyclic olefin resin (B) is an ethylene / cyclic olefin random copolymer (a). (4) A packaging sheet or film comprising the polyolefin-based multilayer sheet or film according to any one of (1) to (3) above.

The resin used as the material for the polyolefin-based multilayer sheet or film of the present invention will be described below. (A) Crystalline Polyolefin Composition First, the (A) crystalline polyolefin resin composition that is a material for the film of one layer of the polyolefin-based multilayer sheet or film of the present invention will be described. The crystallinity of the crystalline polyolefin used in the present invention is usually 30% or more, preferably 45% or more, more preferably 55% or more, as measured by X-ray diffractometry.

The crystalline polyolefin has a tensile modulus at 23 ° C. of usually more than 2000 kg / cm ² , preferably 5000 to 20000 kg / cm ^2.
2 , more preferably 10,000 to 20,000 kg / c
m ² .

The crystalline polyolefin used in the present invention preferably has the following physical properties. The density is usually 0.88 to 0.92 g / cm ³ , and the melt flow rate (MFR) is usually 0.01 to 300 g / 1.
0 min, preferably 0.1 to 100 g / 10 min, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) is usually 0.5 to 5 dl / g, and the melting point is usually 120 to 180.
C., the glass transition temperature is usually −20 to 20 ° C., and the softening temperature is usually 100 to 170 ° C.

Specific examples of such crystalline polyolefin include crystalline polypropylene. The crystalline polypropylene used in the present invention may be a propylene homopolymer or a copolymer of propylene and another α-olefin.

Examples of other α-olefins forming a propylene copolymer include α-olefins having 2 to 20 carbon atoms excluding propylene, and specifically, ethylene, 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-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1
-Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.

Propylene used in the present invention and other α-
The copolymer with an olefin contains a structural unit derived from propylene in an amount of 50 mol% or more, preferably 80 mol% or more.

The crystalline polyolefin used in the present invention contains a structural unit derived from a chain non-conjugated diene and / or a structural unit derived from a cyclic non-conjugated diene within a range that does not impair the crystallinity. It may be contained in an amount of usually 5 mol% or less, preferably 3 mol% or less.

The crystalline polyolefin as described above is produced by various conventionally known methods. For example, a composite catalyst containing an organoaluminum compound such as triethylaluminum and a solid titanium catalyst component such as titanium chloride is used. Reaction pressure is 1 to 40 atm, reaction temperature is 20 to 1
Produced by subjecting propylene or propylene and another α-olefin to liquid phase polymerization in an unsaturated hydrocarbon solvent under the condition of 20 ° C., decomposing and removing the catalyst with water, and then removing the solvent. To be done.

As the hydrogenated (hydrogenated) alicyclic petroleum resin used in the present invention, a cyclopentene fraction or a cyclohexene fraction is homopolymerized or copolymerized [hereinafter,
(Co) polymerization] and hydrogenated. For example, a hydrogenated alicyclic petroleum resin obtained by (co) polymerizing a cyclopentene-based fraction and hydrogenating the same can be represented by the following formula.

[0016]

[Chemical 3]

Further, as the hydrogenated alicyclic petroleum resin used in the present invention, for example, a resin obtained by hydrogenating an alicyclic polymer obtained by (co) polymerizing the following monocyclic or polycyclic olefins Can be given. This alicyclic polymer does not include the (b) cyclic olefin ring-opening (co) polymer described below.

The above-mentioned monocyclic or polycyclic cyclic olefins include cyclopentene derivatives, cyclohexene derivatives, bicyclo [2.2.1] hept-2-ene derivatives, tetracyclo [ ^4.4.0.12,5 . 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-icosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4.3.1 0.1 ^2,5] -3-decene derivatives, tricyclo [4. 4.0 .1 ^2,5 ] -3-Undecene derivative, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] -4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo [ 4.7.1 0.1 ^2,5. 0 ^8,13. 1 ^{19, 12]} -3-pentadecene derivatives, heptacyclo [7.8.3 0.1 ^3,6. 0 ^2,7. 1
^{10, 17.} 0 ^{11, 16.} 1 ^12,15] -4-eicosene derivatives, and Nonashikuro [9. 10. 1.1 ^4,7. 0 ^3,8. 0 ^2,10. 0 ^{12 and 21.} 1
^{13, 20.} 0 ^{14, 19,} etc.. 1 ^{15,1 8]} -5-pentacosene derivatives.

Specific examples of such a hydrogenated alicyclic petroleum resin include "Arcon P-100" manufactured by Arakawa Chemical Co., Ltd. and "Escorets E5000" manufactured by Tonex. The hydrogenated alicyclic petroleum resin used in the present invention usually has a softening point of 80 to
It is 140 ° C.

The crystalline polyolefin resin composition (A) used in the present invention comprises the crystalline polyolefin and a hydrogenated alicyclic petroleum resin, and the crystalline polyolefin and the hydrogenated alicyclic petroleum resin are combined. , 99: 1 to 70:30 by weight, preferably 95: 5 to 80:20 by weight.

To the crystalline polyolefin resin composition (A) used in the present invention, a rubber component for improving impact strength is added as another component within a range not impairing the object of the present invention, and other components are used. Resin component, heat stabilizer, weather stabilizer, light stabilizer, antistatic agent, slip agent, antiblocking agent, antifog agent, nucleating agent, lubricant, dye that absorbs only light of a specific wavelength, pigment, natural oil, Synthetic oil, wax, a transparent filler, or the like can be added.

Such a resin composition can be prepared by applying a conventionally known melt-kneading method. Specifically, a crystalline polyolefin, a hydrogenated alicyclic petroleum resin, and the above-mentioned other components may be dry-blended and melt-kneaded with an extruder, and these components are dissolved in an appropriate good solvent. Alternatively, they may be separately dissolved and then mixed, the solvent may be removed, and the mixture may be melt-kneaded by an extruder.

(B) Cyclic Olefin Resin Next, the (B) cyclic olefin resin which is the material of the film of the other layer used in the present invention will be described.
As the cyclic olefin resin used in the present invention,
(A) a random copolymer of ethylene and a cyclic olefin represented by the above formula [1], (b) a ring-opening (co) polymer of a cyclic olefin represented by the above formula [1] or a hydride thereof,
Alternatively, (c) the graft modified product of the above (a) or (b) can be used.

The cyclic olefin resin used in the present invention has a softening temperature (TMA) of 50 ° C. or higher as measured by a thermal mechanical analyzer, preferably 60.
-180 degreeC, More preferably, it is 70-180 degreeC.

The cyclic olefin resin has an intrinsic viscosity [η] of 0.01 to 10 measured in decalin at 135 ° C.
dl / g, preferably 0.05 to 2.0 dl /
g, and 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.
˜170 ° C., and the crystallinity measured by X-ray diffractometry is usually 0 to 20%, preferably 0 to 2%.

First, the cyclic olefin represented by the general formula [1] used for forming the cyclic olefin resin as described above 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. As the hydrocarbon group, each independently, usually, the number of carbon atoms is 1 to
Examples thereof include an alkyl group having 20 carbon 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. A group in which at least a part of hydrogen atoms forming an alkyl group as described above is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be given.

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 are 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 (in cooperation with each other) to form a monocyclic or polycyclic ring. And the monocycle or polycycle thus formed may have a double bond. Specific examples of the monocycle or polycycle formed here include the following.

[0030]

[Chemical 4]

In the above exemplification, the carbon atoms numbered 1 or 2 are each represented by R in the formula [1].
^It 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.

Furthermore, examples of the cyclic olefin represented by the above formula [1] include compounds represented by the following general formula [2].

[Chemical 5] (In the formula [2], h is 0 or a positive integer, and j
And k is 0, 1 or 2. m, R ^{7 to} R ¹⁵ and R ^{17 to} R ¹⁸ are the same as those in formula [1]. R ^{19 to} 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 above formula [1]. Further, R ^{19 of the} formula [2]
The hydrocarbon group for R ²⁷ is usually, independently of each other, 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. Examples include hydrocarbon groups. 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 hydrogen atoms forming an alkyl group as described above are 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. , Phenylethyl group and the like.

Examples of the alkoxy group include methoxy group, ethoxy group and 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. May be. That is, when the above 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 —) forms 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. In this case, examples of the monocyclic or polycyclic aromatic ring include R ²³ and R when j = k = 0.
Examples thereof include the groups described below in which ²⁰ further forms an aromatic ring.

[0037]

[Chemical 6]

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 derivative 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. 0.1 ^{2, 5} ] -3-decene derivative, tricyclo [4. 4. 0.1 ^{2, 5} ] -3-undecene derivative, pentacyclo [6. 5. 1. 1 ^{3, 6 .0 2,7} .0 ^9,13 ] -4-Pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo [7.4.0.1 ^{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-hexacocene derivative, 1,4-methano-
1,4,4a, 9a-Tetrahydrofluorene derivative, 1,4-methano
-1,4,4a, 5,10,10a-hexahydroanthracene derivative,
And cyclopentadiene-acenaphthylene adduct.

In the following, the above formula [1] or [2]
More specific examples of the cyclic olefin represented by are shown below.

[0040]

[Chemical 7]

[0041]

[Chemical 8]

[0042]

[Chemical 9]

[0043]

[Chemical 10]

[0044]

[Chemical 11]

[0045]

[Chemical 12]

[0046]

[Chemical 13]

[0047]

[Chemical 14]

[0048]

[Chemical 15]

[0049]

[Chemical 16]

[0050]

[Chemical 17]

[0051]

[Chemical 18]

[0052]

[Chemical 19]

[0053]

[Chemical 20]

[0054]

[Chemical 21]

[0055]

[Chemical formula 22]

[0056]

[Chemical formula 23]

[0057]

[Chemical formula 24]

[0058]

[Chemical 25]

[0059]

[Chemical formula 26]

[0060]

[Chemical 27]

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

These cyclic olefins may be used alone or in combination of two or more. The cyclic olefin resin (B) used in the present invention uses the cyclic olefin represented by the above formula [1] or [2], for example, JP-A-60-168708 and JP-A-61. -120816, JP-A-61-115912
JP-A-61-115916, JP-A-61-115916
-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-2
According to the method proposed by the present applicant in Japanese Patent No. 52407, etc., it can be produced by appropriately selecting the conditions.

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

In this (a) ethylene / cyclic olefin random copolymer, the constitutional units derived from ethylene and the constitutional units derived from cyclic olefin as described above are randomly arranged and bonded to each other, and Has a linear structure. The fact that this copolymer is substantially linear and does not have a substantially gel-like crosslinked structure is confirmed by the fact that this copolymer dissolves in an organic solvent and does not contain insoluble matter. You can For example, when measuring the intrinsic viscosity [η] as described below, this copolymer is
It can be confirmed by completely dissolving it in decalin.

In the ethylene / cycloolefin random copolymer (a) used in the present invention, at least a part of the constitutional units derived from the cycloolefin represented by the above formula [1] or [2] is as follows. Structural formula [1-
a] or [2-a].

[0066]

[Chemical 28] (In the formula [1-a], n, m, q, R ^{1 to} R ^18, and R ^a and R ^b are the same as those in the formula [1].
a], m, h, j, k, R ^{7 to} R ¹⁵ and R ¹⁷
To R ²⁷ represent the same as the formula (2). )

Further, (a) ethylene used in the present invention
The cyclic olefin random copolymer may contain a structural unit derived from another copolymerizable monomer, if necessary, within a range not impairing the object of the present invention.

Examples of such other monomers include olefins other than the above-mentioned ethylene or cyclic olefins, 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, 1-eicosene Number 3-20 α-
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,
Examples thereof include non-conjugated dienes such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.

These other monomers may be used alone or in combination of two or more. In the ethylene / cyclic olefin random copolymer (a), the constituent unit derived from the other monomer 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 uses ethylene and the cyclic olefin represented by the formula [1] or [2], and the production method disclosed in the above publication. Can be manufactured by. Among them, the copolymerization is carried out in a hydrocarbon solvent, and a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent is used as a catalyst (a) ethylene / cyclic olefin random copolymer Is preferably produced.

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

[0072]

[Chemical 29] (In the formula [1-b], n, m, q, R ^{1 to} R ^18, and R ^a and R ^b are the same as those in the formula [1].
b], m, h, j, k, R ^{7 to} R ¹⁵ and R ¹⁷
To R ²⁷ represent the same as the formula (2). )

Such ring-opening polymer or ring-opening copolymer can be produced by the production method disclosed in the above publication. Specifically, it can be produced by polymerizing or copolymerizing the cyclic olefin represented by the above 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 or zirconium. Alternatively, a catalyst composed of a metal halide selected from molybdenum or the like or an acetylacetone compound and an organoaluminum compound can be used.

The hydride of the (b) ring-opening polymer or copolymer used in the present invention is obtained by using the (b) ring-opening polymer or copolymer obtained as described above by a conventionally known hydrogenation catalyst. Hydrogenated in the presence of

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

[0076]

[Chemical 30] (In the formula [1-c], n, m, q, R ^{1 to} R ^18, and R ^a and R ^b are the same as those in the formula [1].
c], m, h, j, k, R ^{7 to} R ¹⁵ and R ¹⁷
To R ²⁷ represent the same as the formula (2). )

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

Examples of the modifier include unsaturated carboxylic acids such as maleic anhydride and derivatives of these acid anhydrides or 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 constituent 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 cyclic olefin resin with a modifying agent so as to obtain a desired modification ratio and graft-polymerizing it. It can also be produced by preparing a modified product and then mixing the modified product with an unmodified cyclic olefin resin.

The cyclic olefin resin (B) 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 kinds thereof. Good. In the present invention, (a) ethylene / cyclic olefin random copolymer is preferably used as the (B) cyclic olefin resin.

The cyclic olefin resin (B) used in the present invention may contain a rubber component for improving impact strength as another component, or another resin, within a range not impairing the object of the present invention. Ingredients, heat stabilizers, weather stabilizers, light stabilizers, antistatic agents, antistatic agents, slip agents, antiblocking agents, antifog agents, nucleating agents, lubricants, dyes that absorb only light of a specific wavelength, pigments, natural oils, synthetics Oil, wax, a transparent filler, or the like can be added.

For example, the stabilizer to be added as an optional component is specifically tetrakis [methylene-3 (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionic acid alkyl ester,
2,2'-oxamidobis [ethyl-3 (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] and other phenolic antioxidants; zinc stearate,
Examples thereof include fatty acid metal salts such as fatty acid calcium such as calcium stearate and 12-hydroxycalcium stearate; and fatty acid esters of polyhydric alcohols.

These may be blended alone, for example, tetrakis [methylene-3- (3,5-di-t-butyl-
4-Hydroxyphenyl) propionate] methane with zinc stearate and glycerin monostearate can be exemplified. Particularly 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 a polyhydric alcohol, a part of alcoholic hydroxyl groups of a polyhydric alcohol having a valence of 3 or more is esterified. And polyhydric alcohol fatty acid ester.

Specific examples of such fatty acid ester of polyhydric alcohol include glycerin monostearate,
Glycerin fatty acid esters such as glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin dilaurate; pentaerythritol monostearate (p
entaerytritol mono stear
ate), pentaerythritol monolaurate, pentaerythritol distearate, pentaerythritol tristearate, and other fatty acid esters of pentaerythritol. These may be used alone or in combination with each other.

The phenolic antioxidant is less than 10 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the total of 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 polyhydric alcohol is preferably used in an amount of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the total of the essential components.

The polyolefin-based multi-layer sheet or film of the present invention comprises a sheet or film comprising the above-mentioned (A) crystalline polyolefin resin composition, or a composition of the crystalline polyolefin resin composition and other components optionally mixed therewith. (B)
It is a laminate of a cyclic olefin resin or a sheet or film made of a composition of the cycloolefin resin or another component optionally blended, that is, a laminate. As the form of lamination, crystalline polyolefin resin composition (A) layer / cyclic olefin resin (B) layer / crystalline polyolefin resin composition (A) layer, cyclic olefin resin (B) layer / crystalline polyolefin resin Composition (A)
Layer / Cyclic Olefin Resin (B) Layer, Crystalline Polyolefin Resin Composition (A) Layer / Cyclic Olefin Resin (B)
Any form such as a layer may be used.

In order to form the polyolefin-based multi-layer sheet or film, a general multi-layer sheet or film forming method such as a multi-layer die method, a co-extrusion forming method such as a multi-layer inflation method, or the like can be employed. The formed polyolefin-based multilayer sheet or film can be used as it is without stretching, or can be used after being uniaxially or biaxially stretched. Further, in order to impart other functions, it can be used by being further laminated 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 is also excellent in vacuum or pressure air moldability, so that it can be used for packaging medicines, foods and cigarettes. Demonstrate sufficient performance as a material. Therefore, the polyolefin-based multilayer sheet or film of the present invention can be preferably used as a packaging sheet or film.

Items to be packaged include medicines, 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 objects to be packaged such as tobacco and tea bags, moisture resistance and transparency are guaranteed. The packaging forms include bags, packs, and PTP (press thro).
Ughpack), blister packs, hand twists, wrappings, shrings, easy peel films and the like.

[0090]

As described above, according to the present invention, a sheet or film made of a specific cyclic olefin resin and a sheet made of a crystalline polyolefin resin composition having good adhesiveness to the sheet or film, or Since it is laminated with a film, it is extremely good as a packaging material with excellent interlayer adhesion, moldability, moisture resistance, transparency, heat sealability and dead hold, and also excellent vacuum or pressure air moldability. A polyolefin-based multilayer sheet or film is obtained.

Further, according to the present invention, it is made of the above-mentioned polyolefin-based multilayer sheet or film and is excellent in interlayer adhesion, moldability, moisture resistance, transparency, heat sealability and dead-holding property, and also in vacuum or pressure air moldability. Also gives excellent packaging sheets or films.

[0092]

EXAMPLES Next, examples of the present invention will be described. Example 1 As a crystalline polyolefin resin composition (A), 230
Melt flow rate at ℃ (Measurement method: ASTM D123
8) is 7.2 g / 10 min, density (measurement method: ASTM
D1505) is 0.91 g / cm ³ , the crystallinity by X-ray diffraction is 58%, the polypropylene having a heat distortion temperature (measurement method: ASTM D648) of 112 ° C. under a load of 4.6 kg / cm ^2, and a C ₅ fraction Produced by cationically polymerizing a mixture of

[Chemical 31] A composition was used in which a hydrogenated alicyclic petroleum resin containing a resin represented by the following formula was melt-blended with an extruder at a polypropylene: hydrogenated alicyclic petroleum resin weight ratio of 8: 2.

As the cyclic olefin resin (B), ethylene and 8-ethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene (in the formula [1], n =
0, m = 1, R ^{7 to} R ¹⁴ and R ^{16 to} R ¹⁸ are hydrogen atoms,
A cyclic olefin in which R ¹⁵ is an ethyl group, hereinafter ETCD-
3), having an intrinsic viscosity [η] of 0.67 dl / g and a softening temperature (TMA) of 9
The thing of 0 degreeC was used.

A two-kind three-layer extruded sheet having a constitution of crystalline polyolefin resin composition (A) layer / cyclic olefin resin (B) layer / crystalline polyolefin resin composition (A) layer was prepared from these raw materials under the following conditions. The sheet was prepared and the sheet physical properties, moldability, and interlayer adhesiveness between the crystalline polyolefin resin composition layer and the cyclic olefin resin layer were evaluated by the following methods.
The results are shown in Table 1.

(Molding conditions) Molding machine: two-kind three-layer extruder Screw: crystalline polyolefin resin composition (A) layer; diameter 30 m
m, L / D = 24, slow compression full flight type cyclic olefin resin (B) layer; diameter 40 mm, L / D
= 28, slow compression full flight type Cylinder temperature: Crystalline polyolefin resin composition (A) layer; 200 ° C Cyclic olefin resin (B) layer; 200 ° C Die: T-die black box type

(Evaluation method) 1. Wall 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: Performed according to ASTM F1249.
40 ° C., 90% relative humidity 4. Interlayer adhesion: Rubbing the edges of the two-kind three-layer sheet,
Those that peeled off failed the interlayer adhesion. 5. Continuous vacuum pressure forming: 10 mm width, 150 mm length
Atmosphere temperature of 2 type 3 layer sheet cut into strips
After holding it for 1 minute, it was pulled with a load of 1 kg / cm ² and the one having an elongation of 1% or less was regarded as a pass.

Example 2 As the polypropylene of the crystalline polyolefin resin composition (A) used in Example 1, the melt flow rate at 230 ° C. was 11.5 g / 10 min and the density was 0.9.
1 g / cm ³ , 59% crystallinity by X-ray diffraction,
The procedure of Example 1 was repeated except that polypropylene having a heat distortion temperature of 110 ° C. under a load of 6 kg / cm ² was used. The results are shown in Table 1.

Comparative Example 1 Instead of the crystalline polyolefin resin composition (A) used in Example 1, no hydrogenated alicyclic petroleum resin was blended, and the polypropylene of Example 1 was used alone. The same procedure as in Example 1 was performed. The results are shown in Table 1.

[0099]

[Table 1]

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

Claims (4)

[Claims] 1. (A) crystalline polyolefin 70-99
% Or at least one layer of a crystalline polyolefin resin composition comprising 1 to 30% by weight of a hydrogenated alicyclic petroleum resin, and (B) (a) the limit measured in decalin at 135 ° C. Viscosity [η] is 0.01 to 10 dl / g, softening temperature (TMA)
Is 50 ° C. or higher, ethylene comprising a copolymer of a cyclic olefin represented by the following general formula [1] and ethylene.
Cyclic olefin random copolymer, (b) intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 10 d
1 / g, a softening temperature (TMA) of 50 ° C. or higher, a ring-opening (co) polymer of a cyclic olefin represented by the following general formula [1] or a hydrogenated product thereof, or (c) the ethylene / cyclic group At least one sheet or film made of a cyclic olefin resin (a), a ring-opened (co) polymer of a cyclic olefin, or a graft modified product of a hydrogenated product (b) thereof is laminated. A polyolefin-based multilayer sheet or film characterized by: [Chemical 1] (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 ^1
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. May be. Here, when q is 0, the respective bonds bond to each other to form a 5-membered ring. ) 2. The crystalline polyolefin has a crystallinity of 3
The polyolefin-based multi-layer sheet or film according to claim 1, wherein the polypropylene is more than 0%. 3. The polyolefin multilayer sheet or film according to claim 1, wherein the cyclic olefin resin (B) is an ethylene / cyclic olefin random copolymer (a). 4. A packaging sheet or film comprising the polyolefin-based multilayer sheet or film according to any one of claims 1 to 3.