JPH02289637A - Sheet or film composed of cyclic olefin-based polymer - Google Patents

Abstract

PURPOSE:To provide the subject sheet or film composed of a specified cyclic olefin-based polymer, excellent in elongation resistance, easy tearing and gas barrier properties and suitable for wrapping materials, etc. CONSTITUTION:One or more cyclic olefin-based resins having 0.01-10dl/g intrinsic viscosity and >=70 deg.C softening temperature selected from a group consisting of ring-opening (co)polymers introduced from a cyclic monomer represented by the formula (n is 0 or positive integer; R<1> to R<12> are H, halogen or hydrocarbon group. R<9> to R<12> mutually bond and form a monocyclic or polycyclic group which may contain double bonds or R<9> and R<10> or R<11> and R<12> form an alkylidene), hydrogenated compounds of the above mentioned (co)polymer, etc., or a composition composed of the above mentioned resins, a specified non-rigid cyclic olefin-based copolymer, a non-crystalline or low crystalline alpha-olefin-based (co)polymer, etc., is formed into a sheet or a film.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sheet or film made of a cyclic olefin polymer. More details <(Translation) The present invention relates to a sheet or film that has excellent stretch resistance, tearability, and gas barrier properties.

i Mamekuya Gomonme 11 Polyethylene, polypropylene, and polystyrene 1 It is formed into a sheet or film and is frequently used as a packaging material for foods, etc., or as an adhesive tape. Such food packaging sheets or films must have excellent gas barrier properties and stretch resistance. In addition, in order to facilitate the opening of packaged products and the cutting of adhesive tapes, it is necessary that the sheet or film be torn with a small amount of force, that is, it must have excellent tearability.

Conventional sheets or films made of polystyrene, polyethylene, etc. are also required to have the above-mentioned stretch resistance, gas barrier properties, and tearability (easy opening).

1 Further A1 An object of the present invention is to provide a sheet or film having excellent stretch resistance, gas barrier properties, and tearability.

1 Skin A Nose 1 Polymer for forming a sheet or film according to the present invention Ring-opening polymer tree derived from a cyclic olefin represented by the following formula [I] Ring-opening copolymer tree Hydrogen of the polymer or copolymer and an addition polymer of a cyclic olefin and ethylene represented by the following formula [I],
Intrinsic viscosity measured in decalin at 135°C [η is 0.
01 to 10 dl/g, and is characterized by being made of at least one type of cyclic olefin resin having a softening temperature of 70°C or higher.

...[IcoHowever, in the above formula [I], it is nt40 or a positive integer, and R1 to RI2 are each independently a hydrogen atom,
Represents an atom or group selected from the group consisting of a halogen atom and a hydrocarbon group. R9 to R l 211 may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, and R9 and Rl1 or Rll and RI2 may form an alkylidene group.

The present invention was completed based on the knowledge that sheets or films formed from cyclic olefin polymers have excellent stretch resistance, gas barrier properties, and tearability. A sheet or film made of the above is characterized in that its permeability to gases such as oxygen and carbon dioxide is lower than that of conventional films.

This indicates that the sheet or film according to the present invention has excellent gas barrier properties, and by using such a sheet or film as a packaging material, the contents can be stored for a long period of time. can.

Another major feature of the sheet or film according to the present invention is that it has excellent stretch resistance. In other words, the sheet or film according to the present invention has a high elongation modulus, and has a low elongation at break, so it is less likely to be stretched and deformed when stretched, unlike conventional films, making it particularly suitable for packaging applications. ing.

Note that even if the sheet or film 1 according to the present invention is a biaxially stretched product of the cyclic olefin polymer, unstretched (
It may also be a pressed sheet, and both have excellent gas barrier properties and elongation resistance.

Furthermore, the sheet or film made of the cyclic olefin polymer according to the present invention has excellent tearability, and when the sheet or film of the present invention is used as a packaging material, it can be opened.

i Sarajigo Junko 11 The sheet or film made of the cyclic olefin polymer according to the present invention will be specifically explained below.

[Cyclic olefin] Resin component constituting the sheet or film according to the present invention Ring-opening polymerization derivative derived from a cyclic olefin represented by the following formula [I] Ring-opening copolymerization method Hydrogenation of the polymer or copolymer and at least one type of resin selected from the group consisting of an addition polymer of a cyclic olefin and ethylene represented by the following formula [l].

You may do so.

... [I] However, in the above formula [1], n is O or a positive integer, and R I x R + 2 11 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group. Furthermore, 1 R● to R I 2 14 may be bonded to each other to form a monocyclic or polycyclic group, and this ring may have a bridged structure. Furthermore, this monocyclic or polycyclic group may have a double bond. Furthermore, it may be a group in which these rings are combined.

That is, the above R9 to Rl2 together form a polycyclic or monocyclic group, for example as described below,
In the above formula, one carbon atom with l and 2
formula[! ] represents a carbon atom of an alicyclic structure to which a group represented by R● to Rl2 is bonded.

Next, these groups may have a substituent such as a methyl group.

Further, R● and Ril+ or Rll and R12 may form an alkylidene group. Saraku R9
~RI2 may contain an ester group or the like.

Preferred examples of such cyclic olefins include cyclic olefins represented by the following formula [n].

The cyclic olefin used as a raw material for preparing the fin polymer also includes a compound represented by the following formula [na].

[n] However, in the above formula [nl, n is 0 or 1, and m is O or a positive integer.

In addition, Rl and Rl● each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. may be formed, and the monocyclic or polycyclic group may have a double bond.

Further: Rl6 and RI6, or RI7 and R
An alkylidene group may be formed with Is.

In addition, in the present invention, an olefin having an alicyclic structure...[
H-a] Just beast In the above formula [■-a], p is 0 or 1
or more, q and r are 0, 1, or 2, and R1 to RI% each independently consist of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group. Represents an atom or group selected from the group. RS (or Re) and R9 (or R?) may be bonded via an alkyl group having 1 to 3 carbon atoms, or may be bonded directly without any group. .

The cyclic olefin represented by the above formula [E], or preferably the formula [n], and further the formula [■-a] can be obtained by condensing cyclopentadiene and the corresponding olefin milk or cyclic olefin by Diels-Alder reaction. It can be easily manufactured by

Specifically, the cyclic olefin represented by the above formula [I] used in the present invention includes bicyclo[2,
2. 11 heptose-2-ene derivative, tetracyclo[
4, 4, 0, 12. S, 1▼Electric 1]-3
-dodecene-derived hexacyclo[5,5, l, 13.6. 111.
13, Q2. ? ,Q9. I4]-4-Heptade, Nsene derivatized oc9 Sikuo [8,8,0.1",1",1"1"
．． 1"=e, 03・●, OI2・+?] -5-Docosen induction I bill pentacyclo [6, 6, 1. 1"・8.
, Q2. v, Qo・14] 4-hexadecene derivative, heptacyclo-5-icosene derivative, heptacyclo-5-eicosene derivative, tricyclo[4. 3. 0. 12.5] 13-Decene induced I bill tricyclo [4, 3, 0. 12・s] 13-undecene induced i-card bentacyclo [6, 5, 1, 13.6.
02・T,09・+3]-4-pentadecene derivative pentacyclo[4, 7, 0. 12・5.0fi・
+3.19・+21-3-pentadecene induction book hentashiku o [7,8+0+ 1s・a, CF-'o
i+"-1+0"-".1 鵞2・Il]-4-eicosene induction 1 [≧!1; and nonasic mouth [9, 10, 1, 1, 4. 7,
03. ●Qll@, Qlltl1+3. te, 0+
a. +*, 1+s. +sl-5-hen9 Cosene derivatives and the like can be mentioned.

Specific examples of such compounds are shown below.

Bicyclo [2, 2. 1] Hept-2-ene derivative; 2, 7. 9- }Limethylthene 5,1O-dimethyltetra C11. 9-inbutyl-2.7-ethyl-11. 12-dime9-isobutyl 11.12 5, 8, 9. 10 Tetrameth. + @]-3-dodecenemethyl-9-ethylte8-chlorotetracyc-3-dodecene8-promotetracyc-13-dodecene8-fluorotetracy1●]-13-dodecene●]-3-dodecene8-methyl Tetrasic 8-ethyltetrasic+i]-3-dodecene 8-hexyltetrasyl 5, 1F II] 3-dodecene e]-3-dodecene-3-dodecene III] Dodecene. 12 5.17 鵞●]-3-dodecene 8-ethylidene-9-iso-dodecene, 12・S,17・1●]-131 dodecene 5.17 1@]-3-dodecene 8-n-propylidene- 9 Tetracyclo[4, 4, 0. 12・5,1
▼・1●]-3-dodecene derivative; (blank below) CH, 8-n-propylidene [4, 4, 0. 12・5,17 ■1-3 -Dodesenkuro [4, 4, 0. 12 111]-3-dodecene 8-n-propylidene [4, 4, 0. 12・5.17 +1]-3 Dodecene 5.17 1 @ ] -3 Dodecene. 1'l-4-heptadecenedeceneheptadecene 1●,03*,Ql2. 7. 5-dococene derivative view '+O' 7. 09 [6. 6, 1. 13・+−]
-L4-hebutadecene derivative 8.11@3, Q2. ? , 09 docosene 2・+y)-5-docosene 15-ethyloctacycdecene 2・t]-pentacyclo[6,6,1,13.8,02.7 such as 5-docosene
．． 091=]-4 etc. [8, 8. 0. 129.14 t, 1st mouth 1+ hexadecene derivative; Hebutashiku mouth [8, 7. 0 5-Methyl-tricyclo etc. [4, 3, 0. 125] 3-decene derivatives: Hebutacyclo-5-icosene derivatives such as cosene or hebutacyclo-5-eicosene 19 conductors; tricyclo-5-icosene derivatives such as cosene; 12S] Undecene derivatives: 1,3-dimethyl-benta1,6-dimethylbentacene and other pentasic compounds [4,7,0.12S, Of! 3,II +2] -3-pentadecene derivative; 14. 15 Pentasic compounds such as dimethylbencosene [6, 5, 1. 1'・6,0
2,7,09,l 3 ] -4-pentadecene derivatives; IJ -4-eicosene, etc. 1'. 6. 02? ,1
1@. Diene compounds such as 1te,0 +s,1+e IJ -4-eicosene derivatives; and further examples of cyclic olefins include. t+,1
eye. 2e Ql a. l9 1+S. l●] -5-pentacocene21. Ql (1@, lls.lI) Nonacyclo [9, 10, 1, la.t, Qi.@, Qt.+
●． o12. t+, 1 glance J 2@, Ql4 IS, II5 ■e] -5-pentacocene derivatives can be mentioned.

(Margin below) can be mentioned.

(The following is a blank space) As an example of the polycyclic cyclic olefin represented by the above formula [I] ({tL of the above compound and 1, 4, 5
．． 8-dimethano-1. 2, 3, 4, 4a,
5, 8, 8a-octahyde naphthalene, 2-methyl-1. 4, 5. 8-dimethano-1. 2, 3
, 4, 4a, 5, 8, 8a-octahyde-naphthalene, 2-ethyl-1.4,5.8-dimethano-1
．． 2, 3, 4, 4a, 5, 8, 8a-octahyde naphthalene, 2-probyl-1. 4, 5
．． 8-dimethano-1. 2, 3, 4. 4a, 5
, 8, 8a-octahyde naphthalene, 2-hexyl-1. 4, 5. 8-dimethano-1. 2, 3
, 4. 4a, 5, 8. 8a-octahydride naphthalene, 2,3-dimethyl 1, 4, 5. 8-dimethano-1. 2, 3, 4, 4a, 5, 8.
8a-Naphthalene, 2-methyl-3-ethyl-1. 4, 5. 8-dimethano-1. 2,
3, 4, 4a, 5, 8, 8a-octahyde naphthalene, 2-chloro-1,4, 5. 8-dimethano-1. 2, 3, 4. 4a, 5, 8, 8
a-octahydronaphthalene, 2-bromo1. 4,
5. 8-dimethano-1. 2, 3, 4. 4a,
5, 8, 8a-octahydronaphthalene, 2-fluoro1. 4, 5. 8-dimethano-1. 2,
3, 4, 4a, 5, 8, 8a-octahyde naphthalene, 2,3-dichloro1. 4, 5.
8-dimethano-1. 2, 3, 4, 4a, 5,
8, 8a-octahyde-naphthalene, 2-cyclohexyl-1. 4, 5. 8-dimethano-1. 2,
3, 4. 4a, 5, 8. 8a-octahydronaphthalene, 2-n-butyl 1, 4, 5. 8
-Dimethano-1. 2, 3, 4. 4a, 5,
8, 8a-octahydronaphthalene, 2-isobutyl 1, 4, 5. 8-dimethano 1, 2, 3,
Mention may be made of octahyde naphthalenes such as 4,4a,5,8,8a-octahyde naphthalene.

These cyclic olefins can be used alone or in combination.

[Cyclic olefin resin] In the present invention, the cyclic olefin resin constituting the sheet or film is (1-a) a ring-opening polymer or ring-opening copolymer derived from the above-mentioned cyclic olefin (1-a). b) at least one type of resin selected from the group consisting of hydrogenation of these polymers or copolymers; and (2) addition polymers of cyclic olefin and ethylene as described above.

First, (1-a) a ring-opening polymer or copolymer derived from a cyclic olefin as described above and (1-b) a hydrogenated product of these polymers or copolymers will be explained.

The cyclic olefin ring-opening polymer can be obtained by subjecting the aforementioned cyclic olefin to ring-opening polymerization of the cyclic olefin represented by formula [■, formula [n], or formula [n-a] by a method known per se. It can be prepared. In the present invention, a cyclic olefin ring-opening polymer prepared using a single cyclic olefin as described above can be used, or a cyclic olefin ring-opening copolymer prepared by ring-opening polymerization of multiple cyclic olefins can be used. You can also use Give an example of such a ring-opened polymer or copolymer1! ,1,
4, 5. 8-dimethano-1. 2, 3, 4,
4a, 5, 8. (Co)polymerization of 8a-octahydride-naphthalenes & 1.4,5.8-dimethano-
1. 2, 3, 4, 4a, 5, 8, 8a-
Octahydronaphthalenes and norbornene (bicyclo[
2. 2. 1] ring-opened copolymers with hept-2-ene).

Double bonds remain in the cyclic olefin ring-opened polymer prepared as described above, and these double bonds can be easily hydrogenated by a known method. In the present invention, a hydrogenated product of the cyclic olefin ring-opened (co)polymer prepared as described above can also be used as the substitute cyclic olefin resin. Such hydrogenation further improves thermal stability and weather resistance.

The ring-opening (co)polymer resin used as the cyclic olefin resin in the present invention and its hydrogenated products are explained using the cyclic olefin represented by the formula [n] as an example. It is thought that the cyclic olefins react as described below to form ring-opening (co)polymerized molecules and hydrogenated products thereof.

In addition, in the above formula, RIx Rl* and m and n +1 have the same meaning as in formula [n].

In the case of ring-opening polymerization, cyclic olefins other than those represented by formula [■], formula [■], or formula [n 1a] are used within the range that does not impair the properties of the ring-opening (co)polymer or hydrogenated product. Cyclic olefins can be ring-opening copolymerized. Examples of such other cyclic olefins include cyclobutene, cyclobentene, cyclohexene, 3,4-dimethylcyclobentene, 3-methylcyclohexene, 2-(
2-methylbutyl)-1-cyclohexene, 2. 3,
3a, 7-needle tetrahydro-4j7-methanol IH-
indene and 3a. Examples include 5,6,7a-tetrahydride↓hydrogenated rho-47-methanol IH-indene.

Next, (2) addition polymer of cyclic olefin and ethylene will be explained. In the present invention, the term "cyclic olefin addition polymer" refers to this addition polymer without particular limitation.

The cyclic olefin addition polymer used as the cyclic olefin resin in the present invention is an addition polymer of a cyclic olefin represented by the above formula [r], formula [n] or [■-a] and ethylene. be.

In this cyclic olefin addition polymer, ethylene is
It is used in a range of 40 to 85 mol%, preferably 50 to 75 mol%. In addition, the cyclic olefin is 15-6
The amount used is 0 mol%, preferably 25 to 50 mol%. That is, in the cyclic olefin addition polymer, the ratio of repeating units derived from ethylene to repeating units derived from cyclic olefin is usually 40/6.
0-85/15, preferably 5 0/5 0-75/2
They are combined in a molar ratio within the range of 5.

Cyclic olefin addition polymers can be produced by polymerizing ethylene and cyclic olefins, for example, in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminium compound. can.

Such a polymerization method is already known, and is disclosed in Japanese Patent Application Laid-Open No. 1986-
It has been proposed in Publication No. 168708 and the like.

In such a cyclic olefin addition polymer, for example, at least a part of the cyclic olefin represented by the above formula [n] has a structure represented by the following formula [m] and is a repeating unit derived from ethylene. It is thought that they are randomly combined.

... [[[I] However, in the above formula [m], R 1 , R and m and n have the same meanings as in formula [n].

In the present invention, as the cyclic olefin addition polymer,
Other than the cyclic olefin component and the ethylene component, α-olefin and the above formula [
It is also possible to use polymers obtained by adding and polymerizing olefins (other olefins) other than the cyclic olefins represented by [2] to [na].

Here, as other olefins, α-olefins other than ethylene can be used. α used here
-Olefins (which may be linear or branched; examples of such α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1
- 3 to 20 carbon atoms, such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene
Examples include a-olefins.

Among these, α-olefins having 3 to 15 carbon atoms, particularly 3 to 10 carbon atoms, are preferably used.

In addition, "other off-line" as used herein refers to a wide range of unsaturated polycyclic hydrocarbon compounds, excluding ethylene and cyclic olefins represented by formulas [I], [■], and [n-a]. Shown in concept. Therefore, in the present invention, "other olefins" include, in addition to the above-mentioned chain α-olefins, cyclic olefins other than those represented by formulas [I], [n], and [na]. You can also use

More specifically, examples of other cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3.4
-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, styrene, α-methylstyrene, 2,3,3a,7a-tetrahydride-4,7-methanol IH-indene and 3
Examples include a, 5, 6, 7a-tetrahydro-4,7-methanol IH-indene.

In addition, when other olefin inks have two or more double bonds in the molecule, the double bonds remaining in the molecule that are not used in addition polymerization are replaced with hydrogen to improve weather resistance. It can also be added.

By carrying out addition polymerization as described above and carrying out hydrogenation if necessary, the iodine value of the cyclic olefin addition polymer used in the present invention is usually 5 or less, and most of them are 1 or less.

In the cyclic olefin addition polymer, the cyclic olefin inker ζ used as a raw material must have, for example, the structure represented by the above formula [[Il]. This type of cyclic olefin addition polymer has a chemically stable structure and exhibits excellent heat aging resistance.

The cyclic olefin ring-opened (co)polymer (1-a
), these hydrogenated products (1-b), and the cyclic olefin addition polymer (2) usually have an intrinsic viscosity ['l7] of 0.01 to 2 when measured in decalin at 135°C.
0 di/g, preferably 0.01 to 10d
l/g, particularly preferably 0.05 to 8 di/g,
More preferably, it is in the range of 0.05 to 5 di/g, and most preferably in the range of 0.08 to 5 di/g.

These cyclic olefin resins are generally non-quality or have low crystallinity, preferably non-quality, and therefore have good transparency. Specifically, when the crystallinity of these cyclic olefin resins is measured by X-rays, the crystallinity is 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%, and in many cases It is 0%. Furthermore, even if the melting point of these cyclic olefin resins is measured using a differential scanning calorimeter (DSC),
In many cases, no melting point is observed.

Other properties of such cyclic olefin resins include high glass transition temperature (Tg) and high softening temperature (TMA). Glass transition temperature (Tg) is usually 5
To the range 0-230°C, often measured in the range 70-210°C. By using such a cyclic olefin, the softening temperature of the resulting composition {usually iL
70°C or less Preferably 70 to 250°C, particularly preferably 90 to 250°C, even more preferably 90 to 230°C, and often measured within the range of 100 to 200°C.

In addition, the thermal decomposition temperature of cyclic olefin resin is 14,350~
420°C, mostly in the range of 370-400'e.

8! As for mechanical properties, the bending strength is 8, usually IX10'
~5 x 10 Jg/l-+/, and the bending strength is usually within the range of 300-1500 kg/e+/.

Density is 0.86 to 1.10g/cl/, mostly 0
．． 88-1. It is in the range of 0 8 g/c7+. Also, the refractive index (ASTM D542) is 1.47 to 1.58.
, most are within the range of 1.48 to 1.56. 'Furthermore, this cyclic olefin resin (Dai) is substantially non-crystalline as described above, so it has a haze rating (Haze: ASTM D1).
003) is usually 20% or less, often 10% or less.

As for electrical properties, the dielectric constant (IKHz) measured by ASTM D150 is 1. 5-3. O, mostly 1.9 to 2.6, dielectric loss tangent 9X10-4 to 8X1
0-8 Most are within the range of 3xlO-4 to 9x10-S.

The sheet or film of the present invention formed from such a cyclic olefin polymer has excellent chemical properties such as sulfuric acid, ammonia, acetone, ethyl acetate, etc.
Even when immersed for about 4 hours, it is unlikely to cause cracks, deformation, or melting.

[Other blended resins] Furthermore, as a resin component constituting the sheet or film of the present invention, a so-called polymer alloy, which is a blend of the aforementioned cyclic olefin resin with various polymers, can be used. Examples of these polymers include the following (1) to 0.

■Polymerization derived from hydrocarbons having one or two unsaturated bonds Specific examples include polyethylene, polypropylene, polymethylbutene-1, poly4-methylbentene-1
, polyolefins such as polybutene-1 and polystyrene (these polyolefins may have a crosslinked structure), ■ halogen-containing vinyl polymers, specifically polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, etc. ■ Polymer imitations derived from α, β monounsaturated acids and their derivatives, specifically polyacrylates, polymethacrylates,
Polyacrylamide, polyacrylonitrile, or copolymerization with monomers constituting the above-mentioned polymers For example, acrylonitrile/butadiene/styrene copolymerization book Acrylonitrile/styrene copolymerization book Acrylonitrile/styrene/acrylic acid ester copolymer, etc. Unsaturated Polymers derived from alcohols and amines or their acyl derivatives or acetals, specifically polyvinyl alcohol, polyvinyl acetate,
Polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine, or copolymers with monomers constituting the above polymers, such as copolymers with ethylene and vinyl acetate, etc. ■ Polymers derived from eboxides, specifically polymers derived from polyethylene oxide or bisglycidyl ether, etc. ■Polyacetals, specifically polyoxymethylene, polyoxyethylene, polymers containing ethylene oxide as a comonomer, etc. such as polyoxymethylene, ■polyphenylene oxide, ■polycarbonate, ■polysulfone, ■polyurethane and urea resins, ■polyamides and cobolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams, in particular nylons. 6, Nylon 66, Nylon 11, Nylon 12, etc. @Polyesters derived from dicarboxylic acids and dialcohols and/or oxycarboxylic acids or corresponding lactones, in particular polyester terephthalate, polybutylene terephthalate, poly-1.4 - Dimethylol cyclohexane terephthalate, etc. ■Polymerized with a crosslinked structure derived from aldehyde and phenol, urea or melamine.Specifically, phenol/formaldehyde resin, urea/formaldehyde resin, melamine/formaldehyde resin, etc. [Co., Ltd.] Alkyd resins include glycerin and phthalate resins, etc.; - unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols; and halogen-containing unsaturated polyester resins obtained using vinyl compounds as crosslinking agents. Modified resins, [Natural Polymer Co., Ltd.] Specifically, cellulose, rubber, protein, or their derivatives, such as cellulose acetate, cellulose probionic acid, and cellulose ether, and soft polymers, particularly those described below (1). ) to (V).

In addition, in a polymer alloy of a cyclic olefin polymer and these rubber-like components, a crosslinking reaction may be performed in the presence of an organic peroxide, and such a crosslinkable polymer alloy may be used. By blending such a soft polymer, the flexibility of the sheet or film can be improved.

The soft polymer preferably used in the present invention will be explained below.

The soft polymer containing one cyclic olefin component unit is the cyclic olefin (formula [1]
, [II] or [m]), ethylene, and a-olefin. As the α-olefin, an a-olefin having 11 carbon atoms from 3 to 20 is preferably used.

Preferred examples of the a-olefin used in the present invention include propylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1- Mention may be made of tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Further, in addition to the above a-olefins, or together with α-olefins, cyclic olefins or cyclic dienes such as 1-norbornene, ethylidene norbornene, and dicyclobentadiene are preferably used.

In the soft polymer (i) containing a cyclic olefin component,
The repeating units derived from ethylene are contained in an amount ranging from 40 to 98 mol%, preferably from 50 to 90 mol%. The repeating unit number derived from a-olefin is contained in an amount within the range of 2 to 50 mol%,
Repeating units derived from cyclic olefins are contained in an amount ranging from 2 to 20 mol%, preferably from 2 to 15 mol%.

Unlike the cyclic olefin polymer, the soft polymer (i) usually has a glass transition temperature (Tg) of 0°C or lower,
It is preferably -10°C or lower, and has an intrinsic viscosity measured in decalin at 135°C [l coca], usually 0.
01-10 di/g, preferably 0.08-7
dl/g. The crystallinity of the soft polymer (i) measured by X-ray diffraction is usually in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

Such a soft polymer (i) is disclosed in Japanese Patent Application Laid-Open No. 1687-1987.
No. 08, No. 61-120816, No. 61-115
No. 912, No. 61-115916, No. 61-271
No. 308, No. 61-272216, No. 62-257,
In accordance with the applicant's proposal described in publications such as No. 406,
It can be manufactured by selecting conditions as appropriate.

A-olefin polymerization ii The α-olefin copolymer (11) used as the soft polymer is a non-quality or low-crystalline copolymer consisting of at least two types of a-olefins.

Examples of low-crystalline copolymers include ethylene/a-olefin copolymer and propylene/a-olefin copolymer.

As the a-olefin constituting the ethylene/a-olefin copolymer, α-olefins having 3 to 20 carbon atoms are used (for example, propylene, 1-butene, 4- Mention may be made of methyl-1-butene, 1-hexene, 1-octene, 1-decene and mixtures thereof.
-10 a-olefins are preferred.

Molar ratio of repeating units derived from ethylene and repeating units derived from a-olefin in the ethylene/a-olefin copolymer (ethylene/a-olefin) lLff - car that varies depending on the type of olefin 40/60 It is preferable to adjust within the range of ~95/5. When the a-olefin used is propylene, the above molar ratio is +440/60 to 90/
It is preferably 10, and when the a-olefin is an a-olefin having 4 or more carbon atoms, it is 50/5.
It is preferable that it is 0-95/5.

As the a-olefin constituting the propylene/a-olefin copolymer, it is common to use a σ-olefin having 4 to 20 carbon atoms.
Mention may be made of 1-butene, 4-methyl-1-bentene, 1-hexene, 1-octene, 1-decene and mixtures thereof. Among these, especially carbon number 4~lO
The a-olefins are preferred.

In the above-mentioned propylene/α-olefin copolymer, the molar ratio of repeating units derived from L propylene and repeating units derived from a-olefin (propylene/a-olefin) is the same as that of the a-olefin. The force varies depending on the type, and is preferably within the range of 50/50 to 95/5.

a-olefin/diene polymerization 1ii a-olefin/diene copolymer used as a soft polymer (
As iii), a wide ethane/a-olefin/diene copolymer rubber and a propylene/α-olefin/diene copolymer rubber are used.

As the a-olefin constituting such a copolymer rubber, an a-olefin having 3 to 20 carbon atoms (4 to 20 in the case of propylene/α-olefin) is usually used. Examples include propylene, 1-butene, 1-pentene, 4-methyl-1-bentene, 1-hexene, 1-octene, 1-decene, and mixtures thereof. Among these, alpha-olefins having 3 to 10 carbon atoms are particularly preferred.

Further, as the diene components constituting these copolymer rubbers, For example, If1 is 1,4-hexadiene, 1.
6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1
．． Chained non-conjugated dienes such as 6-octadiene: cyclohexadiene, dicyclobentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-impropylidene -2-norbornene,
Cyclic non-conjugated genes such as 6-chloromethyl-5-impropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-impropylidene-5-norbornene, 2-probenyl 2
．． Examples include 2-norbornadiene.

The molar ratio of repeating units derived from ethylene and repeating units derived from a-olefin in the above ethylene/α-olefin/diene copolymer rubber (ethylene/a-olefin) is as follows: Types of α-olefins It is preferable that it is within the range of 40/60 to 90/10, depending on the

In addition, the content of repeating units derived from diene in these copolymer rubbers is usually 1 to 20 mol%.
, preferably within the range of 2 to 15 mol%.

Aromatic vinyl hydrocarbons used as soft polymers
As the conjugated diene-based soft copolymer, aromatic vinyl-based hydrocarbon milk, conjugated diene-based random copolymerization block copolymers, or hydrides thereof are used.

Specific examples include styrene/butadiene block copolymer rubber, styrene/butadiene/styrene block copolymer rubber, styrene/isoprone block copolymer rubber, styrene/isoprene/styrene block copolymer rubber, Examples include hydrogenated styrene/butadiene/styrene block copolymer rubber, hydrogenated styrene/isoprene/styrene block copolymer rubber, and styrene/butadiene random copolymer rubber.

The molar ratio of repeating units derived from aromatic vinyl hydrocarbons and repeating units derived from conjugated dienes in these copolymer rubbers (aromatic vinyl hydrocarbon/conjugated diene) is usually 1O/90. ~7 0/3 0
is within the range of

The hydrogenated copolymer rubber is a copolymer rubber in which some or all of the double bonds remaining in the above copolymer rubber are hydrogenated.

Soft polymer or copolymer consisting of isobutylene or imbutylene V) Isoptylene-based soft polymer or copolymer used as a soft polymer (v)
Polyisobutylene rubber, polyisoprene rubber, polyptadiene rubber, imptylene-isoprene copolymer rubber, etc. are used.

The properties of the copolymers (11) to (V), which are soft polymers, are almost the same as those of the cyclic olefin polymer (i), and the intrinsic viscosity measured in decalin at 135°C [vl] (1) Usually in the range of 0.01 to 10 dl/g, preferably in the range of 0.08 to 7 dl/g, and the glass transition temperature (Tg) is usually below 0°C, preferably below -10°C, particularly preferably -20°C. It is as follows. Further, the crystallinity measured by Xi diffraction method is usually in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

Such a soft polymer (converted) can be used as it is, or can be blended into a cyclic olefin resin after forming a crosslinked structure. can also be formed.

In polymer alloys containing such rubbery components and crosslinkable polymer alloys treated with organic peroxides, various (i) to (
The total weight of the polymer V) is 5 to 150 parts by weight, preferably 5 to 100 parts by weight, and particularly preferably 10 to 80 parts by weight. By satisfying such a compounding ratio, a polymer alloy with well-balanced impact strength, rigidity, heat distortion temperature, and hardness can be obtained. And, the melt flow index (MFR; AS
It is preferable to mix the image components so that the TMD1238 condition) is 0.1 to 100.

In addition, in the present invention, when preparing a polymer alloy having a crosslinked structure, an organic peroxide is usually used. Organic peroxides used to form crosslinks include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis(
Peroxyketals such as t-butylbaroxy)cycloxane, 2,2-bis(t-butylbaroxy)octane, t-butylhydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxy Hydroperoxides such as peroxide, 1,1,3.3-tetramethylbutylhydroperoxide
butyl peroxide, 2,5-dimethyl-2,5 di(t
-butylperoxy)hexane, 2,5-dimethyl-2
．． Diasilver oxides such as 5-di(t-butylperoxy)hexyne-3 and other dialkyl peroxides, lauroyl peroxide, penzoyl peroxide, t-butyl peroxy acetate, t-butyl peroxybenzoate, 2,5-dimethyl Peroxy esters such as -2,5-di(penzoylperoxy)hexane and the like can be mentioned.

The amount of the organic peroxide component is usually 0.01 to 1 part by weight, preferably 0.05 to 0.0 parts by weight, per 100 parts by weight of the cyclic olefin polymer and the (soft) polymer.
．． 5 parts by weight.

When treated with organic peroxide, the crosslinking reaction is carried out using a compound with two or more radically polymerizable functional groups in the molecule, improving crosslinking efficiency and producing polymers with excellent impact resistance. Alloy is obtained.

The radically polymerizable functional group used here is contained within the molecule.
Examples of compounds having more than 1 divinylbenzene,
Examples include vinyl acrylate and vinyl methacrylate. These compounds (based on 100 parts by weight of the total amount of cyclic olefin resin and soft polymer,
It is usually used in an amount of 1 part by weight or less, preferably 0.1 to 0.5 part by weight.

[Other additives] A cyclic olefin ring-opening polymer of the sheet or film according to the present invention, a hydrogenated product thereof, a cyclic olefin addition polymer, or a polymer obtained by blending various polymers with these cyclic olefin resins. The alloy has heat resistance stability, weather resistance stability,
Anti-static gunwale slip 41, anti-blocking slip L
Anti-fog II, lubricants, dyes, pigments, natural ponds, synthetic ponds
Contains organic or inorganic fillers.

For example, stabilizers that can be added as optional ingredients include:
Tetrakis[methylene-3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate comethane, β-(3.5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2.2 Phenolic antioxidants such as '-oxamidobis[ethyl-3-(3.5-di-t-butyl-4-hydroxyphenyl)probionate; zinc stearate, calcium stearate, 1,2-
Fatty acid metal salts such as calcium hydroxystearate: Examples include polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin distearate, bentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination. Examples of using combinations of these additives include tetrakis[methylene-3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate]methane, zinc stearate, and glycerin monostearate. can be mentioned.

In addition, examples of organic fillers and inorganic fillers include silica,
Diatomaceous earth, alumina, titanium oxide, magnesium oxide,
Pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite,
Calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmolystomite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, Silicon carbide fibers include polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers.

As a method for mixing the cyclic olefin resin used in the present invention with other components, methods known per se can be applied. For example, there is a method in which each component is mixed at the same time.

[Formation of sheet or film] The cyclic olefin resin prepared as described above was
The sheet or film of the present invention can be obtained by forming it into a sheet or film using a method known per se such as a die method or an inflation method. Thickness of the sheet or film according to the present invention:
It can be set appropriately in consideration of its use. Further, the sheet or film of the present invention may be in an unstretched state, and can be prepared by employing, for example, a press molding method.

Further, the sheet or film of the present invention may be axially or biaxially stretched.

Even if the sheet or film is subjected to glass transition temperature (Tg),
) A method is adopted in which the film is heated to a temperature higher than or equal to and then stretched. In the present invention, the stretching ratio of 1 can be set as appropriate, for example, taking into consideration the required properties such as strength. Further, as the stretching method, commonly used stretching methods such as a roll stretching method, a tenter stretching method, and an inflation method can be employed.

To explain the method for manufacturing the sheet or film of the present invention by showing a more specific example, the cyclic olefin resin prepared as described above is molded into a mold using a T-die molding method or an inflation molding method. Thickness 0.0
5. Produce a sheet or film in steps 5-5. The sheet or film thus prepared can be used as is. When further preparing a stretched film or sheet, the sheet or film prepared as described above can be used to form this sheet or film. The resin (or resin composition) is heated to a temperature higher than the glass transition temperature (Tg) by 0 to 60°C, preferably 10 to 40°C. Next, a biaxially stretched film or sheet can be obtained by stretching this heated sheet or film sequentially in the longitudinal and transverse directions or simultaneously in both directions by 2 to 50 times, preferably 3 to 30 times. .

The sheet or film made of the cyclic olefin polymer according to the present invention thus obtained is particularly excellent in gas barrier properties, elongation resistance, and tearability. Furthermore, the sheet or film of the present invention has good transparency as well as good surface properties. Furthermore, the heat sealability of the film or sheet of the present invention is also good.

As described above, the sheet or film of the present invention has excellent properties and is suitable for packaging materials, particularly food packaging materials.

λhada A Emperor J As explained above. Since the sheet or film according to the present invention is made of a cyclic olefin resin, it has excellent gas barrier properties and elongation resistance.When used as a material for containers, packaging materials, or shielding materials, it is possible to Can be stored sufficiently.

In addition, the sheet or film of the present invention formed from a cyclic olefin resin can be easily torn. This makes it easier to open the package or break your hands when using the tape.

EXAMPLES The present invention will now be described in detail with reference to Examples. The present invention is not limited to these examples.

In addition, the measuring method and evaluation method of various physical properties in this invention are shown next.

(1) Melt flow index (MFRT) Predetermined temperature (T'C) according to ASTM-D1238
, measured at a load of 2.16 kg (2) softening temperature (TMA) DuPont Thermo Mechanical
A quartz needle was placed on the sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5° C./min. (3) Glass transition temperature (Tg) Measured at a temperature increase rate of 10°C/min using DSC-20 manufactured by SE I KO Electronics Co., Ltd. (4) Haze According to ASTM-D1003 Measured (5) Gloss Measured according to ASTM-D523 8 Incident angle is 60-
ASTM TYP
E■ Punch out a dumbbell-shaped piece of paper and measure it using the ASTM-D638 method at a test temperature of 23°C. Cut out a test piece of IOOXIOOE from a film impact molded product and measure it using a Toyo Seiki film impact tester. did
Impact head diameter: 1 inch (8) Tear strength: Measured according to JIS Z1702, according to the Yuelmendorf tear method. Measurement temperature: 23°C.

(9) Heat-sealability Two test pieces cut from the molded product to a size of approximately 120 x 120 m are stacked and heat-sealed using a heat sealer set at a predetermined temperature at a sealing pressure of 2 h/clr and a sealing time of 1 second. The width of the heat-sealed test piece is 15 mm.
．． ．． It was cut into strips and measured at 23°C.
The tensile peel strength was measured at an angle of 0 degrees and the test speed was 300. ．． /minute.

(10) Gas permeability Oxygen gas permeability; Measured using an OX-TRAN100 oxygen gas permeation measuring device manufactured by MODERN CONTROL. PERMAT made by Mocon
As a cyclic olefin copolymer measured using a RANC-rv type carbon dioxide gas permeation tester, ethylene and 1,4
, 5. 8-dimethano-1. 2, 3, 4, 4
a, 5, 8. 8a-octahidone content 71 mol%
The intrinsic viscosity measured in decalin at 135°C [ 1
] 0. 60dl/ton Softening temperature TMA 115℃
, glass transition temperature Tg Q8℃) as a raw material and an extruder (
30. 1) using the T-die molding method to create a wall thickness of 130 μm.
Produce a sheet of m and combine the obtained sheet with the test piece.
The physical properties of the material were measured and the results are shown in Table 1.
A sheet was produced using the T-die molding method using Dφ), and this sheet was further biaxially stretched at 130°C and a stretching ratio of 2 x 2 to produce a stretched sheet (thickness: 95 μm). The sheet was used as a test piece and its physical properties were measured.The results are shown in Table 1.As a cyclic olefin copolymer, ethylene and DMON
Random copolymer with ``MFR 26@'' with an ethylene content of 62 mol% measured by 3C-NMR
C Intrinsic viscosity measured in decalin at 135°C at 35 g/10 min [1] 0.47 dl/ml Softening temperature (TM
A) 3.4 kg of beresotho with a temperature of 148°C, glass transition temperature Tg of 137°C) and an ethylene-propylene random copolymer as a rubbery component (ethylene content of 80 mol%, glass transition temperature of Tg of 137°C, intrinsic viscosity [η]) 2.2a
Example 1 was used in place of the cyclic olefin copolymer of
A test piece was prepared using the obtained sheet and its physical properties were measured.The results are shown in Table 1.11J4 For the pellet 1- obtained in Example 3. , Nihon Yushi■
Add 1 g of Perhexine 25B● manufactured by Perhexine and 3 g of divinylbenzene. Mix thoroughly. This mixture is reacted in a molten state using the twin-screw extruder (cylinder temperature: 230°C), and pelletized using a pelletizer. 8. The obtained beresotho was used in place of the cyclic olefin copolymer of Example 3.
A test piece was made from the sheet and its physical properties were measured.The results are shown in Table 1.

Claims (2)

[Claims] (1) Ring-opened polymers, ring-opened copolymers, and hydrogenated products of the polymers or copolymers derived from cyclic olefins represented by the following formula [I]; At least one polymer selected from the group consisting of addition polymers of cyclic olefin and ethylene, which has an intrinsic viscosity [η] of 0.01 to 10 dl/g measured in decalin at 135°C and a softening temperature of 70°C or higher. A sheet or film characterized by being made of various types of cyclic olefin resin; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [I] [In the above formula [I], n is 0 or a positive integer. Yes, R^1 to R^1^2 each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R^9 to R^1^2 are bonded to each other. may form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, and R^9 and R^1^0 and or R^1^1 and R
may form an alkylidene group with ^1^2]. (2) The sheet or film is a copolymer of ethylene, an α-olefin other than ethylene, and a cyclic olefin represented by the above formula [I], and the intrinsic viscosity [η] measured in decalin at 135°C is 0
．． 01-10dl/g, glass transition temperature (Tg) is 0℃
Soft cyclic olefin copolymer (i) which is the following: an amorphous or low crystalline α-olefin copolymer formed from at least two types of α-olefins and having a glass transition temperature (Tg) of 0°C or lower coalescence (ii), an α-olefin/diene copolymer (iii) formed from at least two α-olefins and at least one non-conjugated diene and having a glass transition temperature (Tg) of 0°C or lower; ), an aromatic vinyl hydrocarbon/conjugated diene random or block copolymer or its hydride (iv) having a glass transition temperature (Tg) of 0°C or lower, a soft polymer formed from isobutylene or a polymer conjugated with isobutylene A soft copolymer (v) formed from a diene, at least one soft polymer selected from the following, and a resin composition comprising the cyclic olefin resin. The sheet or film according to item 1.