JPH02180976A - Sheets or films with excellent tearability and their uses - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a sheet or film that is easily torn in the transverse (TD) direction.

[Conventional technology]

As a sheet or film with easy tearability,
1 polyethylene or polypropylene in the vertical (MD) direction
There are axially stretched or rolled sheets or films.

These are certainly easy to tear in the vertical (MD) direction,
It is used as an easily tearable packaging material. but,
Extremely difficult to tear in the transverse (TO) direction. For this reason,
It is unsuitable for applications that require ease of tearing in the horizontal direction, such as adhesive tapes and packaging bags for confectionery.

[Problem to be solved by the invention]

An object of the present invention is to provide a sheet or film that has the strength and transparency necessary for a packaging material and is easy to tear in the horizontal direction, and further provides an adhesive tape or packaging material made of the sheet or film. It is to be.

[Means to solve the problem]

The present invention provides the following sheets or films with excellent tearability, and adhesive tapes or packaging materials made of the same.

(1) (A) Consisting of an ethylene component and a cyclic olefin component represented by the following formula (I) or (n), 1
Intrinsic viscosity [η] measured in decalin at 35°C is 0.0
1 to lodΩ/g, a cyclic olefin random copolymer with a softening temperature (TMA) of 70°C or higher, or (
B) The following - Vertical (MD) hydrogenation of the ring-opening polymer of the cyclic olefin component represented by formula (1) or [II]
A sheet or film with excellent tearability characterized by being stretched in the direction from 0 to 2 times and stretched in the transverse (TD) direction from 3 to 8 times.

The general formula (A) is a cyclic olefin random copolymer containing an ethylene component and a specific cyclic olefin component as monomer components. The above-mentioned cyclic olefin component is a cyclic olefin represented by the above-mentioned formula (13 or (II)), and in the cyclic olefin-based random copolymer [A) of the present invention, the following-formula [111]
Alternatively, it forms a repeating unit having a structure represented by [IV].

General formula [where n and m are both O or a positive integer, Q is an integer of 3 or more, and R1 to Pa each represent a hydrogen atom, a halogen atom, or a hydrocarbon group. ] (2) An adhesive tape comprising the sheet or film described in (1) above.

(3) A packaging material comprising the sheet or film described in (1) above.

Cyclic olefin random copolymer in the present invention [wherein,
n, m, 12 and R1 to R1O are the same as above. ] Cyclic olefin random copolymer [A
) is at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by formula (I) and general formula (II).
The cyclic olefin represented by formula (1) can be easily produced by condensing cyclopentadiene and the corresponding olefin by Diels-Alder reaction. Similarly, the cyclic olefin represented by the formula (II) can be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by the Diels-Alder reaction.

Specifically, the cyclic olefin represented by the general formula [1] includes the compounds listed in Table 1, or l.

4.5.8-dimethano-1,2,3,4,4a,5,8
, 8a-octahydronaphthalene, as well as 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,5
, 8,8a-octahydronaphthalene, 2-ethyl-1
,4,5,8-dimethano-1,2,3,4,4a,5,
8.8a-octahydronaphthalene, 2-propyl-1
,4,5,8-dimethano-1,2,3,4,4a,5,
8,8a-octahydronaphthalene, 2-hexyl-1
,4,5,8-dimethano-1,2,3,4°4a,5,
8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,
5,8.8a-octahydronaphthalene, 2-methyl-
3-ethyl-1,4,5,8-dimethano-1,2,3,
4,4a,5,8,8a-octahydronaphthalene, 2
-chloro-1,4,5,8-dimethano-1,2,3,4
, 4a.

5.8,8a-octahydronaphthalene, 2-bromo-
1,4゜5.8-dimethano-1,2,3,4,4a,5
, 8,8a-octahydronaphthalene, 2-fluoro-
1,4,5,8-dimethano-1,2゜3.4,4a,5
, 8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a
, 5,8,8a-octahydronaphthalene, 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
-inbutyl-1,4,5,8-dimethano-1,2,3
, 4,4a, 5,8.8a-octahydronaphthalenes such as octahydronaphthalene, and the compounds listed in Table 2.

Furthermore, specific examples of the cyclic olefin represented by the formula CI include the compounds shown in Table 1 and Table 4.

The cyclic olefin random copolymer in the present invention is
It has an ethylene component and the above-mentioned cyclic olefin component as essential components, but in addition to these two essential components, other copolymerizable unsaturated monomers may be used as necessary to the extent that the object of the present invention is not impaired. It may also contain body components. Specific examples of unsaturated monomers that may optionally be copolymerized include propylene, ■-butene, and
4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene.

Examples include α-olefins having 3 to 20 carbon atoms such as 1-hexadecene, 1-octadecene, and 1-eicosene, cyclic olefins such as norbornene, ethylidene norbornene, and dicyclopentadiene, and cyclic dienes.

In the cyclic olefin random copolymer of the present invention,
The structural unit derived from the ethylene component is 40 to 85 mol%,
The structural units derived from the cyclic olefin component are preferably in the range of 50 to 75 mol%, and the structural units derived from the cyclic olefin component are suitably in the range of 15 to 60 mol%, preferably 25 to 50 mol%. The structural units derived from are randomly arranged to form a substantially linear cyclic olefin random copolymer. The above-mentioned cyclic olefin random copolymer is substantially linear and does not have gel-like crosslinked ends.
This can be confirmed by complete dissolution of C in decalin.

The intrinsic viscosity [η] of the cyclic olefin random copolymer [A] constituting the composition of the present invention measured in decalin at 135°C is 0.01 to 10 d1/g, preferably 0.0
It is in the range of 5 to 5 dQ/g.

The cyclic olefin random copolymer in the present invention has a softening temperature (TMA) of 70°C or higher, preferably 90 to 25°C, as measured by a thermomechanical analyzer.
The glass transition temperature of the cyclic olefin random copolymer (Tg
) is usually in the range of 50 to 230°C, preferably 70 to 210°C. In addition, the crystallinity of the cyclic olefin random copolymer measured by X-ray diffraction method is 0 to 10.
%, preferably from 0 to 7%, particularly preferably from 0 to 5%.

As the cyclic olefin random copolymer in the present invention, a copolymer consisting only of those having physical properties within the above range may be used, but a copolymer having physical properties outside the above range may be partially included. In this case, it is sufficient that the entire physical property value is within the above range.

The cyclic olefin random copolymer used in the present invention may contain other resin components, rubber components, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, slip agents, and anti-blocking agents to the extent that the purpose of the present invention is not impaired. , an antifogging agent, a lubricant, a nucleating agent, a dye, a pigment, a natural oil, a synthetic oil, a wax, etc. can be blended, and the blending ratio thereof is an appropriate amount. For example, as a stabilizer that may be added as an optional component, tetrakis[methylene-3 (3,5-di-monobutyl-4-
hydroxyphenyl)propionate comethane, β-(
Phenol oxidation of 3,5-di-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2,2'-oxamidobis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate, etc.] Preventive agent: zinc stearate, calcium stearate,
Fatty acid metal salts such as calcium 12-hydroxystearate; polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, etc. etc. can be given. These may be blended alone or in combination; for example, tetrakis[methylene-3(3,5
A combination of -di-t-butyl-4-hydroxyphenyl)propionate comethane, zinc stearate and glycerin monostearate, etc. can be exemplified.

The sheet or film of the present invention is produced by forming a sheet or film from the cyclic olefin random copolymer or a composition of this with other components blended as necessary, and then rolling the sheet or film in the vertical (MO) direction. The film was stretched in the range of 0 to 2 times, and 3 to 8 times in the transverse (TD) direction.

To form a sheet or film from a cyclic olefin random copolymer or a composition of this and other components, a general sheet or film forming method such as a T-die method or an inflation method can be adopted. . The thickness of the sheet or film formed at this time is not particularly limited.

The sheet or film thus formed is vertically (MD)
By stretching in the direction from 0 to 2 times and in the transverse (TO) direction from 3 to 8 times.

To obtain a sheet or film having excellent tearability according to the present invention. Stretching is performed at a temperature equal to or higher than the glass transition temperature (Tg), and the vertical and horizontal stretching ratios can be arbitrarily selected depending on the required physical properties. Further, as the stretching means, in-shell stretching means such as roll stretching, tenter stretching, and inflation method can be employed.

To specifically explain a preferred method for producing a stretched sheet or film, a cyclic olefin random copolymer or its composition is molded to a thickness of 0.03 to 5III11 by a T-die molding method or an inflation molding method.
, preferably from 0.1 to 311 [+1]. Then, this sheet is heated to 0 to 60°C, preferably 10 to 4°C, higher than the glass transition temperature (Tg) of the copolymer.
0 to 2 in the vertical direction sequentially or simultaneously at a temperature higher than 0°C.
Stretch 3 to 8 times in the horizontal direction.

The stretched sheet or film thus obtained has the property of being easily torn in the horizontal direction, and thus can be used for adhesive tapes.

In addition, the sheet or film of the present invention has excellent transparency and can withstand shocks and vibrations during distribution processes such as cargo handling, transportation, and storage.
It also has the strength to protect the packaged item from external forces such as compression, so it can be used as a packaging material that can be torn horizontally to easily remove the packaged item. For example, packaging containers such as bags made from the film of the present invention can be used to store fruit juice, soft drinks, etc.
It can be used for packaging dry confectionery such as alcoholic beverages, snack foods, rice crackers, rice crackers, bean sweets, etc., and for packaging medical supplies.

Furthermore, the sheet or film of the present invention has high strength;
Since it is easy to tear in the horizontal direction, it can be used for film or sheet packaging materials that can be easily adjusted to any width.

The above explanation is based on the ethylene component and the -release (1) or (
Although the cyclic olefin random copolymer [^] consisting of the cyclic olefin component represented by II) has been explained, instead of this cyclic olefin random copolymer (A), ) may be used, and the same effect can be obtained by using a hydride [8] of a ring-opening polymer of a cyclic olefin component. In this case, a stretched sheet or film having similar properties can be obtained by the same method as for the cyclic olefin random copolymer [A]. Such ring-opened polymers of cyclic olefins are disclosed, for example, in JP-A-60-26024.

In the ring-opening polymer before hydrogenation of the hydride [B] of the ring-opening polymer, the -injection (I) or (II)
) The cyclic olefin component represented by the following - release [■]
Or, it forms a repeating unit with a structure represented by (Vl).

General formula [where n, m, Q and R1 to RIQ are the same as above.] ] The ring-opening polymer before hydrogenation is prepared by conventional ring-opening of a cyclic olefin using the heptamer component selected from the above-mentioned (1) and Cl1l and other monomer components copolymerized if necessary. It can be produced by a polymerization method. Examples of polymerization catalysts include ruthenium, rhodium,
Systems consisting of halides such as palladium, osmium, iridium, platinum, molybdenum, tungsten, nitrates or acetylacetone compounds and reducing agents such as alcohols and tin compounds, or halogen compounds such as titanium, vanadium, zirconium, tungsten, molybdenum, etc.
A system consisting of an acetylacetone compound or the like and an organic aluminum compound or the like can be used.

The ring-opened polymer hydride [13] is obtained by hydrogenating the ring-opened polymer obtained above. Hydrogenation of the ring-opened polymer is carried out by conventional hydrogenation methods.

As the hydrogenation catalyst, those used in the hydrogenation of olefin compounds can generally be used. Specifically, as a heterogeneous catalyst.

Solid catalysts made of nickel, palladium, platinum, etc., or these metals supported on carriers such as carbon, silica, diatomaceous earth, alumina, titanium oxide, etc., such as nickel/silica, nickel/on diatomaceous, palladium/carbon, palladium/silica , palladium/diatomaceous earth, palladium/alumina, etc. Homogeneous catalysts include those based on metals from Group 1 of the periodic table, such as nickel naphthenate 71 and ethylaluminum,
Cobalt octenoate/n-butyllithium, nickel acetylacetone-1/1-ethylaluminum, etc. consisting of Ni, Co compounds and organometallic compounds of group r-+n metals of the periodic table, or Rh compounds, etc. can be given.

The hydrogenation reaction of the ring-opening polymer is carried out in a homogeneous or heterogeneous system depending on the type of catalyst under a hydrogen pressure of 1 to 150 atm at a temperature of 0 to 180°C, preferably 20 to 100°C. be exposed. The hydrogenation rate depends on hydrogen pressure, reaction temperature,
It can be adjusted by adjusting the reaction time, catalyst concentration, etc., but it is preferably 50% or more of the main chain double bonds in the polymer, preferably 8
It is preferred that 0% or more, more preferably 90% or more, be hydrogenated.

〔Effect of the invention〕

According to the present invention, a cyclic olefin-based random copolymer consisting of an ethylene component and a specific cyclic olefin component, or a hydrogenated product of a ring-opening polymer of a specific cyclic olefin component, is mono- or biaxially stretched at a specific magnification. A sheet or film with improved strength and easy tearing in the horizontal direction can be obtained.

Furthermore, adhesive tapes that are easily torn in the horizontal direction, packaging materials that allow easy removal of packaged items, and the like can be obtained from the above-mentioned sheets or films.

〔Example〕

Examples of the present invention will be described below.

Examples 1 and 2 Ethylene and 2-ethyl-1,4,5,8-dimethano-1
, 2, 3, 4, 4a.

E-DMON) copolymer with an intrinsic viscosity [η] of 1.0.
1 clQ/g and a glass transition temperature (Tg) of 113° C. were used as raw materials, and a sheet with a wall thickness of 0.4+n+u was produced by T-die molding using a 30 mmφ extruder. This sheet was heated to 130°C, approximately 20°C higher than Tg, by 1.5 times vertically and 4.0 times horizontally (Example 1) or 2 times vertically.
Simultaneous biaxial stretching was performed at 0 times and 3.0 times in width (Example 2) to produce a film with a thickness of 0.065 mm. The obtained stretched film is stretched by +t in both the vertical and horizontal directions.
Cut into strips of li15m+m.

1. Tear strength by making a 90 degree notch with a width of 5 mm,
Film impact etc. were measured. The results are shown in Table 5.

Comparative Examples 1 and 2 The 0.4 mm thick sheet of Example 1 was stretched 2.3 times vertically and 2.3 times horizontally under the same conditions as Example 1. Comparative Example 1
), and an unstretched film with a wall thickness of 0.065+am was prepared and its tear strength etc. were measured in the same manner as in Comparative Example 2) and Example 1. The results are shown in Table 5.

From the results in Table 5, it can be seen that all of the examples were easier to tear in the horizontal direction than the comparative examples, and the film impact was improved.

Claims (3)

[Claims] (1) [A] Consists of an ethylene component and a cyclic olefin component represented by the following general formula [I] or [II],
The intrinsic viscosity [η] measured in decalin at 135°C is 0.
01 to 10 dl/g, a cyclic olefin random copolymer with a softening temperature (TMA) of 70°C or higher, or [
B] A hydrogenated product of a ring-opening polymer of a cyclic olefin component represented by the following general formula [I] or [II] is stretched in the longitudinal (MD) direction in a range of 0 to 2 times,
A sheet or film with excellent tearability characterized by being stretched 3 to 8 times in the transverse (TD) direction. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ --- [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ --- [ II ] [In the formula, n and m are both 0 or positive integers. Yes, l is an integer greater than or equal to 3, and R^1 to R^1^0
each represents a hydrogen atom, a halogen atom, or a hydrocarbon group. ] (2) An adhesive tape comprising the sheet or film according to claim (1). (3) A packaging material comprising the sheet or film according to claim (1).