U.S. patent number RE33,832 [Application Number 07/557,113] was granted by the patent office on 1992-02-25 for composition for drawn film, cold film made of said composition and process for manufacturing of said film.
This patent grant is currently assigned to Asahi Kasei Kogyo Kabushiki Kaisha. Invention is credited to Hideo Hata, Takashi Kaneko, Isao Yoshimura.
United States Patent |
RE33,832 |
Yoshimura , et al. |
February 25, 1992 |
Composition for drawn film, cold film made of said composition and
process for manufacturing of said film
Abstract
A composition for shrinkable film which excells in
heat-sealability, transparency, strength, and particularly
low-temperature quick shrinking property and, therefore, suits
production chiefly of packaging materials, a film made of the
composition and a process for the manufacture of the film are
disclosed. Specifically, the composition comprises one of the
specific combinations of components (A), (B) and (C), i.e. the
combinations of (A)+(B), (B)+(C) and (A)+(B)+(C), wherein (A) is
non-rigid polyolefine resins such as ethylene vinyl acetate, (B) is
an elastomer comprising a specific ethylene-.alpha.-olefin
copolymer and an elastomer consisting of block copolymer having at
least one monovinyl substituted aromatic, hydrocarbon polymer block
and at least one polyolefin polymer block selected from at least
one saturated polymer or unsaturated polymer made from mainly
aliphatic conjugate diene derivative, and (C) is rigid polyolefin
resins such as polypropylene. The packaging film excelling
particularly in optical property, mechanical strength and
low-temperature shrinking property is obtained by converting a
homogeneous blend of the aforementioned composition, either in its
crosslinked form or in its non-crosslinked form, into a tubular raw
film, which is stretched at a temperature low enough for imparting
a high orientation to the film. The process for the manufacture of
this packaging film is also disclosed.
Inventors: |
Yoshimura; Isao (Fujisawa,
JP), Hata; Hideo (Suzuka, JP), Kaneko;
Takashi (Obama, JP) |
Assignee: |
Asahi Kasei Kogyo Kabushiki
Kaisha (Osaka, JP)
|
Family
ID: |
27464370 |
Appl.
No.: |
07/557,113 |
Filed: |
July 25, 1990 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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825774 |
Feb 3, 1986 |
4701496 |
|
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|
670678 |
Nov 13, 1984 |
|
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|
457362 |
Jan 12, 1983 |
|
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|
|
213461 |
Dec 5, 1980 |
4449241 |
|
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|
949253 |
Oct 6, 1978 |
4277578 |
|
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Reissue of: |
109659 |
Oct 19, 1987 |
04835218 |
May 30, 1989 |
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Foreign Application Priority Data
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Oct 11, 1977 [JP] |
|
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52-120917 |
Nov 22, 1977 [JP] |
|
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52-139431 |
May 30, 1978 [JP] |
|
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53-63870 |
May 30, 1978 [JP] |
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53-63872 |
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Current U.S.
Class: |
525/98; 525/97;
525/221; 525/95; 525/99 |
Current CPC
Class: |
B29C
61/003 (20130101); C08L 23/02 (20130101); C08L
23/02 (20130101); C08L 23/0853 (20130101); C08L
23/10 (20130101); B29C 48/0018 (20190201); C08L
23/16 (20130101); B29C 48/001 (20190201); B29C
48/10 (20190201); C08L 2666/04 (20130101) |
Current International
Class: |
C08L
23/02 (20060101); C08L 23/00 (20060101); B29C
61/00 (20060101); B29C 47/00 (20060101); C08L
23/10 (20060101); C08L 23/08 (20060101); C08L
23/16 (20060101); C08L 053/02 (); C08L 023/16 ();
C08L 023/12 (); C08L 023/08 () |
Field of
Search: |
;525/97,98,99,211,221 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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WO86/04912 |
|
Aug 1986 |
|
WO |
|
2131816 |
|
Jun 1984 |
|
GB |
|
Primary Examiner: Seccuro; Carman J.
Attorney, Agent or Firm: Cushman, Darby & Cushman
Parent Case Text
This application is a continuation-in-part of application of Ser.
No. 06,825,774 filed Feb. 3, 1986, now U.S. Pat. No. 4,701,496
which is a continuation of application Ser. No. 670,678 filed Nov.
13, 1984 and now abandoned; which is a continuation of Ser. No.
457,362, filed Jan. 12, 1983 and now abandoned; which is a division
of Ser. No. 213,461, filed Dec. 5, 1980, and now U.S. Pat. No.
4,449,241 which is a division of Ser. No. 949,253, filed Oct. 6,
1978 and now U.S. Pat. No. 4,277,578.
Claims
What is claimed is:
1. A composition comprising a homogeneous blend of one of the
specific combinations of components, namely the combination of
(A)+(B)+(C); wherein
(A) is at least one selected from the group consisting of
copolymers of ethylene with unsaturated aliphatic monocarboxylic
acids and alkyl esters of said acids which are all copolymerizable
with ethylene.
(B) is a mixed elastomer consists of an elastomer having a density
of not more than 0.91 g/cm.sup.3 and made of an
ethylene-.alpha.-olefin copolymer and an elastomer consisting of
block copolymer having at least one monovinyl substituted aromatic
hydrocarbon polymer block and at least one polyolefin polymer block
selected from at least one saturated polymer or unsaturated polymer
made from mainly aliphatic conjugate diene derivative, and
(C) is at least crystalline polymer selected from the group
consisting of crystalline polypropylene, high-density polyethylene
and crystalline polybutene-1, wherein the components of the
composition are in amounts such as to satisfy
.[.0.05<B/(A+B)<0.90 and 0.05<C/(A+)<2.0.].
.Iadd.0.05.ltoreq.B/(A+B).ltoreq.0.90 and
0.05.ltoreq.C/(A+B).ltoreq..Iaddend.in terms of weight ratio.
2. The composition according to claim 1, wherein the component (A)
is at least one selected from the group consisting of,
ethylene-acrylic acid copolymers, ethylene-metharcylic acid
copolymer, ethylene-ethyl acrylate copolymers, and ethylene-methyl
methacrylate copolymer.
3. The composition according to claim 1, wherein the
ethylene-.alpha.-olefin copolymer as the component (B) has an
ethylene group content of not more than 90 mol % and not less than
20 mol %.
4. The composition according to claim 1, wherein the
ethylene-.alpha.-olefin copolymer as the component (B) has an
ethylene group content of not more than 90 mol % and not less than
40 mol %.
5. The composition according to claim 1, wherein the
ethylene-.alpha.-olefin copolymer as the component (B) is a
non-rigid copolymer having a Vicat softening point of not more than
80.degree. C. and a degree of crystallization of not more than 30%,
wherein the .alpha.-olefin component contained therein is at least
one member selected from the group consisting of .alpha.-olefin
having from 3 to 12 carbon atoms.
6. The composition according to claim 1, wherein the
ethylene-.alpha.-olefin copolymer as the component (B) is a random
copolymer, wherein the .alpha.-olefin component contained therein
is selected from the group consisting of propylene butene-1.
7. The composition according to claim 1, wherein the
ethylene-.alpha.-olefin copolymer as the component (B) has a
polyene copolymerized in addition to the main components of
ethylene and .alpha.-olefin.
8. The composition according to claim 1, wherein the
ethylene-.alpha.-olefin copolymer as the component (B) contains not
more than 5 mol % of a non-conjugate diene selected from the group
consisting of hexadiene and norbornene derivatives.
9. The composition according to claim 1, wherein the elastomer
consisting of block copolymer is at least one selected from the
group consisting of, styrene-butadiene block copolymer,
styrene-isoprene block copolymer, carboxylic acid modified
styrene-butadiene block copolymer, carboxylic acid modified
styrene-isoprene block copolymer, at least one hydrogenized
styrene-butadiene block copolymer, at least one hydrogenized
styrene-isoprene block copolymer, carboxylic acid modified at least
one hydrogenized styrene-butadiene block copolymer and, carboxylic
acid modified at least one hydrogenized styrene-isopreme block
copolymer.
10. The composition according to claim 9, wherein carboxylic acid
modified block copolymer is made of a copolymerized graft
polymerizable monomer containing a monocarboxylic acid or
dicarboxylic acid, which copolymerization ration is in the range of
from 0.2 to 10% by weight.
11. The composition according to claims 1, 9 or 10, wherein the
elastomer consisting of block copolymer contains monovinyl
substituted aromatic hydrocarbon polymer block in the range of from
not less than 10 or not more than 60% by weight.
Description
BACKGROUND OF THE INVENTION
Packages formed with films are manufactured by a good number of
methods which utilize to advantage the characteristics of the films
such as the bag sealing method, twist wrapping method, thermal
shrink wrapping method, cohesive wrapping method by use of specific
films represented by Saran Wrap (product by Asahi-Dow Limited),
stretch wrapping method and the like. These methods require
respective wrapping characteristics. For each packaging method,
therefore, it is important to select a film whose basic material,
composition, form and characteristic attributes best suit the
wrapping characteristics of the particular method employed.
Of these packaging methods, this invention primarily aims to
provide a film particularly suitable for the shrink wrapping
method. Nevertheless the film of the present invention need not
limit its uses but may be put to other uses satisfactorily. Thus,
this is a unique multipurpose film never attained t o date. For the
convenience of illustration, therefore, the present invention will
be hereinafter described with reference to the film formulated t
suit the shrink wrapping method.
Generally, the shrink wrapping method effects required wrapping by
virtue of the thermal shrinkability of a film stretched and
oriented in fixed directions, specifically resorting to a procedure
of loosely prepackaging a given commodity with the film as by
sealing, and thereafter thermally shrinking the film as enclosing
the commodity therein by means of a suitable heat medium such as
the hot air, infrared ray or hot water for thereby causing the film
to shrink and come into skintight contact with the overall
irregular contour of the commodity. This method is characterized by
providing a package which has a beautiful appearance, imparts an
enhanced commercial value to the content, keeps the content in a
hygienic condition and yet permits the content to be examined for
its quality through visual observation or by sensation of touch.
This method enables even a commodity of irregular shape or a
plurality of commodities to be packaged with ample tightness in a
single piece and provides the content with effective protection
against vibrations and other impacts.
Further, the shrink wrapping method provides speedy packaging as
compared with the stretch wrapping method which is extensively used
such as in super markets. As an effective method for industrial
packaging of heavy articles of large dimensions which the stretch
wrapping method is incapable of packaging, this shrink wrapping
method is finding rapidly increasing acceptance and arresting keen
attention.
Moreover, it permits packaging of commodities of shapes so
irregular as to defy effective packaging by the stretching method
and enables desired packaging to be accomplished without use of
trays or other containers. It also enjoys greater tightness of
package. In spite of all these advantages, the shrink wrapping
method has a disadvantage that the package must be amply heated
until the film shrinks to required tightness.
It is the oriented film of plasticized polyvinyl chloride
(hereinafter referred to as PVC) that is now used most widely for
the shrink wrapping. This is ascribable to the film's great merit
of readily undergoing thermal shrinkage of a high rate of
relatively low temperatures and providing satisfactory shrink
wrapping in a wide range of temperatures. On the other hand, this
film nevertheless has a disadvantage that it provides heat
sealability, preservability (liability of the plasticizer to
degrade properties brought about by the orientation of film) and
moistureproofness less than normally required, entails a hygienic
hazard due to use of the plasticizer, emits noxious gases such as
chlorine-based gases when the film is cut by means of heated wire,
issues corrosive gases when the film, after use, is burnt in an
incinerator and, because of its inferior cold resistance, tends to
rigidify, embrittle and rupture when the packages using the film
are stored at low temperatures or handled in cold districts.
In recent years, therefore, increasing attention has come to be
focussed on a polypropylene type (hereinafter referred to as PP)
film for use in the shrink wrapping method. The PP film has a
disadvantage that it provides inferior shrinkability to the PVC
film. The oriented film of the PP type is excellent in mechanical
property, moistureproofness, heat seal strength, heat resistance
and film modulus and, therefore, proves to be highly suitable for
use as a film for the shrink wrapping.
Further, PP is advantageous over PVC in terms of raw material cost
and because of low specific gravity. Because PP is a rigid,
crystalline polymer possessing a high softening point, the PP film
requires heating at a higher temperature for necessary shrinkage
than the conventional oriented films and exhibits a very slight
degree of shrinkage at low temperatures in the neighborhood of
100.degree. C. Thus, the PP film must be heated at high
temperatures in the course of the shrink wrapping. Moreover since
the allowable range of temperatures for the heating is narrow and
the dependency of the rate of shrinkage upon temperature is heavy,
a locally uneven heating possibly given to the film at the time of
wrapping results in a notable uneven shrinkage which tends to cause
creases, dots resembling pockmarks and other surface irregularities
which are undesirable from the viewpoint of practical use of film.
More heating given to the film for the purpose of preventing such
uneven shrinkage brings about a serious drawback that the content
being packaged is excessively heated, the film is deprived of its
transparency, and the film is ruptured along the sealed portion and
around the air vents. Generally, the PP film is available
preponderantly in small thickness. If the thickness is increased,
the PP film becomes too rigid to permit successful shrink wrapping
and tends to sustain rupture readily.
The conventional low-density polyethylene (hereinafter referred to
as LDPE) film in its unaltered form does not permit sufficient
orientation of molecules. The oriented LDPE film resulting from the
treatment of stretching, therefore, exhibits low thermal shrinkage
and particularly low thermal shrink tension, requires high
temperature for shrinkage, offers poor film strength and optical
property, produces low binding force in the package with respect to
the article contained. Because of these inferior properties, the
LDPE film which is produced in an increased thickness is put to
special uses.
In the case of LDPE film, if the film is stretched thoroughly at a
high temperature exceeding its melting point by use of a
high-energy ray so as to cause crosslinking of molecules, the
oriented film enjoys high processibility, permits required
temperature to be set effectively in a range of high temperatures,
exhibits high thermal shrinkage and high thermal shrink tension and
excels the LDPE film in various properties such as optical
properties including transparency and gloss, resistance to heat and
the like. In the range of high temperatures, however, the thermal
shrinkage is not high enough to permit effective heat sealing and
the film strength is degraded to impair the heat sealability and
tear resistance.
Further, the oriented LDPE film has a disadvantage that the cutting
and the sealing of film by means of a heating wire are difficult to
effect, the physical properties, particularly the optical
properties are degraded subsequently to the thermal shrinkage, the
film strength is lowered, and the film tends to sustain rupture and
creases around air vents at the time of shrink wrapping. Because of
these drawbacks, the shrink wrapping by use of the oriented LDPE
film is inferior in terms of speediness of operation and
finish.
As is clear from the foregoing description, one important
requirement for successful shrink wrapping resides in the fact that
the film should permit required packaging to be effectively carried
out at low temperatures. This requirement is particularly
significant when the packaging is given to fresh food.
The oriented PP film is produced by a procedure of extruding the
molten polymer through an annular die into a tubular raw film,
suddenly cooling the extruded tubular raw film, again heating the
raw film at high temperatures in the range of from 150.degree. to
160.degree. C. and simultaneously introducing air into the interior
of tubular raw film. The oriented LDPE film can be produced by the
conventional procedure which is employed in biaxially stretching.
These processes are extremely difficult to accomplish from the
technical point of view because the films are highly liable to
sustain rupture.
Thus, the direct inflation method which involves a procedure of
extruding the molten polymer at a temperature in the range of from
180.degree. to 220.degree. C., for example, and thereafter suitably
cooling the extruded tubular film with ambient air and, at the same
time, inflating the film to a film of a desired size is generally
employed.
The inflation method is characterized by being capable of producing
a desired film readily and inexpensively. It nevertheless suffers
from a disadvantage that the treatment entails irregular flow and
crystallization of molecules and impairs the optical properties of
film and the stretching fails to provide satisfactory setting of
molecular orientation. Consequently, the thermal shrinkage and
thermal shrink tension are deficient and high temperatures are
required for ensuring their sufficiency. The film produced by this
method, therefore, in impracticable unless it is produced in an
increased and put to special uses. To overcome the disadvantage,
there have been developed improved methods resorting inveriably to
a procedure of extruding LDPE in the form of a tubular film,
exposing the film to a high-energy radiant ray under suitable
conditions for thereby inducing a partial crosslinking reaction in
the film and reheating and stretching the film so as to effect
required setting of molecular arrangement sufficiently without
entailing random intermolecular flow. The conventional inflation
method, however, produces a film which is not free from the
aforementioned drawbacks.
A good many methods have heretofore been suggested for producing
films by mixing polymers of different olefins or mixing polyolefins
with other polymers and subsequently inflating the resultant
blends. For example, U.S. Pat. No. 3,682,767 discloses a method for
producing a film possessing improved melt strength and heat
sealaibility and exhibiting improved make-and-fill property at the
time of packaging a liquid commodity by a procedure of mixing
ethylene, an olefin type unsaturated monomer such as, for example,
ethylene-vinyl acetate copolymer (hereinafter referred to as EVA)
and a linear copolymer of ethylene with an .alpha.-olefin having a
density in the range of from 0.93 to 0.96 l g/cm.sup.3, such as,
for example, a modified high-density polyethylene (hereinafter
referred to as HDPE) and subsequently extruding the resultant blend
in the form of a flat or tubular sheet. British Pat. No. 988,299
teaches a process for producing a printable polyethylene film by a
procedure of mixing EVA eith LDPE or HDPE, causing crosslinking in
the resultant blend either before or after molding, and
subsequently stretching the blend in the form of film. And British
Pat. No. 1,035,887 concerns a process for the production of a film
excelling in low-temperature properties by a procedure of mixing
LDPE with a linear medium-density polyethylene obtained by
modifying ethylene with a small amount of butene and stretching the
resultant blend.
As to manufacture of films, British Pat. No. 998,299 mentioned
above involves a procedure of treating the aforementioned
composition with a peroxide or a high-energy ray and thereby
causing crosslinking and subsequently stretching the crosslinked
sheet at temperatures close to or slightly higher than the melting
point of polyethylene and British Pat. No. 992,897 adopts a
procedure of treating EVA with a high-energy ray and thereby
causing crosslinking and subsequently stretching the crosslinked
sheet at elevated temperatures (preferably in the range of from
100.degree. to 120.degree. C., for example). The films obtained of
such compositions are devoid of the excellent optical properties,
strength properties and low-temperature shrinking property enjoyed
by the aforementioned PVC type films and they fail to exhibit
satisfactory film-forming property.
SUMMARY OF THE INVENTION
The new composition of the present invention is a novel composition
of which properties that described later are notably improved by
cold drawing. Therefore, as the use of this nature, it is
advantageously used as films, sheets or molded products etc. this
composition can be used after enhancing its properties by
stretching beforehand, of course, it also exhibits it excellent
properties such as impact strength etc. even if used as
nonstretched molded products. The reason for this is because the
strength is greatly improved by virtue of the cold orientation when
deformed by forces of tention and impact etc. at practical use
regardless of its initial form and orientation condition.
Hereinafter, it is described with the examples of films, however,
not only limited to the films. Furthermore, besides the
abovementioned properties, the printability and paintability of its
surface are also improved.
The inventors carried out a study with a view to improving these
films and their manufacturing methods and thereby eliminating their
inherent drawbacks. They have, consequently, developed a
composition as the raw materials for the film which far excels in
thermal shrinkage properties, particularly thermal shrinkage and
thermal shrink tension at low temperatures and broadness of
temperature range for thermal shrinkage upon temperature, optical
properties, film sealing property and film strength and which,
therefore, excels both plasticized PVC film and PP film and
combines the characteristics of both the films, and a film formed
of said composition and a process for the manufacture of the film
which enjoys an outstanding workability.
BRIEF EXPLANATION OF DRAWINGS
FIG. 1 is a graph which shows the relation between the shrinkage of
film and the heat-treating temperature.
FIG. 2 is a graph which shows the relation between the shrink
tension of the film and the heat-treating temperature.
FIG. 3 shows the result of the practical shrink-wrapping test of
the various films, namely the range capable of obtaining the good
wrapping finish not having a wrinkling, a pockmark and a breakage
when four cucumbers were shrink-wrapped.
FIG. 4 shows the range capable of obtaining the suitable
heat-sealing when the heat-sealing was carried out by the heating
bar type sealer.
FIG. 5 shows the variation of the characteristic properties of the
film of Run No. 1 Example 1 in the stretch-working temperature, the
area (A) is the area of the film of the present invention.
In the figure, curve 1 indicates the film of Run No. 2 Example 1.
Curve 2 indicates the film (17.mu. in thickness) of the commercial
plasticized PVC shrink film. Curve 3 indicates the commercial PP
shrink film (18.mu. in thickness). Curve 4 indicates the commercial
uncrosslinked low density polyethylene shrink film (50.mu. in
thickness). Curve 5 indicates the commercial crosslinked
polyethylene shrink film (17.mu. in thickness).
DETAILED DESCRIPTION OF THE INVENTION
To be specific, the present invention relates to a composition
which comprises one of the combinations of components (A), (B) and
(C), namely the combinations of (A)+(B), (B)+(C), and (A)+(B)+(C),
wherein (A) is at least one selected from the group consisting of
LDPE and copolymers of ethylene with vinyl ester monomers,
unsaturated aliphatic monocarboxylic acids and alkyl esters of said
monocarboxylic acids which are all copolymeriable with ethylene,
(B) is an elastomer comprising a specific ethylene-.alpha.-olefin
copolymer and an elastomer consisting of block copolymer having at
least one monovinyl substituted aromatic hydrocarbon polymer block
and at least one polyolefin polymer block selected from at least
one saturated polymer or unsaturated polymer made from mainly
aliphatic conjugate diene derivative, and (C) is at least one
selected from the group consisting of crystalline PP, HDPE and
crystalline polybutene-1 (hereinafter referred to as PB-1), to a
film manufactured by thoroughly melting and blending said
composition, extruding the resultant homogeneous blend through an
annular die, suddenly cooling the tubular sheet with a liquid
refrigerant, causing the resultant solidified sheet, either
immediately thereafter or subsequently to a treatment with a
high-energy energy ray or incorporation of a peroxide aimed at
inducing crosslinking in the sheet during the subsequent
application of heat, to be heated to temperatures not exceeding
110.degree. C., then cold stretching the heated sheet into a film
at an area stretching ratio of from 5 to 30 times the original
dimension at a stretching temperature in the range of from room
temperature (20.degree. C.) to 100.degree. C., and further to a
process for the manufacture of said film. The film thus produced
from the composition of this invention by the process also of this
invention is characterized by possessing outstanding
low-temperature shrinkability, film strength, optical properties
and other characteristics which have never been attained to
date.
The polymer (A) to be used in the present invention is selected
from the group consisting of LDPE and copolymers of ethylene with
vinyl ester monomers, unsaturated aliphatic monocarboxylic acids
and alkyl esters of said monocarboxylic acids. LDPE possesses a
density of not more than 0.935 g/cm.sup.3, preferably not more than
0.925 g/cm.sup.3, and a melt index [determined in accordance with
ASTM D-1238 (190.degree. C.)] of from 0.2 to 10, preferably from
0.1 to 5. Examples of the copolymers satisfying the requirement
include EVA, ethyleneacrylic acid copolymer, ethylene-methacrylic
acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl
methacrylate copolymer, and the like. In any of these copolymers,
the amount of a monomer contained besides ethylene is desired to be
in the range of from 3 to 30% ;by weight, preferably from 3 to 25%
by weight. If the amount of the monomer is less than 35 by weight,
the cold stretchability is somewhat inferior when the stretching is
carried out on the film in its uncrosslinked form. Besides the
film's strength, thermal shrinkability and sealing property are not
sufficient. If the amount exceeds 30% by weight, the tubular sheet
has inferior processibility and the opposed surfaces of film
undergo the phenomenon of mutual blocking to render the film
handing difficult, and the mixing property of the components to
make up the composition, the strength of film and the oiptical
properties, etc. are impaired. As described above, the melt index
of the polymer is in the range of from 0.2 to 10, preferably from
0.3 to 5. If the melt index is less than 0.2, the mixing property
of the components of the composition and the extrudability of the
resulting blend are not satisfactory. If the melt index exceeds 10,
the blend fails to provide sufficient strength and the extruded
sheet tends to sustain rupture readily at the time of stretching.
These drawbacks are suffered also when the sheet is subjected to
the treatment for crosslinking.
Of the various possible copolymers usable as the component (A) in
the composition of this invention, most desirable is ethylene-vinyl
acetate copolymer. In the case of a low-density polyethylene, the
blend is desired to be subjected to said treatment for
crosslinking.
The elastomer of (B) component consists of an
ethylene-.alpha.-olefin copolymer (BI) and an elastomer of a
specific block copolymer (BII), both are described later, and its
mixing ratio is not limited, however, preferably in the range of
0.05.ltoreq.BII/(BI+BII).ltoreq.0.50. The thermoplastic elastomer
comprising a copolymer of ethylene with at least one .alpha.-olefin
as the component (B) is a non-rigid copolymer of ethylene with at
least one .alpha.-olefin selected from the group consisting of
.alpha.-olefins having from 3 to 12 carbon atoms. As occasion
demands, this elastomer may be further copolymerized with a small
amount of a hydrocarbon of the polyene structure such as, for
example, 1,4-hexadiene, ethylidene, norborene, etc. Examples of the
.alpha.-olefin suitable for this purpose include propylene,
butene-1, hexene-1, heptene-1, 4-methyl-1-pentene, octene-1, etc.
Of these .alpha.-olefins, preferable are propylene and butene-1. In
any of these copolymers, the ethylene content is desired to fall in
the range of from 20 to 90 mol %, more desirably from 40 to 90 mol
%, preferably from 65 to 88 mol %.
These copolymers are of such nature that the density is not more
than 0.91 g/cm.sup.3, the Vicat softening point [as determined in
accordance with ASTM D-1525 (value under 1 kg of load)] is not more
than 80.degree. C., preferably not more than 70.degree. C. and the
crystallinity in the rubbery zone generally ranges from substantial
amorphousness to low partial crystallinity of the order of not more
than 30% of crystallinity degree determined with X-ray.
The component (BI) is particularly desired to be a copolymer of
ethylene with propylene or butene-1, and this copolymer may, when
necessary, incorporate therein a small amount of a compound of the
diene structure in the form of a copolymer. It is, therefore, a
thermoplastic elastomer in the form of a random copolymer obtained
by the polymerization using a catalyst of the system produced with
a vanadium compound and an organic aluminum compound. The elastomer
possesses a melt index of from 0.1 to 10, preferably from 0.2 to
6.
The component (BII) is an elastomer consisting of block copolymer
having at least one monovinyl substituted aromatic hydrocarbon
polymer block and at least one polyolefin polymer block selected
from at least one saturated polymer or unsaturated polymer made
from mainly aliphatic conjugated diene derivative. The elastomer
consisting of block copolymer is at least one selected from the
group consisting of, styrene-butadiene block copolymer,
styrene-isoprene block copolymer, carboxylic acid modified
styrene-butadiene block copolymer, carboxylic acid modified
styrene-isoprene block copolymer, at lest one hydrogenized
styrene-butadiene block copolymer, at least one hydrogenized
styrene-isoprene block copolymer, carboxylic acid modified at least
one hydrogenized styrene-butadiene block copolymer and, carboxylic
acid modified at least one hydrogenized styrene-isopreme block
copolymer. The abovementioned carboxylic acid modified block
copolymer is made from a copolymerized graft polymerizable monomer
containing a monocarboxylic acid or dicarboxylic acid, which
copolymerization ratio is in the range of from 0.2 to 10% by
weight. The elastomer consisting of block copolymer contains
monovinyl substituted aromatic hydrocarbon polymer block in the
range of from not less than 10% to not more than 60% by weight,
preferably in the range of from not less than 10 to not more than
50% by weight.
Among all the components mentioned above, a preferable (BII)
component is a polymer containing a double bonds resulted from the
conjugated diene component which is the rubber component of its
moleculars and at least some of the double bonds are hydrogenized,
preferably substantially not less than 95%. More preferably, a
copolymer obtained by graft copolymerizing and modefying the
abovementioned hydrogenized polymer with a monomer containing a
monocarboxylic acid or dicarboxylic acid.
The monomer to be used for modifying the polymer may be any of
those such as, for example, acryl type derivative, maleic acid type
derivative, fumaric acid type derivative, itaconic acid type
derivative, succinic acid type derivative, adipic acid type
derivative, phthalic acid derivative, or other derivatives which
are well known to the public.
Further, oligomers, prepolymers and polymers obtained from the
monomers having carboxylic acid group mentioned above, which are
graft copolymerizable are also used as well. As for the (BII)
component, a component obtained by reacting a polymer like as a
polyester or a polyamide with the abovementioned modified or not
modified copolymer by following the process already known to the
public may be used.
The polymer (C) is at least one selected from the group consisting
of crystalline, PP, HDPE and high molecular PB-1 which each possess
relatively high rigidity and relatively high degree of
crystallinity. The polymer has relatively high rigidity and
desirably a Vicat softening point of not less than 100.degree.
C.
the crystalline PP which is one of the members of the group from
which the component (C) of the composition of this invention is
selected is a crystalline PP with high isotacticity usually
available on the market. It is desired to be a homopolymer of
propylene or any of the copolymers of propylene with not more than
10 mol % of ethylene, 1-butene or some other .alpha.-olefin. It may
be a mixture of these copolymers.
HDPE as one member of said group is a polyethylene produced by the
medium- or low-pressure process and possessing a density of not
less than 0.935 (g/cm.sup.3) which is usually available on the
market. This polyethylene is desired to possess a melt index in the
range of from 0.1 to 10, preferably from 0.2 to 7. In the case of a
copolymer, the ethylene group content is desired to exceed 90 mol
%, preferably to be about 95 l mol %. When the high-density
polyethylene is used as the component (C), the blend prepared for
film is desired to undergo the aforementioned treatment for
crosslinking. If the melt index is less than 0.1, the film made of
the blend using such a component is impaired in the mixing property
of components and optical properties. If the melt index is more
than 10, the blend fails to offer sufficient strength and the
sheet's stretchability is impaired. The polybutene-1 is desired to
be a crystalline homopolymer or copolymer of more than 90 mol % of
butene-1 with other monomer. Unlike a liquid to waxy low molecular
polymer, these polymers are desired to possess a melt index in the
range of from 0.2 to 10 for the same reason as mentioned above. Of
the three possible members of the aforementioned group, it is
desirable to use chiefly the crystalline polypropylene. A mixture
of polypropylene with high-density polyethylene may be used.
The composition of the present invention comprises one of the
specific combinations of components (A), (B) and (C), i.e. the
combinations of (A)+(B), (B)+(C) and (A)+(B)+(C). The mixing ratio
of these components is such as to satisfy:
0.05.ltoreq.B/(A+B).ltoreq.0.90 in the first combination,
0.30.ltoreq.B/(C+B).ltoreq.0.90 in the second combination,
and
0.05.ltoreq.B/(A+B).ltoreq.0.90 and 0.05.ltoreq.C/(A+B).ltoreq.2.0
in the third combination,
and more desirably to satisfy;
0.07.ltoreq.B/(A+B).ltoreq.0.70 in the first combination,
0.40.ltoreq.B/(C+B).ltoreq.0.87 in the second combination,
and
0.07.ltoreq.B/(A+B).ltoreq.0.70 and 0.07.ltoreq.C/(A+B).ltoreq.1.0
in the third combination,
and preferably to satisfy;
0.10.ltoreq.B/(A+B).ltoreq.0.50 in the first combination,
0.50.ltoreq.B/(B+C).ltoreq.0.85 in the second combination,
and
0.10.ltoreq.B/(A+B).ltoreq.0.50 and 0.10.ltoreq.C/(A+B).ltoreq.1.0
in the third combination.
If the amount of the non-rigid component (B) is less than the
allowable lower limit indicated above, the blend of any of the
first, second and third combinations fails to manifest the expected
synergistic effect and, therefore, suffers from inferior
processibility, lowered film strength and impaired optical
properties and low-temperatures shrinkability. If the amount is
more than the allowable upper limit, the tubular sheet produced
from the blend is degraded in film-forming property and
stretchability and becomes so soft as to entail the phenomenon of
film-to-film blocking and the produced film exhibits insufficient
heat resistance, sealability, strength and optical properties.
Of the three possible combinations of components, particularly
desirable is the third combination, i.e. the combination of
(A)+(B)+(C). To be more specific, if the amount of the resin of the
component (C) used in the composition is smaller than 5 parts by
weight, the blend exhibits insufficient stretchability and the
extruded sheet tends to sustain puncture and regain its original
dimension and does not easily produce a film of uniform thickness
possessing the outstanding properties mentioned above and tends to
give inferior finish to the package. The film, when produced in a
particularly small thickness, fails to provide sufficient modulus.
Consequently, the film has poor dimensional stability and,
therefore, tends to undergo deterioration by aging similarly to the
plasticized PVC film, with the result that the heat resistance,
heat seal strength, heat seal temperature range and finish of
package are all adversely affected.
If the amount is greater than 200 parts by weight, the blend
exhibits inferior stretchability and tends to sustain puncture and
the film suffers from insufficient optical properties, uniformity
of wall thickness and low-temperature shrinkability. The mixed
component (C) serves to improve not only modulus but also seal
properties such as, for example, thermal properties including heat
resistance particularly in the higher portion of the allowable
temperature range.
As described above, this invention permits the quenched tubular
sheet which has been produced from the composition obtained by
using the specific components in their respective specific amounts
to be cold stretched with ample stability in the manner to be
described hereinafter. If the tubular sheet is further treated with
a specific high-energy ray so as to have the gel content
(insolubles in boiling xylene) or the melt index brought into a
specific range, the components in the composition produce a
synergistic effect such as to manifest the desired cold
stretchability (at temperatures in the range of from 20.degree. to
100.degree. C.) under specific stretching conditions, giving rise
to a film of outstanding properties.
Now, the composition produced by using the components in the
preferred mixing ratio will be described. Generally, the
crystalline PP [component (C)] is hardly crosslinked even when it
is subjected to a treatment with a high-energy ray and it offers
rather insufficient compatibility with EVA to be used as another
component (A). In contrast, EVA when treated with a high-energy ray
undergoes the reaction of crosslinking more easily than the
ordinary low-density polyethylene. The elastomer of the copolymer
of .alpha.-olefin (B) exhibits rather high compatibility with both
polypropylene and EVA and induces the reaction of crosslinking as
readily as EVA. This is not only limited to EVA, but it is also the
same with a copolymer of ethyrene and unsaturated carboxylic acid.
Consequently, the synergistic effect brought about from the proper
dispersion of the three components in the composition is coupled
with the synergistic effect which issues from the action of the
high-energy ray. The combination of these synergistic effects is
believed to result in the production of a film wherein there is
formed a specific, molecularly heterogneous crosslinked matrix. The
treatment with the high-energy ray, accordingly, improves notably
the stable cold-stretchability of the tubular sheet and the film's
heat resistance and heat seal strength, enhances the thermal
shrinkability and strength of the film at low temperatures,
represses possible degradation in optical properties and physical
properties after thermal shrinkage (such as optical properties,
seal strength and mechanical strength) and expands the range of
packaging temperatures. Thus, the properties possessed by the film
which is produced from the crosslinked tubular sheet far excel
those possessed by the plasticized PVC film and PP film which have
heretofore been rated to be the best films.
The commercially available polyethylene film which has been
thoroughly crosslinked by the treatment with a high-energy ray
possesses the drawbacks mentioned above and, therefore, differs
from the film of this invention. No matter whether the treatment
for crosslinking is to be involved or not, the film made of the
specific composition described above is required to possess a gel
content of from 60 to 0% and a melt index of not more than 10,
preferably a gel content of from 50 to 8% and a melt index of not
more than 5. Particularly in the case of the film to be modified by
the treatment with the high-energy ray, the insoluble gel content
in boiling xylene is not more than 60% by weight and the melt index
is not more than 1.0. Desirably, the gel content is not ore than
50% by weight and the melt index is not more than 0.5. More
desirably, the gel content is not more than 30% by weight and the
melt index is not more than 0.2. Preferably, the gel content is not
more than 20% by weight and the melt index is not more than 0.1 If
the insoluble gel content is greater than the allowable upper limit
mentioned above, the elongation of the stretched film is inferior
and the heat sealability and the melt cutting and sealing of the
film by the heating wire are inferior, the residual tension
generated at the time of thermal shrinkage is high and the film
tends to sustain rupture at the time of packaging. Further, the
optical properties of the film are insufficient. If the melt index
is greater than the allowable upper limit indicated above, the
synergistic effects brought shout by the treatment with the
high-energy ray, namely the improvements in the processibility, the
film's heat resistance, strength and heat sealability cannot be
expected. Thus, the gel content and the melt index are desired to
fall within the respective ranges indicated above.
In the present invention, the composition of this invention may be
effectively used when it is mixed with some other composition
insofar as the amount of the additive composition does not impair
the stretchability and various other properties of the film.
the film of the present invention is characterized by the optical
property [the value of Haze determined in accordance with ASTM
D-1003-52] not exceeding 4.0%, more desirably 3.0% and preferably
2.0%. For example, the film of Run No. 2 of Example 1 is shown to
possess a highly satisfactory value of Haze of 0.8%. This value is
peculiar to the composition and the process of manufacture involved
in this particular run of experiment. Because, the film can be
processed without impairing the properties acquired in consequence
of the quenching of the composition in the tubular sheet. Moreover
the tubular sheet can stably be stretched in the form of bubbles at
low temperatures below the melting point of the composition or
preferably below the softening point of the composition. And, the
synergistic effects originating in the composition itself preclude
otherwise possible occurrence of structural defects such as voids
and permit the tubular sheet to be stretched in conjunction with
mixed components distributed in fine particles, giving rise to a
film of flat surfaces involving no appreciable scattering of light.
This possibly explains why the film has particularly high
transparency.
The low-temperature shrinkability is one of the important
properties which a given film is required to possess when the film
is used for the purpose of shrink wrapping. When the film is tested
for its thermal shrinkage at varying temperatures, the
low-temperature shrinkability is expressed by the value of the
temperature which is required for the purpose of obtaining a
specific shrinkage of 20% or 40% (to be expressed by an average
shrinkage in the longitudinal and lateral directions). The lower
the value of this temperature, the better the low-temperature
shrinkability. Generally, the shrinkage which the film to be used
for shrink wrapping is required to possess is not less than 20%,
preferably not less than 40%. To be specific, the thermal shrinkage
is obtained by a procedure of preparing a square test piece but
from a given film, inscribing a longitudinal and a lateral mark
each of a specified dimension on the test piece, sprinkling the
test piece with a powder such as of talc so as to repress its
surface tackiness which often impedes convenience of handling,
treating it with hot air of a prescribed temperature for five
minutes for thereby causing the test piece to shrink, finding
changes in the longitudinal and lateral dimensions of the marks and
the found changes. The thermal shrinkage is expressed by the
average of the longitudinal and lateral shrinkage. This thermal
shrinkage is found at a varying temperature. The temperatures at
which the film gives 20% and 40% of thermal shrinkage are reported
as temperatures for shrinkages of 20% and 40% respectively.
In the case of the film of this invention to be used for shrink
wrapping, the value of this temperature is small. As shown in FIG.
1 to be described afterward, the commercially available
polypropylene film for shrink wrapping has 120.degree. C. as the
temperature of 20% of shrinkage and 134.degree. C. as that of 40%
of shrinkage as indicated by the curve 3, whereas the film of this
invention has 53.degree. C. as the temperature for 20% of shrinkage
and 72.degree. C., as that of 40% of shrinkage as indicated by the
curve 1. The magnitude of low-temperature shrinkability in this
invention is expressed by the temperature of 20% of shrinkage. It
is desired to be not more than 85.degree. C., desirably not more
than 75.degree. C. and preferably not more than 70.degree. C.
Although this value is affected secondarily by the stretching
temperature and the composition, the fact that this value is on a
low level constitutes one of the characteristics of the cold
orientation of the present invention. If this value is large,
required thermal shrinkage is not effected unless the film is
exposed at a fairly high temperature for a long time at the time of
its actual use. Consequently, the magnitude of heat generated by
the heater must be increased and the speed of the packaging
operation is lowered. Further, there is a possibility of the heat
being transferred to the commodity being packaged. Such transfer of
heat proves undesirable where the commodity being packaged is
highly vulnerable to heat, degradable or deformable by the action
of heat such as fiber or fresh food. In the case of a film whose
curve of shrinkage rises sharply at high temperatures, the film's
shrinkage is heavily varied even by a very slight change near the
shrinkage temperature at the time of packaging. When the film is
loosely wrapped around a commodity and the loose package is passed
through a shrinkage tunnel, a slight shortage in the overall
temperature of the hot air blown against the film results in
insufficient shrinkage, so that the film fails to come into
skintight contact with the contour of the commodity. If the
temperature is slightly higher, the film is fused and sustains
rupture or it is deprived of transparency and optical
homogeneity.
If the value of this temperature is extreme, the film wound up in a
roll undergo a dimensional change even at normal room temperature.
The commercially available PVC plasticized film to be used for
shrink wrapping has 58+ C. for 20% of shrinkage and 88.degree. C.
for 40% of shrinkage as indicated by the curve 2 in the graph of
FIG. 1. This suggests that this film possesses desirable
low-temperature shrinkability, the shrinkage property varied
smoothly with the temperature.
To date, no other commercially available film than the plasticized
PVC film has had such desirable shrinkage property and
strength.
The film of this invention has attained such excellent properties
and, in this respect, defies all comparisons. The thermal shrink
tension exhibited at the time of shrinkage constitutes one of the
important thermal shrinkage properties, comparable with the thermal
shrinkage which is an important factor when the film is used for
the purpose of shrink wrapping. Even if the thermal shrinkage is
high, the film fails to fit tightly to the commodity being packaged
during or after the step of packaging when the tension generated in
the film at the time of shrinkage is low or deviates in the
direction of higher temperatures as will be described afterward.
The film, then, fails to produce desired binding force and can no
longer serve for the purpose of shrink wrapping.
If the value of this tension is insufficient even to the slightest
extent for the purpose of producing binding force, the film is
required to have its thickness increased to make up for the
insufficiency. Such increase in the film thickness is uneconomical
and inconvenient. Generally, this maximum value is desired to be
not less than 50 g/mm.sup.2, preferably not less than 80
g/mm.sup.2. As shown in FIG. 2, the commercially available
polyethylene film for shrink wrapping has a thermal shrink tension
of not more than 10 g/mm.sup.2, about 5 g/mm.sup.2 as indicated by
the curve 4. Thus, the film is applicable to limited uses. The film
of this invention has a value of 230 g/mm.sup.2 as indicated by the
curve 1 in the same graph. Generally, the film of this invention
has a sufficiently high value in the range of from 100 to 400
g/mm.sup.2.
In the case of the low-temperature shrinkable film, this shrink
tension is not significant unless it is manifested at a temperature
close to the temperature corresponding to the shrinkage. The
temperature-dependency curve of the shrink tension must be well
balanced with the shrinkage-temperature curve (expressed by the
average of the values for longitudinal and lateral directions). At
times, the thermal shrink tension is desired to occur in an
increased range of temperatures. In this respect, the film of the
present invention can be adjusted by properly selecting the
composition and treatment.
In the present invention, the stiffness of the film can freely be
adjusted in the range of from fair softness to considerable
rigidity by varying the composition within the specified range.
The film of the present invention is further characterized by
possessing a particularly high tensile strength. The strength at
rupture is at least 5 kg/mm.sup.2 (as determined in accordance with
the method of ASTM D-882-67), preferably not less than 7
kg/mm.sup.2. The elongation at rupture is desired t be not less
than 50%, preferably not less than 100%, and more preferably not
less than 150%. The dart impact strength is determined by following
the method of ASTM D-1709-67 with necessary modifications. It is
expressed by the value which is obtained by using a special dart
whose missile head is provided with a grooved edge to facilitate
rupture of the film. The film of this invention is also
characterized by the fact that the dart impact strength has a
particularly high value. For example, while the PVC film and the PP
film have 18 and 12 kg.cm, the film in the Run No. 16 has a value
of 48 kg.cm, the value comparable with that obtained by heavy bags
of LDPE of 100 to 150.mu. in thickness available on the market. The
dart impact strength is generally not less than 15 kg.cm,
preferably not less than 20 kg.cm, and more preferably not less
than 25 kg.cm (as expressed on the basis of 17.mu.).
The fact that the tensile strength is high and the elongation is
great as described above means that the film is tough and highly
resistant to tear. Thus, the film proves highly advantageous for
the protection of packages and permits a reduction in the film
thickness.
The film of this invention possesses a strength at rupture of 14.5
kg/mm.sup.2 and an elongation of 185% as shown afterward in Run No.
2. Generally, when the strength is enhanced by orientation, the
film tends to lose its elongation to an extreme extent. In the case
of the commercial film which is thoroughly crosslinked (with the
insoluble gel content is boiling xylene brought to 67% by weight)
and consequently oriented sufficiently as described hereinafter,
the strength is 6.9 kg/mm.sup.2 and the elongation is 45%,
indicating that the film is highly liable to rupture. The film of
this invention is not limited to use in shrink wrapping. By virtue
of its excellent toughness, it an be utilized widely as an
industrial film.
By the after-treatment resorting to heat setting, the temperature
for thermal shrinkage and the orientation balance in the
longitudinal and lateral directions can freely be adjusted so as to
adapt the film of this invention for other uses or enable the film
to be laminated with various other films.
Now, a typical process for manufacturing a film for shrink wrapping
from the composition of this invention will be described in detail
herein below.
This is a process for manufacturing a high-strength oriented film
excelling in optical properties and low-temperature shrinkage
properties and having a wide range of effective packaging
temperatures, which process comprises thoroughly mixing and melting
one of the aforementioned combinations of components, i.e. the
combination of (A)+(B), (B)+(C), and (A)+(B)+(C), extruding the
resultant homogeneous blend through an annular die, suddenly
solidifying the extruded tubular raw film with a liquid refrigerant
for thereby producing a tubular raw film sufficiently free from
partiality in thickness, causing the tubular sheet, either
immediately stretching thereafter or subsequently to a treatment
conducted by irradiation of a high-energy ionizing radiant ray with
a view to modifying the composition of the tubular raw film so that
it acquires an insoluble gel content of not more than about 60% in
boiling xylene and a melt index of not more than 1.0, to be heated
to a temperature in the range of from normal room temperature to
110.degree. C., and introducing air into the interior of the
tubular raw film at a stretching temperature in the range of from
20.degree. C. (room temperature) to 100.degree. C. for thereby
effecting cold orientation at an area stretching ratio of from 5 to
30 times the original dimension.
Now, the process of the present invention will be described with
reference to the most desirable combination of components. The
components of the combination are melted under heat and thoroughly
blended. The resultant blend is extruded at an extruding
temperature in the range of from 180.degree. C. to 280.degree. C.
through a shape die adapted effectively to avoid giving to the
extruded sheet uneven wall thickness and imparting thereto heat and
time hysteresis, and the extruded tubular raw film is suddenly
cooled on the outer periphery thereof uniformly with a liquid
refrigerant to produce a tubular raw film of ample homogeneity (in
terms of both external shape and internal structure). This tubular
sheet is immediately subjected in its unaltered form to the
subsequent heat treatment followed by the step of stretching.
Alternatively, it is irradiated with a high-energy ionizing radiant
ray of 2 to 15 Mrads such as, for example, an electron ray,
.beta.-ray or .gamma.-ray radiated from a radioisotope or it is
radiated with an ultraviolet ray in the presence of a sensitizer
(such as, for example, benzophenone or peroxide) incorporated in
advance in the composition for the purpose of modification such
that the resultant tubular sheet exhibits an insoluble gel content
of not more than about 60% by weight in boiling xylene and a melt
index of not more than 1.0. The reason for these particular ranges
has already been described. Any deviation from the specified range
of energy of the irradiation is undesirable; If the irradiation
exceeds 15 Mrads, there ensue undesirable phenomena such as
severance of molecules due to decomposition (embrittlement of
resin) and coloration and odorization of the resin. If the
irradiation falls short of 2 Mrads, the desired effect of
irradiation cannot be obtained. From the viewpoint of physical
properties and case of processibility, preferable irradiation is
obtained in the range of from 2.5 to 10 Mrads. This modification
may otherwise be obtained by a thermal crosslinking method using a
peroxide. The tubular raw film thus treated is then heated to a
temperature in the range of from normal room temperature to
110.degree. C., preferably not more than 90.degree. C., and more
preferably not more than 80.degree. C., i.e. the temperature at
which the main crystalline component used in the composition
remains undissolved and, at the same time, inflated in the form of
a bubble with an ample inner pressure in the range of from 100 to
1000 mm H.sub.2 O of water column at a temperature in the range of
from room temperature (20.degree. C.) to 100.degree. C., preferably
from 30.degree. C. to 90.degree. C., and more preferably from
30.degree. C. to 80.degree. C., i.e. the temperature which is lower
than the melting point of the main crystalline component used in
the mixed composition, preferably lower than the Vicat softening
point of the mixed composition, In this manner, the film of the
present invention is obtained advantageously. The optimum area
stretching ratio, though variable to some extent with the
prevailing temperature at the time of stretching, is desired to
fall in the range of from 5 to 30 times the original dimensions,
preferably from 7 to 30 times the original dimensions, and more
preferably from 10 to 20 times the original dimension. The lateral
stretching ratio is generally desired to fall in the range of from
2 to 7 times the original dimension, preferably from 3 to 6 times
the original dimensions. For the cold orientation to be obtained
effectively without entailing the possibility of film puncture, it
is imperative that the composition should fall within the range
specified herein and it is equally important that the tubular sheet
should enjoy ample uniformity. If the wall thickness of the tubular
raw film involves a derivative of 20% or more, there is a fair
possibility of the raw film sustaining puncture in the course of
stretching, making effective stretching impracticable. The
allowable derivation of wall thickness of the tubular raw film is
within .+-.5%, preferably within .+-.3%. Stable stretching of the
tubular raw film into a film is advantageously accomplished by
first fixing the longitudinal stretching ratio through adjustment
of the ratio of rotating speeds of the feed nip rolls and the
takeup nip rolls and thereafter adjusting the introduction of air
into the tubular raw film now inflated in the form of a bubble so
as to effect the stretching up to the end point of bubble inflation
(immediately before the point of blushing) and bring the lateral
stretching to termination. Because of the relation between the
inner pressure applied to best on the bubble and the diameter of
the bubble, the tubular raw film is desired to have as large a
diameter as possible, generally greater than 50 mm, preferably
greater than 100 mm. In due consideration of the physical
properties of the film to be produced, the stretching temperature
in desired to be the lowest level at which the stability of the
bubble is retained. For practical purpose, it suffices to determine
the degree of stretching on the basis of the composition being
used, with due consideration paid to the balance with the bubble
stability (enough to preclude possible film puncture). Since the
transfer of heat to he film is small, a fact which characterizes
the process of the present invention, the thickness of the film can
be freely selected from a wide range from a very small order of 5
to 6.mu. to a very large order of 100 to 150.mu.. This general
choice of the film thickness afforded by the present invention has
never been attained with the conventional films.
The film which is obtained by the process of this invention
possesses the outstanding properties mentioned above and, more
often than not, has a highly limited deviation of film thickness of
the order of .+-.5% after the step of stretching. A possible reason
for this advantage is that the high inner pressure applied to bear
upon the bubble imparts a strong stretching force t the film and
the heat hysteresis generally involved in the course of heating and
cooling is notably small and, consequently, the film enjoys high
uniformity and stability. The optical properties (both Haze and
gloss) of the tubular raw film appear to be quite inferior. They
are notably improved, however, after the tubular raw film has
undergone the treatment for cold orientation by the process of this
invention. A possible reason for this improvement of optical
properties may be that the resin particles distributed in the form
of islands throughout the sheet are changed in change in
consequence of the cold orientation. Since the process of this
invention enables the distributed resin particles to be oriented
and flattener out, the film no longer causes random scattering of
light. It is, accordingly, inferred that the stretching of the film
is advantageously attained even at low temperatures to produce a
strong film, notwithstanding the composition is a blend not mixed
so thoroughly as to induce dispersion of molecules.
In the present invention, the components which make up the
composition manifest synergistic effects respectively. When any of
the components used in the composition is relied upon to impart
added strength to the film, it will neither bring about a drawback
often experienced in a similar situation nor cause any degradation
of strength. This advantage is never attained by the ordinary
stretching method which requires the sheet to be heated up to or
over its melting point. In the case of the conventional film, the
stretching temperature must be elevated to have the optical
properties of the film improved. Use of the elevated stretching
temperature renders the desired orientation all the more difficult
and tends to degrade the film strength.
The same thing also applies to the use of a stretching temperature
which is close to the melting point. At such a stretching
temperature, the optical properties of the film obtained are far
from being satisfactory and the mixed composition happens to reach
the point where the tubular sheet becomes intolerably brittle.
Thus, the film sustains puncture and fails to acquire advantageous
properties. As illustrated in the preferred embodiments of this
invention afterward, the cold orientation aimed at by the present
invention can be effectively attained at a very low temperature
such as, for example 32.degree. C. This is an unprecedented
achievement, which is not materialized unless the specific
composition, the specific treatment with a high-energy ray which is
optionally carried out, the uniform quenching of the tubular raw
film and the specific conditions of stretching are combined to
produce synergistic effect. It goes without saying that the film
sustains puncture and cannot be effectively stretched when the
quenching given to the tubular raw film lacks uniformity and the
film of the present invention can never to obtained when the
stretching temperature actually used deviates from the specific
range described above. When the stretching of the tubular raw film
is carried out simply by the tenter method, the film obtained
readily sustains rupture and fails to exhibit the outstanding
properties peculiar to the film of this invention. It is ideal to
have the tubular film stretched monoaxially or biaxially, more
preferably biaxially in a tubular form under the stretching
conditions mentioned above.
The characteristic processibility of the film and the
characteristic attributes of the film obtained by the present
invention are believed to be ascribable to the fact that the
components making up the composition possess suitably balanced
compatibility, the fact that the components on which the individual
properties such as crystallinity, softening point and modulus of
elasticity all function independently and the components on which
such properties function in good harmony cooperate synergistically
to bring about ideal effects and the fact that the effect of the
treatment with a high-energy ray also participates in the
synergistic function mentioned above.
As described in one of the comparative examples afterward, when an
attempt was made to stretch a tubular raw film obtained from EVA,
the bubble of the raw film punctured before it was sufficiently
inflated, making it impossible to continue the biaxial stretching
of the raw film at the low temperatures specified herein. U.S. pat.
No. 3,244,680 cites an example wherein a high-molecular EVA
copolymer was compression molded into a circular disc and
subjecting the circular disc to batch stretching by use of a
multiaxial chuck (radial stretcher) at temperatures in the range of
from 30.degree. to 60.degree. C. The film obtained by this method
can never be obtained by the process of this invention. Thus, this
invention differs from the process of said U.S. patent in terms of
composition, process and film.
The mixed composition of this invention can be converted
effectively into a film by a procedure of closing the free end of
the tubular raw film batchwise and stretching the tubular raw film
by hand while introducing air into the interior thereof through the
other end for thereby allowing the tubular raw film to form a
cold-oriented bubble stably in the ambient air maintained at
temperatures in the range of from 20.degree. to 40.degree. C. None
of the components, when used singly, can form a bubble and can be
stretched biaxially even in a continuous operation by the process
of this invention.
FIG. 5 represents the processibility data obtained in Run No. 1 and
expressed in terms of characteristic elements. The zone (A)
contains the data obtained of the stable processing according to
the present invention and the zone (B) those of unstable
processing. In the latter zone, the optical properties, strength
and film thickness at the time of stretching are heavily degraded.
In the zone (C), the molecular flow in the film is so heavy as to
impede effective setting of orientation, so that the film strength
is lower and the elongation is greater. This trend substantially
exists when the tubular raw film is given a treatment for
crosslinking. The crosslinking treatment serves to alleviate the
decline of strength in the zones (B) and (C) and tends to enhance
only slightly the strength in the zone (A). The trend with respect
to the optical property (Haze) and the low-temperature
shrinkability remain unaffected by the crosslinking treatment.
The composition and the process of this invention may be applied
effectively to the manufacture of a film by monoaxial stretching.
In this case, the properties of the film are attained in the
direction of the stretching. Further, the tubular raw film which is
obtained by extruding the homogeneous blend of the composition and
subsequently quenching the extruded raw film can be used as a film
of high strength at rupture and as a composition with improved heat
sealability and elastic modulus and good seal strength, because it
has been modified so as to be readily cold oriented at normal
temperatures and good for stability at inflation. For example, it
may be used as a film for general wrapping or as a low-oriented
film for stretch wrapping, bag film, etc.
Besides, the composition, treatments, and stretching method
involved in the present invention can be applied in any freely
chosen combination to the component layers of a multi-layered film
taken singly or in combination.
Now, the composition and film of this invention, and the process
for the manufacture of this film will be described more
specifically hereinafter with reference to preferred embodiments,
which are solely illustrative of and never limitative of this
invention.
The composition of the present invention is used as films and
sheets, however, not only limited to it but is also usable when
used as molded products, particularly for car parts (bamper, for
example) requiring excellent properties of impact strength,
weatherability and paintability, etc.
Further, as an admixture other than the admixtures described in the
present invention, a brend of inorganic type fillers, carbonblack
type fillers, additives and other polymers may be used for a
certain extent by which the feature of the present invention is not
deprived.
EXAMPLE 1
To 100 weight parts of the composition composed of 82% by weight of
EVA (a.sub.1)(the vinylacetate unit content 10% by weight, the melt
index 1.0) and 18% by weight of the ethylene-.alpha.-olefin
copolymer (b.sub.1)(.alpha.-olefin is propylene, said copolymer
comprises 15 mol % of propylene and 4% by weight of ethylidine
norbornene) having the melt index of 0.45, the Vicat softening
point of not more than 40.degree. C. and the density of 0.88
g/cm.sup.3, were mixed 18 weight part of the crystalline PP
(c.sub.1) having the melt index of 1.0, the density of 0.88
g/cm.sup.3 and the Vicat softening point of 146.degree. C., and the
plasticized kneading composition was extruded at the maximum
temperature of the cylinder part of 250.degree. C. from the annular
die 150 mm in diameter having the slit of 1.5 mm provided with the
mixing head type screw 65 mm in diameter and the ratio (L/D) of 37.
Then the extruded product was quenched at the position which was
about 10 cm distance from the lip of the die by water which was
uniformly flowed out from the ring. Thus, there was obtained the
raw tubular film 100 mm in diameter, 200.mu. in thickness partially
of .+-.1.8% in thickness. The said composition had the Vicat
softening point of 75.degree. C. The obtained raw tubular film was
treated with the electron ray of 500 KV energy in the dose of 5
Mrad at the normal temperature so as to be the gel % of 3% by
weight in the boiling xylene and the melt index of 0.07 (Run No.
2), while the said composition was directly proceeded to the
following stretching step without radiating the high energy ray
(Run No. 1).
The raw tubular film was passed between the two pairs of the
delivery nip rolls and the draw nip rolls respectively, while
passing said rolls, the raw tubular film was heated to the
temperature of 36.degree. C. by the hot air and then was
continuously inflated under the inner pressure of the water head of
400 mm by blowing air within the tubular film and stretched by 3.5
times in the longitudinal direction and 3.3 times of the transverse
direction, the cold air of 20.degree. was blown to the film from
the air ring apparatus at the end of the stretching step to cool
the film. The film was fold up by the deflator and then taken up by
the nip rolls and separated to the two sheets of film by slitting
the edges of the film in the longitudinal direction. Each of which
was winded up under the certain tension whereby the films 17.mu. in
thickness (Run No. 1 and No. 2) were obtained. Table 2 showed the
characteristic properties of the resulting film in comparison with
those of the commercial three sorts of films.
The stretched film obtained (for example Run No. 2) had good
optical character of Haze of 0.8% and the superior strengths of the
tensile strength of 14.5 kg/cm.sup.2, the elongation of 185% and
the dart impact strength of 37 kg.cm in comparison with that of 20
kg.cm in the commercial plasticized PVC shrink film (17.mu. in
thickness), 12 kg.cm in the PP shrink film (16.mu. in thickness).
The high dart impact strength was one of the characteristics of the
film of the present invention. As shown in Table 1 and FIG. 1, the
film had the following low temperature shrinking properties;
53.degree. C. at 20% shrinkage, 72.degree. C. at 40% shrinkage. The
curve in FIG. 1 showing the interrelation between the heat-treating
temperature (.degree.C.) and the shrinkage (%) displayed the gentle
sloping pattern similar to the commercial PVC shrink film.
Furthermore, this film had good shrinkage character toward the low
temperature side.
This film had the maximum shrink tension of 230 g/mm.sup.2 which
was a high level. In the practical test of wrapping four cucumbers,
wrapping was carried out by passing the wrapped film for 3 seconds
through the conventional tunnel over which was blown out the hot
air of 90.degree. C. thereby obtaining the good wrapping finish
tightly fitted with goods and not having any wrinkling and not
depressing a good optical character after shrinkage. As shown in
the oblique portion of FIG. 3 No. 1, the various tests were carried
out by changing the hot air temperature when the shrinking wrapping
was carried out and the staying time within the tunnel. From the
test result, it was found t be able to smoothly carry out good
wrapping at the broader range of the heating temperature with the
broader speed range from the low temperature side.
While the commercial shrink film of polypropylene did not almost
shrink at 90.degree. C. and remained the wrinkle on the sample, the
satisfactory shrinking could not be accomplished without the high
shrinking temperature of 170.degree. C. Even if the heating
temperature was further raised and the staying time was lengthened,
the wrapping film was broken due to pitting and became opaque. The
optimum shrink temperature range of the film was very narrow. The
commercial shrink film of PVC had lack of the shrinkage and
remained the wrinkle under the same wrapping condition as mentioned
above. Therefore, the shrinking temperature of 150.degree. C. was
demanded.
The shrink film of the commercial crosslinked polyethylene was not
suitable to the wrapping film since it could not shrink without the
high temperature of 170.degree. C., the film was easy to break at
the sealed part and moreover, was apt to occur much breakage, the
good wrapping range of the film was judged from the shrinkage, the
binding force, the hole at the sealing part, the rupture from the
air vent part and the devitrification phenomenon of the film after
wrapping. Furthermore, judging from good wrapping finish, the film
Run No. 2 of the present invention was the best one. Similar
results were obtained in the film Run No. 1 of the present
invention.
Hereafter, the strength, the elongation and the heat-shrinking
property of the film were shown by the mean value between those of
the longitudinal and transverse directions since said characters of
the film had in the longitudinal and transverse direction in good
balance.
TABLE 1
__________________________________________________________________________
Shrinking temp. (.degree.C.) 50 60 80 100 120 140 160 180 200
__________________________________________________________________________
Heat shrink- 16/17 26/27 49/47 65/63 71/70 74/74 76/77 77/78 83/80
age (%) Run No. 1/ Run No. 2
__________________________________________________________________________
TABLE 2
__________________________________________________________________________
Comparative Run No. sample Property Unit 1 2 I II III
__________________________________________________________________________
Haze % 1.0 0.8 1.7 2.8 2.5 Gloss (20.degree.) -- 142 150 123 105
103 Thermal property 20% shrinkage temperature .degree.C. 53 53 58
120 100 Maximum shrinkage % 83 80 58 72 76 Maximum shrink tension
g/mm.sup.2 180 230 108 208 192 Temperature at peak .degree.C. 60 69
115 115 102 Tensile strength kg/mm.sup.2 12.0 14.5 8.0 14.4 6.9 at
break Elongation at break % 200 185 145 125 45 Dart impact strength
kg .multidot. cm 32 37 20 12 8.5
__________________________________________________________________________
Note: Gloss was measured in accordance with ASTM D 245465T I is
commercial PVC shrink film. II is commercial PP shrink film. III is
commercial crosslinked polyethylene shrink film.
The film of the present invention was remarkably good in the range
and strength of heat-sealing in comparison with another comparative
Run Nos. 1, 2 and 3 when said film was heat-sealed by the heating
bar type heat-sealing machine.
The extent capable of heat-sealing was that surrounded by the
oblique lines of No. 1, FIG. 4. The axis of abscissa showed the
temperature of the heat-sealing bar. The lower limit of the
temperature was that corresponding to 50% probability between the
case of immediately peeling off the film without being sealed and
the case of causing breakage of the film from the sealed part when
the sealed film was pulled. The upper limit of the temperature was
that capable of cutting off the film by melting when the film was
pressed with the heating bar. Press was carried out under the
pressure of 1.3 kg/cm.sup.2. The sealing strength under the optimum
condition was 1.3 and 1.5 kg/15 mm width in Run No. 1, 2
respectively, while said strength was 0.6, 1.1 and 0.7 kg/15 mm
width in another comparative examples a, b and c respectively. The
film of the present invention had large strength and broad sealing
range.
EXAMPLE 2
EVA (a.sub.2)(the vinyl acetate group content; 15% by weight, the
melt index; 0.7) and ethylene-.alpha.-olefin copolymer elastomer
(b.sub.2)(.alpha.-olefin is propylene, and 20 mol % of
.alpha.-olefin group are contained, the melt index; 0.25, the
density; 0.88 g/cm.sup.3, and the Vicat softening point; less than
40.degree. C.) and the crystalline PP (C.sub.2)(ethylene group
content; 5% by weight, the melt index; 0.6, the Vicat softening
point; 120.degree. C., the density; 0.87 g/cm.sup.3) were mixed in
the ratio as mentioned in Table 3 and extruded according to the
process of Example 1 to obtain the raw tubular film (150.mu. in
thickness and partiality of .div.1.8% in thickness). Then the
obtained film was extruded without any cross-linking treatment at
the stretching temperatures of 41.degree., 51.degree., 53.degree.,
60.degree., 75.degree. and 79.degree. C. in Run Nos. 3-8
respectively thereby being manufactured the stretched films having
good stability and 14.mu. in thickness.
Each of the stretched film had less partiality of .+-.6-8% in
thickness the good stretching workability and dart impact strength
of more than 25 kg.cm.
The physical properties of each film were shown in Table 4.
TABLE 3 ______________________________________ Run No. Composition
3 4 5 6 7 8 ______________________________________ a.sub.2 90 70 50
80 60 40 b.sub.2 10 30 50 20 40 60 c.sub.2 10 30 30 70 100 70 Vicat
softening point of the 64 68 62 88 93 84 mixed composition
(.degree.C.) ______________________________________
TABLE 4
__________________________________________________________________________
Run No. Property Unit 3 4 5 6 7 8
__________________________________________________________________________
Haze % 0.8 1.0 1.1 1.2 1.3 1.3 Thermal property 20% shrinkage
temperature .degree.C. 55 57 59 63 68 60 40% shrinkage temperature
.degree.C. 75 78 75 80 82 79 Maximum shrinkage % 80 78 75 74 72 73
Maximum shrink tension g/mm.sup.2 220 180 280 175 160 150
Temperature at peak .degree.C. 60 68 72 71 80 75 Breakage strength
kg/mm.sup.2 11.5 13.7 15.0 14.0 12.9 11.6 Elongation at break % 180
190 250 220 160 170
__________________________________________________________________________
As mentioned above, the practical wrapping test of the resulted
film was carried out according to the wrapping operation of Example
1. The film had good wrapping finish without occurring any
wrinkling on the finishing surface. The film was suitable to
various uses with good result in the wrapping. The wrapping test
was carried out using the shrink films of Run No. 4, the commercial
PP and PVC respectively. The test was carried out by wrapping with
the film to be test a king crab which is the representative
angulated goods. The test results were as follows; The PP and PVC
films caused the breakage by spines of the king crab, while the
film of Run No. 4 have good wrapping finish. The PP and PVC films
became brittle during the storage and was apt to cause the breakage
since the PP and PVC films were inferior to the low temperature
resistance, while the film of Run No. 4 was no problems in wrapping
ability.
EXAMPLE 3
EVA (a.sub.3)(the melt index; 0.7, the vinylacetate group content;
13 weight %), ethylene-.alpha.-olefin copolymer elastomer
(b.sub.3)(the melt index; 0.25, the Vicat softening point; less
than 50.degree. C., the density; 0.88 g/cm.sup.3, .alpha.-olefin is
butene-1 and .alpha.-olefin group content; 20 mol %) and the
crystalline PP (C.sub.2) (mentioned above) were extruded and stably
stretched in the mixing ratio and the conditions as shown in Table
5 according to the process of Example 1 under the stretching
temperatures of 32.degree., 35.degree., 40.degree., 51.degree.,
53.degree. and 50.degree. C. which were the temperatures less than
the Vicat softening point of the mixed composition in Run Nos. 9-14
respectively whereby the stretched films having 18.mu. in thickness
were obtained.
Each of the film had less partiality of +6-8% in thickness.
The physical properties of the resulted films were shown in Table
6.
TABLE 5 ______________________________________ Run No. Composition
9 10 11 12 13 14 ______________________________________ a.sub.3 90
70 50 80 60 40 b.sub.3 10 30 50 20 40 60 c.sub.2 10 30 30 70 100 70
Dose (Mrad) 3 5 10 7.5 7.5 5 Gel (%) 1.5 2.5 20 12 8 1.0 MI 0.1
0.07 less than 0.08 0.09 0.15 0.05
______________________________________ Note: Unit is based on the
weight part.
TABLE 6
__________________________________________________________________________
Run No. Property Unit 9 10 11 12 14 14
__________________________________________________________________________
Haze % 0.6 0.6 1.0 1.2 1.5 1.1 Gloss (20.degree.) -- 157 155 153
147 138 150 Thermal property 20% shrinkage temperature .degree.C.
50 51 52 53 57 54 Maximum shrinkage % 77 76 77 78 82 79 Maximum
shrink tension g/mm.sup.2 240 230 220 215 200 205 Temperature at
peak .degree.C. 60 64 65 72 75 70 Tensile strength kg/mm.sup.2 12.8
13.9 15.9 16.0 13.5 13.5 at break Elongation at break % 250 230 210
255 195 220 Dart impact strength kg .multidot. cm 38 35 32 40 32 30
__________________________________________________________________________
As mentioned above, the practical wrapping test was carried out
using the said films according to the wrapping operation of Example
1. The good wrapping finish without causing any wrinkling on the
finishing surface was obtained in all tests.
EXAMPLE 4
The raw tubular films 200.mu. in thickness and partiality of
.div.2.0% in thickness were manufactured using the polymer
composition, the ratio as shown in Table 7 according to the process
of Example 1. The resulted raw tubular films were stretched under
the stretching temperatures of 42.degree., 52.degree., 48.degree.,
66.degree., 49.degree., 35.degree. and 70.degree. C. which was less
than the Vicat softening point of each film of Run Nos. 15-21, and
stably stretched respectively thereby obtaining the films having
17.mu. in thickness.
The characteristic properties of this films showed in Table 8.
In order to test the bubble stretching stability by batch method,
test pieces were cut out from the raw tubular films of Run Nos.
15-21 before the films were stretched and sealed at one end of the
film while the compressed air was blown in the tubular film from
another end thereof, and then the test piece was pulled by hand at
the temperature of 30.degree. C. The films of the present invention
had the good stability and could be bubbled up, especially the test
films of Run Nos. 17 and 20 were easy to stretch.
The films had good properties of the optical character, the low
temperature shrinkage and the heat shrink tension. The breaking
strength of a commercial polyethylene film which was directly
inflated from the die was only about 2.5 kg/mm.sup.2, while the
film of the present invention was the strong film difficult to
break, since it had the moderate degree of elongation. Especially
the wrapping films of Run Nos. 16 and 18 had high dart impact
strength and toughness and were superior in the wrapping test and
the heat-sealing property.
TABLE 7
__________________________________________________________________________
Run No. (weight part) No. 15 16 17 18 19 20 21 22 23
__________________________________________________________________________
a.sub.2 EVA 80 75 80 80 a.sub.3 EVA 80 60 a.sub.4 EVA 70 80 (Melt
index: 1.5, vinylacetate group content: 20% by weight) b.sub.3
Ethylene-.alpha.-olefin elastomer 20 30 20 40 20 25 80 20 b.sub.4
Ethylene-.alpha.-olefin copolymer (EPM) 20 (.alpha.-olefin in
propylene, .alpha.-olefin group content: 42 mol %, density: 0.87
g/cm.sup.3 Vicat softening point: less than 30.degree. C.) c.sub.3
Crystalline PP 18 30 10 25 20 (Melt index: 0.8 ethylene group
content: 6% by weight) c.sub.4 HDPE 20 60 (Melt index: 0.8,
density: 0.960 g/cm.sup.3 modified buten-1 group content: 0.6 mol
%) c.sub.5 Polybutene-1 30 (Melt index: 0.4, density 0.913
g/cm.sup.3 c.sub.6 Polybutene-1 70 (Melt index: 1.0, density: 0.908
g/cm.sup.3, modified ethylene group content: 8% by weight) Dose
(Mrad) 5 7 -- 10 -- 5 -- -- -- Gel % 4 23 -- 24 -- 5 -- -- -- MI
0.08 less than less than 0.09 0.05 0.05
__________________________________________________________________________
TABLE 8
__________________________________________________________________________
Run No. Property Unit 15 16 17 18 19 20 21 22 23
__________________________________________________________________________
Haze % 0.6 0.5 0.9 0.8 0.6 0.7 1.2 1.5 1.0 Gloss (20.degree.) --
157 162 143 150 155 149 138 140 160 Thermal property Temperature at
20% shrinkage .degree.C. 52 55 56 60 57 61 99 99 56 Maximum
shrinkage % 78 78 76 74 72 75 74 74 76 Maximum shrink tension
g/mm.sup.2 230 240 220 230 185 160 190 140 150 Temperature at peak
.degree.C. 62 75 68 77 70 72 70 69 70 Tensile strength at break
kg/mm.sup.2 13.6 18.3 12.8 16.7 16.8 15.2 10.2 9.5 14.8 Elongation
at break % 230 195 197 210 170 165 185 185 175 Dart impact strength
kg .multidot. cm 36 48 35 43 31 32 26 25 34
__________________________________________________________________________
No. 4 Example 2 and stretched at 50.degree. C. to obtain the
uniform film 45.mu. in thickness. Even if the thickness of the
finished film was thick, the stretch was stably accomplished. The
characteristic property of the film was the Haze of 1.0%, the
tensile strength at break of 13.5 kg/mm.sup.2, and the elongation
of 185%. The film was superior in the optical character and the
strength and had the temperature of 60.degree. C. at 20% shrinkage
and the maximum shrink tension of 230 g/mm.sup.2, until now, as
mentioned above, the directly blown LDPE film had been used in the
thicker shrink film in the market (curve 4 in FIGS. 1 and 2). The
film had less heat shrinkage at the low temperature side and the
relative high shrinking temperature. The film had high shrinking
temperature of 117.degree. C. at 20% shrinkage and exceedingly low
shrink tension of 5 g/mm.sup.2 whereby the use was very limited.
The thick film was the useful one in the industrial
application.
In the practical test of wrapping the wood, as the result, the
speedy shrink-wrapping could be accomplished with the fine wrapping
finish having no wrinkling, while the uncrosslinked low density
commercial polyethylene film was required higher temperature and
longer time for the heat-shrinkage and created the wrinklings on
the surface of the wrapping film and the partial deritrifications
of the film. The unsatisfactory result was obtained. If the
temperature was raised to accelerate the wrapping, the temperature
reached to the melting point of the film before the film was
uniformly and sufficiently heated thereby dissolving the most part
of the film and transferring heat to the goods.
When the film of the present invention was stabilized by
heat-treating at the desired temperature and heat-setting, the film
having the good dimensional stability was obtained at the
relatively high temperature of for example about 80.degree. C. This
shrinking film was not only limited to the specific use but also be
applicable for the generic wrapping, the agricultural and the
industrial uses.
EXAMPLE 6
Seventh weight parts of LDPE (a.sub.5)(the melt index; 0.3, the
density; 0.917 g/cm.sup.3), 30 weight parts of
ethylene-.alpha.-olefine copolymer (b.sub.2) (referred to above)
and 15 weight parts of the crystalline PP (c.sub.1) were extruded
according to the process of the Example 1 to obtain the raw tubular
film (Run No. 24). As this film was apt to break in stretching, the
film wa crosslinked by radiating the high energy ray of 10 Mrad so
as to have the melt index of less than 0.05 l and contain about 40%
by weight of gel and then stretched at the stretching temperature
of 65.degree. C. thereby obtaining the film 16.mu. in thickness.
This film had the following properties: Haze; 1.8%, Temperature at
20% shrinkage; 70.degree. C., Heat shrink tension; 210 g/mm.sup.2,
Tensile strength; 8.5 kg/mm.sup.2, Elongation; 155%, Dart impact
strength; 22 kg/cm.
EXAMPLE 7
The stable stretching was carried out under the same condition to
those of Run No. 2, Example 1, using ethylene-ethyl acrylate
copolymer (a.sub.6) (the ethyl acrylate unit content: 10 weight %,
the melt index: 2.5) (Run No. 25) or the ethylene-methyl
metharcylate copolymer (a.sub.7) (the methyl methacrylate unit
content: 15 weight %, the melt index: 2.0) (Run No. 26) instead of
EVA (Run No. 2). These films had the following properties
respectively: Haze, 1.4%, 1.7%, Tensile strength; 8.9 kg/mm.sup.2,
9.8 kg/mm.sup.2, Elongation; 200%, 180%, Dart impact strength; 26
kg.cm, Temperature at 20% shrinkage; 60.degree. C., 65.degree. C.,
Shrink tension; 140 g/mm.sup.2, 165 g/mm.sup.2. The gel % was 12,
15 weight % by radiating the high energy ray of 7.5 Mrad.
COMPARATIVE EXAMPLE 1
The raw tubular films having the compositions of Table 9 were
extruded from the die and quenched to obtain the extruded film 100
mm in diameter, 200.mu. in thickness and partiality of +1.8% in
thickness. The said film was stretched under the same processing
condition as those of Example 1.
TABLE 9 ______________________________________ Com- po- Comparative
example Run No. sition 1 2 3 4 5 6 7 8 9 10
______________________________________ a.sub.2 100 80 a.sub.3 100
b.sub.2 100 20 20 c.sub.1 100 20 70 c.sub.3 100 70 c.sub.4 100
c.sub.5 100 ______________________________________ Note: Unit is
based on the weight part.
The films of the comparative sample Run Nos. 1 and 2 could not be
continuously stretched at all under the temperatures of 40.degree.
C., 50.degree. C., 60.degree. C., 70.degree. C., 80.degree. C. and
90.degree. C. respectively and were caused breakage when air was
blown in the tube. The batch test of this film could not be carried
out. These raw films were difficult to continuously stretch without
heating the films at the temperature of more than 140.degree. C.
These films had Haze of 4.1% and 5.1%, the breaking strength of 2.5
and 28 kg/cm.sup.2, the elongation of 580% and 450% respectively.
These films had not the low temperature shrinkage, and the shrink
tension was almost null. These raw films were similar one wit the
film manufactured from the die by direct inflation and inflating
while cooling by air. These raw films contained the gel of 38, 21%
by weight respectively when they were radiated with the energy ray
(hereinafter it is called E-treatment for short). These films had a
similar tendency with the above example.
The raw film having the composition of Comparative Example Run No.
3 could not be inflated like the bubble at all since it was caused
breakage at the temperature not more than 140.degree. C. This raw
film could not be stretched in the continuous or batch process.
This raw film was different from that of the present invention.
This raw film was somewhat inflated at the temperature more than
140.degree. C. and it was apt to cause breakage immediately after
the inflation. This film had the bad transparence having Haze of
5.2% and could not carry out the low temperature shrinkage. This
film did not contain the gel even if the E-treatment was carried
out. The film was almost the same to the film that the E-treatment
was not carried out.
The raw film having the composition of Comparative Example Run No.
4 had lower stretching temperature than that of Comparative Example
Run No. 3. This film had the exceedingly unstable stretching
character and could not carry out the low temperature shrinkage and
was inferior in the strength and had Haze of 4.7% and the
temperature of 117.degree. C. at 20% shrinkage.
The raw film having the composition of Comparative Example Run No.
5 could not be inflated at all at the temperature of not more than
the melting point (135.degree.C.) and was caused breakage in
continuous or batch process. The film which was inflated at the
higher temperature of 150.degree. C. in the same manner to the
conventional direct inflation process could not be highly oriented
and had the bad optical character. This film was opaque and had
Haze of 20%.
the film having the composition of Comparative Example Run No. 6
had high Haze and was opaque as the film of Comparative Example Run
No. 5.
The film having the composition of Comparative Example Run No. 7
had elasticity as rubber. This raw film was somewhat inflated at
the low temperature of not more than 90.degree. C. However it was
caused breakage and shrinkage of bubble. The satisfactory film
could not be obtained. As the raw tubular film occurred blocking at
the high temperature of about 140.degree. C., the said film could
not be stretched at the high temperature.
The raw films having the compositions of Comparative Example Run
Nos. 8, 9 and 10 were caused breakage and could not form the film
at low temperatures even if the batch and continuous processes were
carried out. At high temperatures of the melting point of the
crystalline PP (165.degree. C.) (c.sub.1) or at the temperature
somewhat less than the said temperature, namely the temperatures of
140.degree. C. (Comparative Example Run No. 9) and 133.degree. C.
(Comparative Example Run No. 10), the films were unstable and
caused breakage immediately after the inflation. However the films
could be hardly stretched. These films had Haze of 4.6% and 3.9%,
the temperature of 109.degree. C. and 104.degree. C. at 20%
shrinkage respectively and had not the low shrinkage temperature as
the raw film carried out the E-treatment of Example 1. The tensile
strength at break was 5.1 kg/mm.sup.2 and 6.2 kg/mm.sup.2
respectively and it was not so high level.
The film of the Comparative Example 1, Run No. 11 having the
composition composed of 70 weight parts of the crystalline PP
(c.sub.1) and 30 weight parts of LDPE (the melt index; 1.5, the
density; 0.918 g/cm.sup.3) was instable at the temperature of
140.degree.-160.degree. C. near to the melting point (165.degree.
C.) of the crystalline PP and had high Haze of 5.6%. Of course,
this raw film had the low oriented film not having the low
temperature shrinkage and having the rough surface of Haze of 18.6%
at the temperature of not less than 165.degree. C. this film could
not be inflated at the temperature of not more than 140.degree. C.
since the bubble was caused breakage.
The raw film of Comparative Example Run No. 12 composed of 80weight
parts of the crystalline PP (c.sub.1), 10 weight parts of LDPE (the
melt index; 1.5, the density; 0.918 g/cm.sup.3) and 10 weight parts
of the ethylene-.alpha.-olefin copolymer elastomer (b.sub.2) was
unsatisfactory as in Comparative Example Run No. 11.
COMPARATIVE EXAMPLE 2
Two raw tubular films as in Example 1 were heated to 115.degree. C.
and 150.degree. C. respectively and then stretched, one of which
was the film 200.mu. in thickness manufactured according to the
composition and the process of Example 1 l without the E-treatment,
another of which was the film 200.mu. in thickness manufactured
according to the composition and process of Example 1 with the
E-treatment. The satisfactory stretched film could not be
manufactured from these raw films, since said film was brittle and
was caused breakage when the stretching was carried out at
115.degree. C. by blowing the compressed air within the raw tubular
film. This film was whitish and opaque in appearance. While the
satisfactory stretching could be accomplished at 150.degree. C. and
these raw films were inflated to 3 times in the vertical direction
and 4.4 times in the lateral direction. The resulted films had the
fillowing properties respectively; Haze; 3.8%, 3.6%, Temperature at
20% shrinkage, 107.degree. C., 106.degree., Shrink tension; 3, 10
g/mm.sup.2, Breaking strength; 2.9 kg/mm.sup.2, 3.5 kg/mm.sup.2,
Elongation; 520%, 480%. The film had not the low temperature
shrinking property and had the bad optical character and the low
breaking strength ;and the shrink tension of almost null. The said
films were different from the film of the present invention in the
use. These raw tubular films were caused breakage when the film
were stretched to 6 times in the vertical direction only at
60.degree. C. and the stretching elongation was returned. The film
had the bad optical character and was lack of uniformity. The raw
tubular film was cut off and heated at the temperature of
40.degree.-90.degree. C. and stretched to 2 times in the vertical
and lateral directions by the tenter for the biaxial stretching
use. The stretched film was lack of uniformity in thickness and
caused breakage. Thus this film could not be satisfactorily
stretched. This film was brittle and easily broken at the
temperature of about 100.degree.-110.degree. C. There was merely
obtained the film having the bad optical character (Haze: 11.5%) at
the temperature of 140.degree. C.
COMPARATIVE EXAMPLE 3
Two raw tubular films containing the gel of 62% and 65%
respectively were manufactured from LDPE (the melt index: 1.5, the
density: 0.918 g/cm.sup.3) only and EVA (a.sub.1) only by radiating
the energy ray of 15 Mrad according to the process of Example 1.
The resulted raw films were heated to the temperature of
150.degree. C. and then stretched to 4.0 times in the vertical
direction and 6.0 times in the lateral direction to obtain the film
16.mu. in thickness. These films had the fillowing properties
respectively: Haze, 2.5%, 2.1%, Temperature at 20% shrinkage;
97.degree. C., 87.degree. C., Shrink tension; 115 g/mmhu 2, Tensile
strength at breakage; 6.2 kg/mmhu 2, 8.3 kg/mm.sup.2, Elongation;
80%, 95%, Dart impact strength; 7.2 kg.cm, 10.3 kg.cm.
These films were difficult to be heat-sealed and the temperature
range for heat-sealing was narrow and the high temperature side and
were difficult to melt-cut with a heating wire at the time of
wrapping.
EXAMPLE 8
The compositions composed of the components as shown in Table 10
except Run No. 31 were plasticized and kneaded at the maximum
temperature of cylinder part of 260.degree. C. by the mixing head
type screw 45 mm in diameter (L/D.times.44) and pelletized to form
pellet. The composition of Run No. 31, Table 10 was manufactured by
kneading PP (c.sub.2) and EPM (b.sub.4) into Banbury mixer to make
the master batch pellet and diluting the resultant with other
components (a.sub.1). The compositions were extruded through an
extruder 45 mm in diameter (L/D-37) fitted with T-type die which
had a slit 1 mm in thickness and 40 cm in width, while extruding a
liquid additive was injected into the rear part of cylinder under
pressure. The melted polymer compositions extruded from the die
were introduced into water to form raw tubular films 100.mu. in
thickness. One of the resulted films was treated with the radiation
of energy ray and the other was treated. They were examined for
comparison. The results were shown in Table 11.
TABLE 10 ______________________________________ Run No. Composition
27 28 29 30 31 ______________________________________ a.sub.1 85 85
80 85 b.sub.4 15 b.sub.1 15 15 20 b.sub.2 80 c.sub.1 20 c.sub.2 20
80 20 Dose (Mrad) -- 7 -- 10 5 Gel % -- 33 -- 8 20 MI less than
0.07 less than 0.05 0.05 ______________________________________
The films had tensile strength, impact strength, heat sealing
strength and tear strength in high level. The films had wide
temperature aptitude for heat-sealing and good sealing strength.
Especially, the film of Run No. 30, Table 10 was treated by
radiating energy ray of 10 Mrad. However, the film had wide
temperature aptitude for sealing and good sealing strength. The
films of No. 27, No. 30, Table 10 had good stiffness and were
superior as the wrapping film.
TABLE 11 ______________________________________ Run No. Property 27
28 29 30 31 ______________________________________ Haze (%) 1.8 1.5
1.6 2.5 2.2 Tensile 3.5 3.3 3.0 3.8 3.4 strength at break
(kg/mm.sup.2) Elongation (%) 820 840 730 670 700 Dart impact 73 64
54 80 66 strength (kg .multidot. cm) Heat sealing strength 2.1 1.8
1.5 2.3 1.7 (kg/15 mm width)
______________________________________
EXAMPLE 9
The compositions of Run No. 27, Table 10 and the vinylidene
chloride-vinylchloride copolymer (hereinafter referred to as PVDC)
were extruded using an annular die having three layer structures
with three extruders and then inflated by the water cooling type
inflation process to obtain co-extrusion film composed of a film of
the composition Run No. 27, 25.mu. in thickness as the outer layer,
a film of the composition Run No. 27, 30.mu. in thickness as the
inner layer and a film of the composition PVDC 10.mu. in thickness
as the middle layer. The film has the fillowing properties:
Haze--21%, Tensile strength at break--5.1 (kg/mm.sup.2),
Elongation--460(%) , Dart impact strength--78 (kg.cm), Heat-sealing
strength--2.2 (kg/15 mm width). The inflation process could be
carried out very stably and had a less problem. On the other hand,
when (a.sub.1) alone was used instead of the composition of Run No.
27 for the outer and inner layers, the film prepared suffered
surging and so the inflation process was instable.
EXAMPLE 10
The compositions composed of the components as shown in Table 12
were made up and test samples were prepared in the same manner as
Example 8, then the properties of the test samples were
evatuated.
TABLE 12 ______________________________________ Run No. (weight
part) Composition 32 33 34 35 36 37
______________________________________ a.sub.1 70 20 a.sub.6 60 50
80 a.sub.8 40 60 b.sub.1 15 25 25 15 30 12 b.sub.5 15 b.sub.6 15 10
b.sub.7 25 15 10 8 c.sub.2 25 30 35 40 80 c.sub.3 15 20
______________________________________ Note: a.sub.8 :
Ethyleneacrylic acid copolymer (MI: 2.0, acrylic acid contained 15
wt %) b.sub.5 : Styrenebutadiene copolymer [MFR (L condition): 1.5,
combined styrene: 35 wt % b.sub.6 : Hydrogenized styrenebutadiene
block copolymer [MFR (L): 3.4, combined styrene: 32 wt %,
hydrogenation ratio b.sub.7 : Modified b.sub.6 with maleic
anhydride [MFR (L): 2.1, combined styrene: 32 wt %, graft ratio:
2.5 wt %
TABLE 13 ______________________________________ Run No. Property 32
33 34 35 36 37 ______________________________________ Tensile
strength 3.9 3.7 4.0 3.8 4.3 3.6 at break (kg/mm.sup.2) Elongation
(%) 800 770 840 790 800 750 Dart impact 78 76 84 80 85 72 strength
(kg .multidot. cm) ______________________________________
All of them are excellent particularly in impact strength. As to
the weatherability, after the 500 hour exposure test with a
sunshine weather meter according to JIS K 1415, the retaining ratio
of the tensile strength of Run No. 32 was 89%, however, the
retaining ratio of that of Run Nos. 33 to 37 were apploximately
100%. As to the paintabiity, the peel test with adhesive cellophan
tape was carried out after paint was cooled and sufficiently dried.
As the test results, Run Nos. 32 to 37 were all superior to Run No.
27, especially Run Nos. 34, 35 and 36 were excellent. After holding
long period, however, Run No. 32 has exhibited slight degradation
in its printability.
* * * * *