SPECIFICATION
LAMINATE FILM AND PACKAGING BAG USING SAME
5 TECHNICAL FIELD
[0001]
The present invention relates to a laminate film and a packaging
bag using the same.
BACKGROUND ART
10 [0002]
In general, in a film for packaging various hydrous foods
typified by meat, processed meat foods such as sausage, fresh
vegetables and seafood, and_other processed foods, food is hardly
visible due to fogging caused by water vapor that is vaporized from
15 the food, adheres to and condenses on the inner surface of the film.
Thus, the film is required to have antifogging properties to prevent
fogging.
[0003]
In order to exhibit antifogging properties, there are proposed
20 methods for imparting antifogging properties by adding a surfactant
to a film of the innermost surface layer as an antifogging agent to
improve wettability of the surface (for example, Patent Documents
1 to 3) . However, in this method, when a large amount of surfactant
is used, there is a concern of bleed-out occurring over the surface
25 of the film.
[0004]
Another known method for imparting antifogging properties is
2
a method of imparting wettability by performing a corona treatment
on the surface of a film. However, in the case of performing a corona
treatment, the strength of a heat-sealed portion may be decreased
by the treatment. In order to prevent the strength from being
5 decreased, for example, a method of selectively performing a corona
treatment on only portions other than the sealed portion is proposed
(for example, Patent Document 4). However, the method of performing
a corona treatment on only a specific region of the surface of the
film has complicated the operations and the number'of steps increases.
10 Thus, there has been a demand for establishing an industrially
advantageous method.
RELATED DOCUMENT
PATENT DOCUMENT
[0005]
15 [Patent Document 1] Japanese Laid-open Patent Publication No.
H05-69521
[Patent Document 2] Japanese Laid-open Patent Publication No.
H07-52334
[Patent Document 3] Pamphlet .of International Publication WO.
20 2001/78980
25
[Patent Document 4] Japanese Laid-open Patent Publication No.
2009-241975
SUMMARY OF THE INVENTION
[0006]
The present invention has been made in consideration of the above
circumstances, and an object thereof is to provide a packaging bag
in which water drops immediately spread not to cause fogging due to
3
high wettability even in a case in which a content having a high water
content is sealed with the packaging bag, that is, a laminate film
for a packaging bag excellent in antifogging properties, and
exhibiting sufficient strength even in a case of adopting a known
5 heat sealing temperature during heat sealing, and a packaging bag
obtained from the film. The concept is also applied to, for example,
a packaging bag which is subjected to a corona treatment for improving
printability.
10
15
[0007]
That is, the present invention can adopt the following
constitutions.
[ 0008 J
[1] A laminate film including: a heat sealing layer composed
of a resin composition including,
with respect to 20 to 95 parts by weight of a propylene-based
polymer (A) having a melting point (Tm) of equal to or higher than
120°C and equal to or lower than 170°C as measured by differential
scanning calorimetry (DSC),
a total of 5 to 80 parts by weight of two or more kinds of
20 copolymers selected from the group consisting of
25
a propylene·l-butene copolymer (B) containing a unit derived
from propylene in an amount of 51 to 95 mol% and a unit derived from
1-butene in an amount of 5 to 49 mol%, wherein the total of the unit
derived from propylene and the unit derived from 1-butene is 100 mol%,
a copolymer (C) of ethylene and an ex-olefin having 3 to 20 carbon
atoms, and
a copolymer (D) of 1-butene and an ex-olefin having 3 carbon atoms
4
or 5 to 20 carbon atoms containing a constitutional unit derived from
1-butene in an amount of 50 to 99 mol% and a constitutional unit derived
from an a-olefin having 3 carbon atoms or 5 to 20 carbon atoms in
an amount of 1 to 50 mol%, wherein the total of the unit derived from
5 1-butene and the unit derived from the a-olefin is 100 mol%,
10
15
wherein each of Component (B), Component (C), and Component (D)
does not correspond to Component (A) , and the total amount of Component
(A), Component (B), Component (C), and Component (D) is 100 parts
by weight; and
a base layer,
in which a surface of the heat sealing layer opposite to the
base layer has a wet tension of 32 to 45 mN/m.
[2] The laminate film according to [1], in which the surface
of the heat sealing layer is modified by a corona treatment.
[3] The laminate film according to [1] or [2], in which two or
more kinds of copolymers selected from the group consisting of the
Component (B) , the Component (C) , and the Component (D) include the
Component (B) as a required component, and the content of the Component
(B) is 3 to 25 parts by weight [wherein the total amount of Component
20 (A), Component (B), Component (C), and Component (D) is 100 parts
by weight].
[4] The laminate film according to any one of [1] to [3], in
which the copolymer (C) of ethylene and an a-olefin having 3 to 20
carbon atoms contains a constitutional unit derived from ethylene
25 in an amount of 50 to 99 mol% and a constitutional unit derived from
an a-olefin having 3 to 20 carbon atoms in an amount of 1 to 50 mol%,
therein the total of the unit derived from ethylene and the unit
5
derived from the a-olefin is 100 mol%.
[5] The laminate film according to any one of [1] to [4] which
is not stretched.
[6] The laminate film according to any one of [1] to [4] which
5 is biaxially stretched.
10
[7] A packaging bag which is formed by fusing the heat sealing
layers of the laminate films according to any one of [1] to [6].
[8] A laminate film including: a heat sealing layer composed
of a resin composition .including,
w.ith respect to 20 to 95 parts by weight of a propylene-based
polymer (A) having a melting point (Tm) of equal to or higher than
120°C and equal to or lower than 170°C as measured by differential
scanning calorimetry (DSC),
a total of 5 to 80 parts by weight of two or more kinds of
15 copolymers selected from the group consisting of
20
a propylene·l-butene copolymer (B) containing a unit derived
from propylene in an amount of 51 to 95 mol% and a unit derived from
1-butene in an amount of 5 to 4 9 mol%, wherein the total of the unit
derived from propylene and the un.i t der.i ved from 1-butene is 100 mol%,
a copolymer (C) of ethylene and an a-olefin having 3 to 20 carbon
atoms, and
a copolymer (D) of 1-butene and an a-olefin having 3 carbon atoms
or 5 to 20 carbon atoms containing a constitutional unit derived from
1-butene .in an amount of 50 to 99 mol% and a const.i tutional unit derived
25 from a-olefin having 3 carbon atoms or 5 to 20 carbon atoms in an
amount of 1 to 50 mol%, wherein the total of the unit derived from
1-butene and the unit derived from the a-olefin is 100 mol%,
5
6
wherein each of Component (B), Component (C), and Component (D)
does not correspond to Component (A) , and the tot.al amount of Component
(A), Component (B), Component (C), and Component (D) is 100 parts
by weight; and
a base layer,
in which the heat sealing layer included in the laminate film
is subjected to a modification .treatment.
[9] The laminate film according to [8], in which the surface
of the heat sealing layer opposite to the base layer has a wet tension
10 of 5 to 30 mN/m.
[0009]
The laminate film of the present invention includes a heat
sealing layer formed of a resin composition composed of specific
Components (A) to (D) and although the heat sealing layer is designed
15 to have wet tension, for example, exhibiting an antifogging effect
and printability by a corona treatment, the laminate film exhibits
sufficient strength even in a case in which the heat sealing layer
is sealed at a known heat sealing temperature. Therefore, it is
possible to provide a packaging bag having antifogging properties
20 and printability and excellent in heat sealing strength in a case
of heat-fusing heat sealing layers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010]
The above object, other objects, characteristics, and
25 advantages will be further clarified using preferable embodiments
described below and the following drawing attached to the
embodiments.
7
[0011]
FIG. 1 is a schematic cross-sectional view showing a laminate
film according to an embodiment.
DESCRIPTION OF EMBODIMENTS
5 [0012]
Hereinafter, the embodiments of the invention will be described
in detail using an appropriate drawing. In addition, "A to B" in
the present specification indicates "equal to or more than A and equal
to or less than B" unless otherwise specified.
10 [0013]
[Laminate Film]
A laminate film according to an embodiment includes a heat
sealing layer composed of a resin composition including, with respect
to 20 to 95 parts by weight of a propylene-based polymer (A) having
15 a melting point (Tm) of equal to or higher than 120°C and equal to
or lower than 170°C as measured by differential scanning calorimetry
(DSC), a total of 5 to 80 parts by weight of two or more kinds of
copolymers selected from the group consisting of a propylene ·1-butene
copolymer (B) containing a unit derived from propylene in an amount
20 of 51 to 95 mol% and a unit derived. from 1-butene in an amount of
5 to 49 mol%, wherein the total of the unit derived from propylene
and the unit derived from 1-butene is 100 mol%, a copolymer (C) of
ethylene and an ex-olefin having 3 to 20 carbon atoms, and a copolymer
(D) of 1-butene and an ex-olefin having 3 carbon atoms or 5 to 20 carbon
25 atoms containing a constitutional unit derived from 1-butene in an
amount of 50 to 99 mol% and a constitutional unit derived from ex-olefin
having 3 carbon atoms or 5 to 20 carbon atoms in an amount of 1 to
8
50 mol%, wherein the total of the unit derived from 1-butene and the
unit derived from the a-olefin is 100 mol%, wherein each of Component
(B), Component (C), and Component (D) does not correspond to Component
(A), and the total amount of Component (A), Component (B), Component
5 (C), and Component (D) is 100 parts by weight, and a base layer, and
the surface of the heat sealing layer opposite to the base layer has
a wet tension of 32 to 45 mN/m.
[0014]
Hereinafter, the laminate film according to 'the embodiment will
10 be described while referring to FIG. 1.
A laminate film 30 shown in FIG. 1 includes a heat sealing layer
10 and a base layer 20. The heat sealing layer 10 constituting the
laminate film 30 of the embodiment is formed by blending a
propylene-based polymer (A) having a melting point (Tm) of equal to
15 or higher than 120°C and equal to or lower than 170°C as measured
by differential scanning calorimetry (DSC) (hereinafter, also
referred to as "Component (A)") as a required component, and blending,
in addition to Component (A), two or more kinds of copolymers selected
from the group consisting of a propylene·l-butene copolymer (B)
20 conta.ining a unit derived from propylene in an amount of 51 to 95
mol% and a unit derived from 1-butene in an amount of 5 to 49 mol%,
wherein the total of the unit derived from propylene and the unit
derived from 1-butene is 100 mol% (hereinafter, also referred to as
"Component (B)"), a copolymer (C) of ethylene and an ex-olefin having
25 3 to 20 carbon atoms (hereinafter, also referred to as "Component
(C)"), and a copolymer (D) of 1-butene and an a-olefin having 3 carbon
atoms or 5 to 20 carbon atoms containing a constitutional unit derived
I
! ~
I
I
!J
!
I
9
from 1-butene in an amount of 50 to 99 mol% and a constitutional unit
derived from an ex-olefin having 3 carbon atoms or 5 to 20 carbon atoms
in an amount of 1 to 50 mol% , wherein the total of the unit derived
from 1-butene and the unit derived from the ex-olefin is 100 mol%
5 (hereinafter, also referred to as "Component (D)") at a specific
ratio.
More specifically, an embodiment in which Component (B) and
Component (C) are blended with respect to Component (A), an embodiment
in which Component (B) and Component (D) are bl.ended with respect
10 to Component (A), an embodiment in which Component (C) and Component
(D) are blended with respect to Component (A), and an embodiment in
which Component (B), Component (C), and Component (D) are blended
with respect to Component (A) are exemplified.
Among these embodiments, from the viewpoint of ease of blending
15 of each component, an embodiment in which Component (B) and Component
(C) are blended with respect to Component (A) and an embodiment in
which Component (B) and Component (D) are blended with respect to
Component (A) are preferable.
In the embodiment, the heat sealing layer surface of the laminate
20 film 30, which is on the side close to the heat sealing layer 10 and
is opposite to the base layer 20, has a wet tension of 32 to 45 mN/m.
[0015]
The laminate film 30 of the embodiment may be an unstretched
film or a stretched film according to the application of use. However,
25 it is preferable to use a stretched film which is excellent in tensile
strength, stiffness, or impact strength. Examples of the stretched
film include monoaxially and biaxially stretched films.
5
10
In addition, from the viewpoint of improving heat resistance,
tear strength, flexibility, and the like, an unstretched film may
be used.
[0016]
In the case in which the laminate film 30 of the embodiment is
an unstretched film, the laminate film 30 can be prepared by, for
example, using two extruders connected with a T-die, supplying the
resin composition constituting the heat sealing layer 10 and the resin
composition constituting the base layer 20 to the respective
10 extruders, and molding the compositions by coextrusion.
In this case, the thickness of the entire laminate film 30 can
be set to be within a range of, for example, 50 ~m to 5,000 ~m.
In addition, a ratio between the thickness of the heat sealing
layer 10 and the thickness of the base layer 20 can be set to be within
15 a range of, for example, 1:99 to 99:1.
The aforementioned thickness can be changed to be appropriate
according to the application of use of the laminate film 30.
[0017]
In the case in which the laminate film 30 of the embodiment is
20 a stretched film, the laminate film ::SO can be prepared by stretching
the aforementioned unstretched film, for example, using a stretching
machine.
In this case, the thickness of the entire laminate film 30 can
be set to be within a range of, for example, 1 ~m to 500 ~m.
25 [0018]
In the laminate film 30 of the embodiment, the heat sealing layer
surface which is on the side close to the heat sealing layer 10 and
11
is opposite to the base layer 20 has a wet tension of 32 to 45 mN/m.
The heat sealing layer surface having a wet tension of 32 to 45 mN/m
is obtained by, for example, subjecting a modification treatment on
the heat sealing layer surface. The surface modification may be
5 performed by a known treatment method and for example, a corona
treatment, a plasma treatment, a flame treatment may be used.
Particularly, since a specific environment is not required and the
surface can be easily treated, a corona treatment is desirable. The
wet tension can be controlled by adjusting the 'degree of surface
10 modification.
[0019]
By performing such a treatment, the wet tension of the surface
of the heat sealing layer 10 can be improved. In the embodiment,
the value of the wet tension is set to be within a range of 32 to
15 45 mN/m but within this range, the wet tension can be appropriately
set according to the application of use of the laminate film 30,
preferably set to 34 to 43 mN/m and more preferably set to 36 to 41
mN/m. By setting the wet tension to be within this range, sufficient
antifogging properties can be exhibited when the film is formed into
20 a packaging bag.
In the embodiment, the wet tension can be measured according
to ASTM-D-2578-67T in an environment of 23°C and 65% RH.
[0020]
The conditions for performing the corona treatment can be
25 appropriately set as long as it does not impair the object of the
present invention, and as an example thereof, for example, the
condition that a one-way corona treatment is performed using a moving
12
table type corona treatment apparatus, manufactured by Kasuga
electric works Ltd., or the like can be.selected.
The rate of the treatment for the film in this case is, for example,
5 em/ sec to 2 0 em/ sec (3m/min to 12m/min) . In addition, the condition
5 for discharge output is set to be within a range of, for example,
1 A to 5 A.
[0021]
In the case in which the laminate films 30 of the embodiment
are superposed in such a manner that, for example, the heat sealing
10 layers 10 are superposed with each other and heat sealing is performed
at a temperature of 120°C at the upper portion of a heat seal bar
by the method described in (Measurement of Heat Sealing Strength)
in [Example 1], which will be described later, the heat sealing
strength can be set to be equal to or more than 2. 0 N/mm, preferably
15 set to be equal to or more than 2.5 N/mm, and more preferably set
to be equal to or more than 3.0 N/mm.
[0022]
In the embodiment, the laminate film shown below is also
important to solve the problems of the present application.
20 A laminate film including: a heat sealing layer composed of a
resin composition including,
with respect to 20 to 95 parts by weight of a propylene-based
polymer (A) having a melting point (Tm) of equal to or higher than
120°C and equal to or lower than 170°C as measured by differential
25 scanning calorimetry (DSC) ,
a total of 5 to 80 parts by weight of two or more kinds of
copolymers selected from the group consisting of
5
13
a propylene·l-butene copolymer (B) containing a unit derived
from propylene in an amount of 51 to 95 mol% and a unit derived from
1-butene in an amount of 5 to 4 9 mol%, wherein the total of the unit
derived from propylene and the unit derived from 1-butene is 100 mol%,
a copolymer (C) of ethylene and an a-olefin having 3 to 20 carbon
atoms, and
a copolymer (D) of 1-butene and an a-olefin having 3 carbon atoms
or 5 to 20 carbon atoms containing a constitutional unit derived from
1-butene in an amount of 50 to 99 mol% and a constitutional unit derived
10 from an a-olefin having 3 carbon atoms or 5 to 20 carbon atoms in
an amount of 1 to 50 mol%, wherein the total of the unit derived from
1-butene and the unit derived from the a-olefin is 100 mol%,
wherein each of Component (B), Component (C), and Component (D)
does not correspond to Component (A) , and the total amount of Component
15 (A), Component (B), Component (C), and Component (D) is 100 parts
by weight]; and a base layer,
20
in which the heat sealing layer included in the laminate film
is subjected to a modification treatment.
[0023]
That is, in the aforementioned laminate film, a specific wet
tension can be achieved by performing a modification treatment to
the heat sealing layer.
In a laminate film which is not subjected to the modification
treatment, for example, the wet tension of the surface of the heat
25 sealing layer which is opposite to the base layer is set to be within
a range of 5 to 30 mN/m and more preferably set to be within a range
of 10 to 30 mN/m.
5
14
[0024]
Subsequently, the heat sealing layer 10 and the base layer 20
constituting the laminate film 30 will be described.
[0025]
[Heat Sealing Layer]
The heat sealing layer 10 of the embodiment is formed by blending
the following four components at an appropriate ratio:
a propylene-based polymer (A) having a melting point (Tm) of
equal to or higher than 120°C and equal to or l'ower than 170°C as
10 measured by differential scanning calorimetry ( DSC) (Component (A));
a propylene·l-butene copolymer (B) containing a unit derived
from propylene in an amount of 51 to 95 mol% and a unit derived from
1-butene in an amount of 5 to 4 9 mol%, wherein the total of the unit
derived from propylene and the unit derived from 1-butene is 100 mol%
15 (Component (B));
a copolymer (C) of ethylene and an a-olefin having 3 to 20 carbon
atoms (Component (C)); and
a copolymer (D) of 1-butene and an a-olefin having 3 carbon atoms
or 5 to 20 carbon atoms containing a constitutional unit derived from
20 1-butene in an amount of 50 to 99 mol% and a constitutional unit derived
from an a-olefin having 3 carbon atoms or 5 to 20 carbon atoms in
an amount of 1 to 50 mol%, wherein the total of the unit derived from
1-butene and the unit derived from the a-olefin is 100 mol% (Component
(D) ) •
25 [0026]
Here, the resin composition constituting the heat sealing layer
10 of the embodiment includes 20 to 95 parts by weight of Component
II
I
15
(A), and 5 to 80 parts by weight of two or more kinds of components
selected from the group consisting of Component (B), Component (C),
and Component (D).
In addition, the total amount of Component (A), Component (B),
5 Component (C), and Component (D) is 100 parts by weight.
[0027]
Regarding a more preferable content of each of these components,
the content of Component (A) is preferably 30 to 90 parts by weight,
more preferably 40 to 90 parts by weight, and particularly preferably
10 50 to 85 parts by weight.
In addition, the content (total content) of two or more kinds
!ji
of components selected from the group consisting of Component (B),
Component (C) , and Component (D) is preferably 10 to 70 parts by weight,
more preferably 10 to 60 parts by weight, and particularly preferably
15 15 to 50 parts by weight.
[0028]
The resin composition constituting the heat sealing layer 10
is preferably a composition including, as required components,
Component (A) and Component (B), as described above. Specifically,
20 two or more kinds of copolymers selected from the group consisting
of the Component (B), the Component (C), and the Component (D) include
Component (B) as a required component and further, the content of
the Component (B) is 3 to 25 parts by weight, preferably 4 to 23 parts
by weight, and more preferably 5 to 20 parts by weight [wherein the
25 total amount of Component (A), Component (B), Component (C), and
Component (D) is 100 parts by weight].
[0029]
16
Hereinafter, each component included in the resin composition
constituting the heat sealing layer 10 will be described.
[0030]
[Component (A)]
5 Component (A) used in the embodiment is a propylene-based
polymer having a melting point (Tm) of equal to or higher than 120°C
and equal to or lower than 170°C as measured by differential scanning
calorimetry (DSC). The propylene-based polymer may be a
homopropylene, a random copolymer of propylene and an a-olefin having
10 2 to 20 carbon atoms (excluding propylene), or a propylene block
copolymer, and is preferably a homopropylene or a random copolymer
of propylene and an a-olefin having 2 to 20 carbon atoms.
[0031]
In the resin composition constituting the heat sealing layer
15 10 of the embodiment, from the viewpoint of imparting heat resistance
and rigidity to the heat sealing layer 10, it is particularly
preferable to use a homopropylene. From the viewpoint of imparting
flexibility and transparency to the heat sealing layer 10, it is
preferable to use a random copolymer of propylene and an a-olefin
20 having 2 to 20 carbon atoms.
[0032]
Here, examples of the a-olefin to be copolymerized with
propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene,
1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,
25 1-tetracene, 1-hexadecene, 1-octanedecene, and 1-eicosene.
[0033]
In addition, as Component (A) used in the embodiment, an
17
isotactic propylene-based polymer can also be preferably used.
The isotactic propylene-based polymer is a propylene-based
polymer in which an isotactic pentad fraction measured by a NMR method
is equal to or higher than 0.9 and is preferably equal to or higher
5 than 0. 95. The isotactic pentad fraction of the isotactic propylene
polymer is equal to or higher than 90% and preferably equal to or
higher than 95% in terms of percentage.
[0034]
The isotactic pentad fraction (rrnnrrnn fraction) indicates the
10 ratio of presence of isotactic chains in a pentad fraction unit in
the molecule chain measured using a 13C-NMR spectrum, and is the ratio
of propylene monomer unit presence in the center of a chain consisting
of five propylene monomer units continuously meso-bonded to each
other. Specifically, the isotactic pentad fraction (rrnnrrnn fraction)
15 is a value calculated as the fraction of mmmm peaks among all
absorption peaks iri the methyl carbon region measured from a 13C-NMR
spectrum. The isotactic pentad fraction (rrnnrrnn fraction) is measured
as follows.
20
25
[0035]
The rrnnrrnn fraction is obtained from the absorption peaks of Prrnnrrnn
(the peak intensity derived from the third methyl group in a moiety
in which five propylene units are continuously isotactically bonded)
and Pw (the absorption intensity derived from all methyl groups of
a propylene unit) in the 13C-NMR spectrum by the following equation.
mmmm fraction = Pmmmm/Pw
NMR measurement is performed as follows, for example. That is,
0.35 g of a sample is dissolved in 2.0 mL of hexachlorobutadiene by
18
heating. The solution is filtered through a glass filter (G2) and
0. 5 mL of deuterated benzene is added to the filtrate. The mixture
is put into an NMR tube having an inner diameter of 10 mm. Then,
13C-NMR measurement is performed at 120°C using NMR apparatus JNM
5 GX-500 manufactured by JEOL LTD. The number of integration times
is set to be equal to or more than 10,000 times.
[0036]
In addition, Component (A) obtained in the embodiment has a
melting point (Tm) of equal to or higher than 120°C and equal to or
10 lower than 170°C and preferably equal to or higher than 125°C and
equal to or lower than 168°C, which is obtained by differential
scanning calorimetry (DSC) .
When Component (A) having a melting point ( Tm) within this range,
moldability, heat resistance, and transparency can be imparted to
15 the heat sealing layer 10.
Further, it is preferable that the fusion heat amount (6H)
obtained at the same time is equal to or more than 50 mJ/mg.
[0037]
The melting point (Tm) and the fusion heat amount (6H) of
20 Component (A) are measured as follows, for example.
That is, a sample of about 5 mg is heated to 200°C in a nitrogen
atmosphere (20 ml/min) using DSCPyrisl or DSC7 manufactured by Perkin
Elmar Co., Ltd., held for 10 minutes, and then cooled to 30°C at
l0°C/min. After holding the sample at 30°C for 5 minutes, the sample
25 is heated to 200 °C at 10 °C/min, wherein the melting point is calculated
from the top of the crystalline melting peak.
[ 0038]
19
The melt flow rate (MFR; measured at 230°C and a load of 2.16
kg according to ASTM Dl238) of Component (A) is preferably 0.01 to
400 g/10 min, and more preferably 0.1 to 100 g/10 min. When using
Component (A) having such a MFR value, the flowability of the resin
5 composition is improved and a relatively large sheet is easily molded.
[0039]
In the case in which Component (A) is a propylene ·ex-olefin random
copolymer, it is preferable that the a-olefin is selected from
ethylene and an ex-olefin having 4 to 20 carbon 'atoms. The amount
10 thereof is preferably 0.1 to 8 mol%, more preferably 0. 2 to 7. 5 mol%,
and even more preferably 0.3 to 7 mol%.
[0040]
In addition, the molecular weight distribution (Mw/Mn) of
II
il
Component (A) obtained by gel permeation chromatography (GPC) is
15 preferably equal to or less than 3.0, more preferably 2.0 to 3.0,
and even more preferably 2.0 to 2.5.
The molecular weight distribution (Mw/Mn) can be measured by
using, for example, a gel permeation chromatograph Alliance GPC-2000,
manufactured by Waters Corporation, as follows. Separation columns
20 used are two columns of TSKgel GNH6-HT and two columns of TSKgel
GNH6-HTL, each having an inner diameter of 7.5 mm and a length of
300 mm, and the column temperature is set to 140 °C. The mobile phase
is composed of a-dichlorobenzene (manufactured by Wako Pure Chemical
Industries, Ltd.) and 0. 025% by weight of BHT (manufactured by Takeda
25 Pharmaceutical Company Limited.) as an antioxidant, and is moved at
1. 0 ml/min, and the sample concentration is adjusted to 15 mg/10 mL.
The injection amount of the sample is 500 microliters and a
20
differential refractometer is used as a detector. With regard to
standard polystyrenes, for those having a molecular weight of Mw <
1,000 and Mw > 4 x 106
, those manufactured by Tosoh Corporation are
used; and for those having a molecular weight of 1,000 ~ Mw ~ 4 x
5 106
, those manufactured by Pressure Chemical Company are used.
[0041]
As Component (A) used in the embodiment, a component having a
tensile modulus of elasticity of equal to or more than 500 MPa can
be preferably used. The tensile modulus of elasticity is a value
10 measured using JIS No. 3 dumbbell with a span of 30 mm at a tensile
rate of 30 mm/min and 23 °C according to JIS K6301.
[0042]
Component (A) used in the embodiment can be produced by various
methods and can be produced by using, for example, a stereoregular
15 catalyst. Specifically, Component (A) can be produced by using a
catalyst formed of a solid titanium catalyst component and an
organometallic compound catalyst component, and an electron donor
as required. Specifically, as solid titanium catalyst component,
a solid titanium catalyst component in which titanium trichloride
20 or a titanium trichloride composition is carried by a carrier having
a specific surface area of equal to or more than 100 m2/g, or a solid
titanium catalyst component including magnesium, halogen, an
electron donor, (preferably an aromatic carboxylic acid ester or
alkyl group-containing ether), and titanium as required components,
25 in which these required components are carried by a carrier having
a specific surface area of equal to or more than 100 m2/g may be used.
In addition, Component (A) can be produced by using a metallocene
21
catalyst.
[0043]
As the organometallic compound catalyst component,
organoaluminum compounds are preferable. Specific examples of the
5 organoaluminum compounds include trialkylaluminum, dialkylaluminum
halide, alkylaluminum sesquihalide, and alkylaluminum dihalide.
The organoaluminum compound can be appropriately selected according
to the kind of the titanium catalyst component to be used.
[0044]
10 As the electron donor, an organic compound having a nitrogen
atom, a phosphorus atom, a sulfur atom, a silicon atom, a boron atom
or the like can be used, and preferable is an ester compound or an
ether compound having such an atom.
The catalyst may be activated by a method such as copul verization,
15 and may be a catalyst onto which such an ex-olefin as described above
has been prepolymerized.·
[0045]
[Component (B) l
Component (B) used in the embodiment is a propylene·l-butene
20 copolymer containing a unit derived from propylene in an amount of
51 to 95 mol% and a unit derived from 1-butene in an amount of 5 to
49 mol% (wherein the total of the unit derived from propylene and
the unit derived from 1-butene is 100 mol%). Such a
propylene·l-butene copolymer may be appropriately selected from
25 known components according to the application of use and is preferable
that the propylene·l-butene copolymer satisfy, for example, the
following requirements.
.I
I
•
I
I
I
'I J p .I
II II
II
II
1
... -~---···-,· I
I 'I
I
22
[0046]
(1) It is preferable that Component (B) contains a
constitutional unit derived from propylene in an amount of 60 to 90
mol% and a constitutional unit derived from 1-butene in an amount
5 of 10 to 40 mol%, in which the total of the constitutional unit derived
from propylene and the constitutional unit derived from 1-butene is
100 mol%.
A more preferable embodiment is a component that contains a
constitutional unit derived from propylene in an' amount of 70 to 90
10 mol% and a constitutional unit derived from 1-butene in an amount
of 10 to 30 mol%, in which the total of the constitutional unit derived
from propylene and the constitutional unit derived from 1-butene is
100 mol%.
When the amounts are set to be within such ranges, handleability
15 is excellent and heat sealing is easily performed at a relatively
low temperature.
[0047]
(2) It is preferable that Component (B) has a melting point (Tm)
of equal to or lower than 110 °C as measured by differential scanning
20 calorimetry (DSC) or does not have a melting point peak as measured
by DSC.
More preferably, the melting point (Tm) is 50 to ll0°C, more
preferably 60 to 100°C, and even more preferably 65 to 90°C. When
the temperature is set to be within such a range, heat sealing is
25 easily performed at a relatively low temperature.
The melting point of Component (B) can be measured by the
following manner.
- -~---------------
23
That is, using DSC manufactured by Seiko Instruments Inc., a
sample of about 5 mg is placed in an aluminum pan for measurement,
heated to 200°C at 100°C/min, and held at 200°C for 5 minutes. Then,
the sample is cooled to -150°C at l0°C/min and heated to 200°C at
5 10 °C/min.to obtain an endothermic curve. The melting point can be
obtained from the endothermic curve.
[0048)
(3) The molecular weight distribution (Mw/Mn) of Component (B)
is obtained by gel permeation chromatography (GPC) and the molecular
10 weight distribution is preferably equal to or less than 3.0, more
preferably 2.0 to 3.0, and even more preferably 2.0 to 2.5.
[0049)
When Mw/Mn is set to be within the above range, the content of
low molecular weight can be controlled for Component (B) and thus
15 bleeding from the surface layer of the laminate film hardly occurs
and stickiness and blocking of the surface when the laminate film
is stored can be suppressed.
The method of measuring Mw/Mn can adopt the same method as the
measurement method of Mw/Mn of Component (A) .
20 [0050)
(4) It is preferable that the melting point (Tm) of Component
(B) measured by a differential scanning calorimeter is 50 to ll0°C,
more preferably 60 to 100 °C, and particularly preferably 65 to 90°C,
and a relationship between the melting point (Tm) and the 1-butene
25 constitutional unit amount M ( mol%) satisfies
-2.6 M + 130 ~ Tm ~ -2.3 M + 155.
When Tm and M satisfies the above relationship, it is possible
!;
I~
1)
lj
!i
I
I
24
to obtain a laminate film excellent in low temperature heat sealing
properties, and having high heat sealing strength and hardly
suffering from a reduction in sealing strength by aging after
stretching.
5 [0051]
In addition, the melt flow rate (MFR; measured at 230°C and a
load of 2.16 kg according to ASTM Dl238) of Component (B) used in
the embodiment is preferably 0.1 to 30 g/10 min, more preferably 0.5
to 20 g/10 min, and particularly preferably 1.6 to 10 g/10 min.
10 [0052]
The propylene ·1-butene copolymer used in the embodiment can be
suitably obtained by copolymerizing propylene and 1-butene under the
presence of a catalyst including a metallocene compound and can be
preferably produced by the method described in W02004/087775 or
15 WOOl/27124.
[0053]
It is more preferable that Component (B) used in the embodiment
can be desirably obtained by copolymerizing propylene and 1-butene
under the presence of a catalyst including a transition metal compound
20 represented by the following Formula (la) . The transition metal
compound (la) is a compound in which a ligand in which a substituted
cyclopentadienyl group and a substituted fluorenyl ring are
crosslinked with carbon is coordinated with a transition metal atom.
25
[0054]
Here, the catalyst including the transition metal compound (la)
is desirably a compound including at least one of (2a) organometallic
compounds, (2b) organoaluminum oxy compounds, and (2c) compounds
--- -~~-" --··--~----------------
25
capable of reacting with the transition metal compound ( la) to form
an ion pair, together with the transition metal compound (la).
[0055]
· · · ( 1 a )
5 In Formula (la), R
1 and R
3 each represent hydrogen, and R
2 and
R4 are each selected from hydrocarbon groups and silicon-containing
groups, each of which may be the same or different from each other.
5 6 7 8 9 R10 11 12 13 14 l d f h d R , R , R , R , R , , R , R , R , and R are se ecte rom y rogen,
hydrocarbon groups and silicon-containing groups and may be the same
10 or different from one another, and adjacent substituents of R5 to
R12 bonded to carbon may be bonded with each other to form a ring.
R13 and R14 may be the same or different from each other and may be
bonded with each other to form a ring. M represents a Group 4
transition metal, Y represents a carbon atom, Q is selected in the
15 same or different combination from halogen, a hydrocarbon group, an
anionic ligand, and a neutral ligand which can be coordinated to a
lone pair of electrons, and j represents an integer of 1 to 4.
[0056]
Examples of the hydrocarbon groups include linear hydrocarbon
20 groups such as a methyl group, an ethyl group, an n-propyl group,
I ,j
'I
II
I
I
I
;J
··;·.·:'C:_·c:•
26
an allyl group, ann-butyl group, an n-pentyl group, an n-hexyl group,
an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decanyl
group; branched hydrocarbon groups such as an isopropyl group, a
tert-butyl group, an amyl group, a 3-methylpentyl group, a
5 1,1-diethylpropyl group, a 1,1-dimethylbutyl group, a
1-methyl-1-propylbutyl group, a 1,1-propylbutyl group, a
1,1-dimethyl-2-methylpropyl group, and a
1-methyl-1-isopropyl-2-methylpropyl group; saturated cyclic
hydrocarbon groups such as a cyclopentyl group, a cyclohexyl group,
10 a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an
adamantyl group; unsaturated cyclic hydrocarbon groups such as s
phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a
phenanthryl group, and an anthracenyl group; saturated hydrocarbon
groups substituted with unsaturated cyclic hydrocarbon groups, such
15 as a benzy.l group, a cumyl group, an 1,1-diphenylethyl group, and
an triphenylmethyl group; and heteroatom-containing hydrocarbon
groups such as a methoxy group, an ethoxy group, a phenoxy group,
a furyl group, an N-methylamino group, an N,N-dimethylamino group,
an N-phenylamino group, a pyrryl group, and a thienyl group.
20 [0057]
Examples of the silicon-containing groups include a
trimethylsilyl group, a triethylsilylgroup, a dimethylphenylsilyl
group, a diphenylmethylsilyl group, and a triphenylsilyl group.
[0058]
25 In addition, adjacent substituents of R5 to R12 bonded to carbon
may be bonded to each other to form a ring. Examples of such
substituted fluorenyl groups include a benzofluorenyl group, a
27
dibenzofluorenyl group, an octahydrodibenzofluorenyl group, an
octamethyloctahydrodibenzofluorenyl group, and an
octamethyltetrahydrodicyclopentafluorenyl group.
[0059]
5 It is preferable that R13 and R14 are each an aryl group. Examples
of the aryl group include the aforementioned cyclic unsaturated
hydrocarbon groups, saturated hydrocarbon groups substituted with
cyclic unsaturated hydrocarbon groups, and heteroatom-containing
cyclic unsaturated hydrocarbon groups such as a furyl group, a pyrryl
· 10 group, and a thienyl group. In addition, R13 and R14 are the same or
different from each other and may be bonded to each other to form
a ring.
[0060]
In Formula (1a), R2 and R4 which are substituents bonded to a
15 cyclopentadienyl ring are preferably hydrocarbon groups having 1 to
20 carbon atoms. Examples of the hydrocarbon groups having 1 to 20
carbon atoms include the aforementioned hydrocarbon groups. Among
these, more preferably, R2 is a bulky substituent such as a tert-butyl
group, an adamantyl group or a triphenylmethyl group, and R4 is a
20 substituent sterically smaller than R2 such as a methyl group, an
ethyl group or an n-propyl group. As used herein, the expression
of "sterically smaller" means the volume which the substituent
occupies.
[0061]
25 In Formula ( 1a) , among R5 and R12 which are substi tuents bonded
to the fluorene ring, arbitrary two or more groups of R6
, R7
, R10
, and
R1 1 are preferably hydrocarbon groups having 1 to 20 carbon atoms.
I
I
J
I
I j
I
I
I
J
i-l
H
l( n,,
li !' li
~- --~------------ -------------
28
Examples of the hydrocarbon groups having 1 to 20 carbon atoms include
the aforementioned hydrocarbon groups. Particularly, for the
purpose of easy synthesis of the ligand, the fluorene ring is
preferably syrmnetrical, that is, R6 and R11 are the same groups and
5 R7 and R10 are the same groups. In one of such preferable embodiments,
R6 and R7 form an aliphatic ring (AR-l) and R10 and R11 form an aliphatic
ring (AR-2) identical to the aliphatic ring (AR-1).
[ 00 62]
In Formula ( la), Y which cross links a cyclopentadienyl ring and
10 a fluorenyl ring is a carbon atom. R13 and R14 which are substituents
bonded to Y are preferably both aryl groups having 6 to 20 carbon
atoms. Examples of the aryl groups having 6 to 20 carbon atoms include
the aforementioned cyclic unsaturated hydrocarbon groups, saturated
hydrocarbon groups substituted with cyclic unsaturated hydrocarbon
15 groups, and heteroatom-containing cyclic unsaturated hydrocarbon
groups. In addition, R13 and R14 may be the same or different from
each other and may be bonded to each other to form a ring. Preferable
examples of such substituents include a fluorenylidene group, a
10-hydroanthracenylidene group, and a dibenzocycloheptadienylidene
20 group.
[0063]
In Formula (la), M is a Group 4 transition metal and specific
examples thereof include Ti, Zr, and Hf.
In addition, Q is selected in the same or different combination
25 from halogen, a hydrocarbon group, an anionic ligand, and a neutral
ligand which can be coordinated to a lone pair of electrons. j is
an integer of 1 to 4. When j is 2 or greater, plural Qs may be the
H
II
I' II
!
29
same or different from each other.
[ 00 64]
Specific examples of the halogen include fluorine, chlorine,
bromine and iodine. Specific examples of the hydrocarbon groups are
5 as described above. Specific examples of anionic ligand include
alkoxy groups such as methoxy, tert-butoxy, and phenoxy, carboxylate
groups such as acetate and benzoate, and sulfonate groups such as
mesylate and tosylate. Examples of the neutral ligand capable of
coordination through a lone pair of electrons include
10 organophosphorus compounds such as trimethylphosphine,
triethylphosphine, triphenylphosphine and diphenylmethylphosphine,
and ethers such as tetrahydrofuran, diethyl ether, dioxane and
1, 2-dimethoxyethane. It is preferable that at least one Q is halogen
or an alkyl group.
15 [0065]
Examples of the transition metal compounds (la) include but are
not limited to dimethylmethylene
(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium
dichloride, isopropylidene
20 ( 3-tert-butyl-5-methylcyclopentadienyl) (2, 7-di -tert-butylfluoren
yl)zirconium dichloride,
isopropylidene(3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-ter
t-butylfluorenyl)zirconium dichloride,
isopropylidene(3-tert-butyl-5-methylcyclopentadienyl) (octamethyl
25 octahydridodibenzofluorenyl)zirconium dichloride,
diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl) (fluoren
yl)zirconium dichloride, diphenylmethylene
l-1
'I I
I I
I
30
( 3-tert -butyl-5-methylcyclopentadienyl) ( 2, 7 -di -tert-butylfluoren
yl)zirconium dichloride,
diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl) (3,6-ditert-
butylfluorenyl)zirconium dichloride and
5 diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl) (octamet
hyloctahydridodibenzofluorenyl)zirconium dichloride.
[0066]
The catalysts that are suitably used in the production of
Component (B) used in the embodiment preferably includes at least
10 one compound selected from the group consisting of (2a)
organometallic compounds, (2b) organoaluminum oxy compounds, and
(2c) compounds capable of reacting with the transition metal compound
(1a) to fom an ion pair, together with the transition metal compound
(1a) described above. These compounds (2a), (2b), and (2c) are not
15 particularly limited. Preferable compounds include compounds
described in W02004/087775 and W001/27124, and the following
compounds may be used.
[0067]
As the organometallic compounds (2a), the following organic
20 compounds of Groups 1, 2, 12, and 13 metals are used.
(2a-1) Organoaluminum compounds represented by the Fomula:
(in the formula, Ra and Rb may be the same or different from each
other and each represent a hydrocarbon group having 1 to 15 carbon
25 atoms and preferably 1 to 4 carbon atoms, X represents a halogen atom,
m is 0 < m ~ 3, n is 0 ~ n < 3, p is 0 ~ p < 3, q is 0 ~ q < 3, and
m + n + p + q = 3)
31
[0068]
Specific examples of such compounds include trimethylaluminum,
triethylaluminum, triisobutylaluminum and diisobutylaluminum
hydride.
5 [0069]
(2a-2) Alkyl complex compounds of Group 1 metal and aluminum,
represented by the Formula: M2A1Ra 4
(In the formula, M2 represents Li, Na or K, R" represents
hydrocarbon group of 1 to 15 carbon atoms and preferably 1 to 4 carbon
10 atoms)
Specific examples of such compounds include LiAl (C2H5 ) 4 and
[0070]
(2a-3) Dialkyl compounds of Group 2 or 12 metal represented by
15
(In the formula, Ra and Rb may be the same or different from each
other and each represent a hydrocarbon group of 1 to 15 carbon atoms,
and preferably 1 ·to 4 carbon atoms, and M3 represents Mg, Zn or Cd)
[0071]
20 Among the above organometallic compounds (2a), the
organoaluminum compounds are preferable. The organometallic
compounds (2a) may be used alone or two or more kinds thereof may
be used in combination.
[0072]
25 The organoaluminum oxy-compounds (2b) may be conventionally
known aluminoxanes, or benzene-insoluble organoaluminum oxy
compounds as disclosed in Japanese Laid-open Patent Publication No.
32
H02-78687.
[0073]
For example, the conventionally known aluminoxanes can be
prepared by the following methods and are usually obtained as a
5 solution in a hydrocarbon solvent.
1) A method in which an organoaluminum compound such as
trialkylaluminum is added to a hydrocarbon medium suspension of a
compound containing adsorbed water or a salt containing water of
crystallization, such as magnesium chloride hydrate, copper sulfate
10 hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous
chloride hydrate), to allow the organoaluminum compound to react with
the adsorbed water or the water of crystallization.
2) A method in which water, ice or water vapor is allowed to
act directly on an organoaluminum compound such as trialkylaluminum
15 in a medium such as benzene, toluene, diethyl ether or
tetrahydrofuran.
3) A method in which an organoaluminum compound such as
trialkylaluminum is allowed to react with an organotin oxide such
as dimethyl tin oxide or dibutyltin oxide in a medium such as decane,
20 benzene or toluene.
[0074]
The aluminoxane may contain small amounts of organometallic
components. After the sol vent or unreacted organoaluminum compound
are distilled away from the recovered solution of the aluminoxane,
25 the aluminoxane obtained may be redissolved in a solvent or suspended
in a poor solvent for the aluminoxane. Examples of the organoaluminum:
compounds used in preparing the aluminoxanes include the
ti
I
I
I
I
il
I
~
I
I
!I !;
l_:,
r"
33
organoaluminum compounds mentioned above as the organoaluminum
compounds (2a-1) . Among those compounds, trialkylaluminum and
tricycloalkylaluminum are preferable, and trimethylaluminum is
particularly preferable. The organoaluminum compounds may be used
5 alone or two or more kinds thereof may be used in combination.
[0075]
The benzene-insoluble organoaluminum oxy compounds (2b) usually
contain Al components that will dissolve in benzene at 60°C in an
amount of equal to or less than 10 millimols, p'referably equal to
10 or less than 5 millimols, and particularly preferably equal to or
less than 2 millimols in terms of Al atoms (the amount can be obtained
by suspending an organoaluminum oxy compound equivalent to 100
milligrams of Al atoms in 100 ml of benzene, mixing the materials
with stirring for 6 hours at 60°C, filtering the mixture at 60°C by
15 using a G-5 glass filter with jacket, washing the solids remaining
on the filter with 50 ml of benzene at 60°C four times, and then
measuring the amount (x%) of the Al atoms (x millimols) which are
present in the filtrates). That is, it is preferable that the
organoaluminum oxy compounds are insoluble or hardly soluble in
20 benzene. The organoaluminum oxy compounds (2b) may be used alone
or two or more kinds thereof may be used in combination.
[0076]
The compounds (2c) that can react with the transition metal
compound ( la) to form an ion pair include Lewis acids, ionic compounds,
25 borane compounds and carborane compounds as disclosed in Japanese
Laid-open Patent Publication No. HOl-501950, Japanese Laid-open
Patent Publication No. HOl-502036, Japanese Laid-open Patent
-!
I
i[
34
Publication No. H03-179005, Japanese Laid-open Patent Publication
No. H03-179006, Japanese Laid-open Patent Publication No. H03-207703,
Japanese Laid-open Patent Publication No. H03-207704 and US Patent
No. 5, 321,106. Further, heteropoly compounds and isopoly compounds
5 can be also used. The compounds (2c) may be used alone or two or
more kinds thereof may be used in combination.
[0077]
In the production of Component (B) used in the embodiment, when
the catalyst contains the transition metal compound (la) and the
10 organoaluminum oxy compound (2b) such as methylaluminoxane,
particularly high polymerization activity can be achieved.
[0078]
In addition, the polymerization catalysts for the production
of Component (B) used in the embodiment may contain a carrier or a
15 cocatalyst component as required.
[0079]
Such catalysts may be prepared by mixing the respective
components in advance or after the components are carried by carriers.
Alternatively, the respective components may be added to the
20 polymerization system simultaneously or successively.
Component (B) used in the embodiment is obtained suitably by
copolymerizing propylene and 1-butene under the presence of the
aforementioned catalyst. During the copolymerization, the
respective monomers may be used in amounts such that the desired ratio
25 of constitutional units in Component (B) to be produced.
Specifically, the monomers are desirably used such that a ratio
between propylene and 1-butene molar is 50/50 to 95/5, preferably
, I
I
'I
'I
'
I
I
!
I I I
,I
'I
I !
35
60/40 to 90/10, and more preferably 70/30 to 90/10.
[0080]
The conditions for copolymerization are not particularly
limited. For example, the polymerization temperature may be usually
5 in a range of --50 to +200°C, preferably 0 to 170°C, and the
polymerization pressure may generally range from normal pressure to
10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge
'I' I j
pressure. In addition, the polymerization reaction may be performed
batchwise, s'emi -continuously or continuously. Further, the
10 polymerization may be performed in two or more stages under different
reaction conditions.
The molecular weight of Component (B) may be controlled by the
presence of hydrogen in the polymerization system or by changing the
polymerization temperature. The molecular weight can be also
15 controlled by adjusting the amount of the compound (2a), (2b), or
(2c) . In the case of in which hydrogen is added, a suitable amount
thereof is within a range of about 0.001 to 100 NL per 1 kg of the
monomers.
[0081]
20 [Component (C)]
Component (C) used in the embodiment is a copolymer of ethylene
and an a-olefin having 3 to 20 carbon atoms. The a-olefin can be
appropriately selected according to the application of use of the
laminate film and a copolymer of ethylene and an a-olefin having 3
25 to 10 carbon atoms is used.
[0082]
In addition, as Component (C) used in the embodiment, components
36
having the following properties are preferably used:
(a) the density (measured at 23°C according to ASTM 1505) is
within a range of 0.850 to 0.910 g/cm3
, preferably 0.860 to 0.905
g/cm3
, and more preferably 0.865 to 0.895 g/cm3
; and
5 (b) the melt flow rate (MFR; measured at l90°C and a load of
2.16 kg according to ASTM 01238) is 0.1 to 150 g/10 min and preferably
0.3 to 100 g/10 min,
When Component (C) having such properties is used, heat sealing
is easily performed at a relatively low temperature.
10 [0083]
The production method of Component (C) is not particularly
limited and can be produced by copolymerizing ethylene and the
a-olefin with a radical polymerization catalyst, Philips catalyst,
Ziegler-Natta catalyst, or a metallocene catalyst.
15 Among these, when Component (C) is produced using a metallocene
catalyst, the copolymer usually has a molecular weight distribution
(Mw/Mn) of equal to or less than 3, and thus this case is preferable.
[0084]
The crystallinity of Component (C) measured by X-ray
20 diffractometry is usually equal to or less than 40%, preferably 0
to 39%, and more preferably 0 to 35%.
[0085]
Specific examples of the a-olefin having 3 to 20 carbon atoms
used in the production of Component (C) include propylene, 1-butene,
25 1-pentene, 1-hexene, 4-methylpentene, 1-octene, 1-decene, and
1-dodecene. These may be used alone or two or more kinds thereof
may be used in combination.
I
I
I
i
I
'I 'l
II
ii
li
37
Among these a-olefins, propylene, 1-butene, 1-hexene, and
1-octene are preferable and 1-butene is particularly preferable.
[0086]
It is preferable that Component (C) contains a constitutional
5 unit derived from ethylene in an amount of 50 to 99 mol% and a
constitutional unit derived from an a-olefin having 3 to 20 carbon
atoms in an amount of 1 to 50 mol%, and the total of the constitutional
unit derived from ethylene and the constitutional unit derived from
the a-olefin is 100 mol%.
10 As a more preferable embodiment, Component (C) contains a
constitutional unit derived from ethylene in an amount of 60 to 95
mol% and a constitutional unit derived from an a-olefin having 3 to
20 carbon atoms in an amount of 5 to 40 mol%, and the total of the
constitutional unit derived from ethylene and the constitutional unit
15 derived from the a-olefin is 100 mol%.
When the amounts are set to be within the above ranges, heat
sealing is easily performed even at a relatively low temperature.
[0087]
The molecular structure of Component (C) may be linear or
20 branched with long or short side-chains. Further, plural different
ethylene·a-olefin random copolymers can be used as a mixture.
[0088]
Component (C) can be produced by known methods using a vanadium
catalyst, a titanium catalyst, a metallocene catalyst, or the like.
25 For example, the component can be produced by the method described
in Japanese Patent Laid-Open Publication No. Hl0-212382. As
Component (C), commercially available products may be used.
I
I
I
I
i
I !
l
I
'i ~
I
I!
38
[0089]
[Component (D)]
Component (D) used in the embodiment is a copolymer of 1-butene
and an a-olefin having 3 carbon atoms or 5 to 20 carbon atoms containing
5 a constitutional unit derived from 1-butene in an amount of 50 to
99 mol% and a constitutional unit derived from an a-olefin having
3 carbon atoms or 5 to 20 carbon atoms in an amount of 1 to 50 mol%
(wherein the total of the constitutional unit derived from 1-butene
and the constitutional unit derived from the a-olefin js 100 mol%).
10 The a-olefin can be appropriately selected according to the
application of use of the laminate film and an a-olefin having 3 to
10 carbon atoms (excluding 1-butene) is preferably used.
[0090]
Specific examples of the a-olefin that can be used as Component
15 (D) include ethylene, propylene, 1-hexene, 4-methyl-1-pentene,
1-octene, 1-decene and 1-dodecene. Among these, ethylene and
propylene are preferable, and propylene is particularly preferable.
[0091]
It is preferable that Component (D) contains a constitutional
20 unit derived from 1-butene in an amount of 60 to 95 mol% and a
constitutional unit derived from an a-olefin having 3 carbon atoms
or 5 to 20 carbon atoms in an amount of 5 to 40 mol%, and the total
of the constitutional unit derived from 1-butene and the
constitutional unit derived from the a-olefin is 100 mol%.
25 As a more preferable embodiment, Component (D) contains a
constitutional unit derived from 1-butene in an amount of 70 to 90
mol% and a constitutional unit derived from an a-olefin having 3 carbon
, I
I
39
atoms or 5 to 20 carbon atoms in an amount of 10 to 30 mol%, and the
total of the constitutional unit derived from ethylene and the
constitutional unit derived from the a-olefin is 100 mol%.
When the amounts are set to be within the above ranges, heat
5 sealing is easily performed even at a relatively low temperature.
[0092]
The melt flow rate (MFR; measured at 230°C and a load of 2.16
kg according to ASTM Dl238) of Component (D) is within a range of
0.1 to 50 g/10 min, preferably 0. 2 to 40 g/10 min, imd more preferably
10 0.5 to 25 g/10 min.
[0093]
Such Component (D) can be produced by polymerization using a
known Ziegler-based catalyst or metallocene-based catalyst.
Specifically, the component can be produced by polymerization methods
15 using a stereoregular catalyst described in Japanese Examined Patent
Application No. 364-7088, Japanese Laid-open Patent Publication No.
359-206415, Japanese Laid-open Patent Publication No. 359-206416,
Japanese Laid-open Patent Publication No. H04-218508, and Japanese
Laid-open Patent Publication No. HOB-225605.
20 As Component (D), commercially available products may be used.
[0094]
(Base Layer)
The laminate film 30 according to the embodiment is obtained
by laminating the base layer 20 on the aforementioned heat sealing
25 layer 10.
The base material for constituting the base layer 20 may adopt
conventionally known materials according to the application of use.
- ,--L'-~
40
I . '
Specific examples thereof include thermoplastic resin films such as
films composed of polyesters typified by polyethylene terephthalate
and polyethylene naphthalate, polycarbonate films, films composed
of polyamides such as nylon 6 and nylon 66, ethylene·vinyl alcohol
5 copolymer films, polyvinyl alcohol films, polyvinyl chloride films,
polyvinylidene chloride films and films composed of polyolefins such
as polypropylene.
In addition, a single layer or two or more layers composed of
the base material may be used according to the application of use.
10 As the thermoplastic resin film, a film obtained by depositing
an inorganic substance such as aluminum, zinc, or silica, or an oxide
may be used.
[0095]
(Application)
15 The laminate film 30 according to the embodiment can be sued
to produce a packaging bag by fusing (for example, heat-fusing) the
heat sealing layers 10 of the laminate films 30.
The packaging bag obtained by the embodiment includes a heat
sealing layer composed of a resin composition including specific
20 Component (A) to Component (D), and although the heat sealing layer
is subjected to a corona treatment, even in the case of performing
sealing at a known heat sealing temperature, a sufficient strength
can be exhibited. Therefore, in the case in which the heat sealing
layers are heat-fused, a packaging bag having antifogging properties
25 and excellent in strength can be obtained.
Therefore, it is possible to use the packaging bag as a packaging
bag for various hydrous foods typified by meat, processed meat foods
41
such as sausage, fresh vegetables and seafood, and other processed
foods.
Needless to say, the application of use of the packaging bag
of the embodiment is not limited to food and as long as antifogging
5 properties are required in the application, for example, application
of packaging ornamental plants and the like, the packaging bag can
be suitably used.
[0096]
The embodiments of the present invention have been described
10 above but these are merely examples of the present invention. Various
configurations other than the above embodiments can be adopted.
[Examples]
[0097]
Next, the laminate film of the present invention and the
15 packaging bag obtained from the laminate film will be described in
more detail with reference to examples but the present invention is
not limited to these examples.
[0098]
The methods of measuring each physical property of Component
20 (A), Component (B), Component (C), and Component (D) are as follows.
[0099]
[Molecular Weight Distribution (Mw/Mn)]
The molecular weight distribution (Mw/Mn) was measured by using
a gel permeation chromatograph Alliance GPC-2000, manufactured by
25 Waters Corporation as follows. Separation column used were two
columns of TSKgel GNH6-HT and two columns of TSKgel GNH6-HTL, each
having an inner diameter of 7.5 mm and a length of 300 mm, and the
42
column temperature was set to 140°C. The mobile phase was composed
of a-dichlorobenzene (manufactured by Wako Pure Chemical Industries,
Ltd.) and 0.025% by weight of BHT (manufactured by Takeda
Pharmaceutical Company Limited.) as an antioxidant, and was moved
5 at 1. 0 ml/min, and the sample concentration was adjusted to 15 mg/10
mL. The injection amount of the sample was 500 microliters and a
differential refractometer was used as a detector. With regard to
standard polystyrenes, for those having a molecular weight of Mw <
1, 000 and Mw > 4 x 106
, those manufactured by Tosoh Corporation were
10 used; and for those having a molecular weight of 1,000 ~ Mw ~ 4 x
106
, those manufactured by Pressure Chemical Company were used.
[0100]
[Content of Ethylene, Propylene, and a-Olefin in Polymer]
The contents of ethylene, propylene, and a-olefin were
15 determined using a JNM GX-500 Model NMR measuring apparatus
manufactured by JEOL LTD. as follows. 0. 35 g of a sample was dissolved
in 2.0 ml of hexachlorobutadiene by heating. The solution was
filtered through a glass filter (G2) , 0. 5 ml of deuterated benzene
was then added thereto, and the mixture was put into an NMR tube having
20 an inner diameter of 10 mm. The 13C-NMR was measured at 120°C. The
number of integration times was set to be equal to or more than 10,000
times. The composition of ethylene, propylene, and a-olefin was
determined from the obtained 13C-NMR spectrum.
25
[0101]
[Melting Point (Tm) of Component (A)]
A sample of about 5 mg was heated to 200°C in a nitrogen atmosphere
(20 ml/min) using DSCPyris1 or DSC7 manufactured by Perkin Elmar Co.,
5
43
Ltd., held for 10 minutes, and then cooled to 30°C at l0°C/min. After
holding the sample at 30°C for 5 minutes, the sample was heated to
200°C at l0°C/min, wherein the melting point was calculated from the
top of the crystalline melting peak.
[0102]
[Melting Point (Tm) Component (B), Component (C), and Component
(D) ]
Using DSC manufactured by Seiko Instruments Inc., a sample of
about 5 mg was placed in an aluminum pan for measurement, heated to
10 200°C at 100°C/min, and held at 200°C for 5 minutes. Then, the sample
was cooled to -150°C at l0°C/min and heated to 200°C at 10 °C/min
to obtain an endothermic curve.
[0103]
[Melt Flow Rate (MFR) of Component (A), Component (B), Component
15 (C), and Component (D)]
The melt flow rate (MFR) of Component (A), Component (B), and
Component (D) was measured at 230°Cand a load of 2.16 kg according
to ASTM Dl238.
In addition, the melt flow rate (MFR) of Component (C) was
20 measured at 190°C and a load of 2.16 kg according to ASTM Dl238.
[0104]
[Heat Sealing Strength]
The films which had been subjected to a corona treatment, which
will be described later, were superposed in such a manner that the
25 corona-treated surfaces thereof were superposed, and the both
surfaces of the superposed films were sandwiched by a Teflon
(registered trademark) sheet having a thickness of 50 pm to form a
44
test piece. Next, heat seal bars of a heat seal tester (TB-7018
manufactured by TESTER SANGYO CO., LTD.) were installed so as to be
5 mm in width 5 mm x 300 mm in length and the temperature of the lower
seal bar was set to 70°C. The test piece (Teflon (registered
5 trademark) sheet/film/film/Teflon (registered trademark) sheet),
which was held by the heat seal bars, was heat-sealed at a pressure
of 0. 2 MPa for 1. 0 second. After the Teflon (registered trademark)
sheet was detached, the heat-sealed part of the composite films was
allowed to stand under a room temperature of about 23°C for 2 days.
10 The films including their heat-sealed parts were slit, the slit part
measuring 15 mm in width, while the non-sealed parts were chucked
to a tensile tester ("IM-20ST manufactured by "INTESCO"). At a rate
of 300 mm/min, the 180 o peeling strength between the films was measured.
The above operation was performed five times, and an average value
15 thereof was defined as heat sealing strength.
[0105]
Next, a synthesis example of a metallocene complex which is a
constitutional component of an olefin polymerization catalyst, and
a preparation example of a propylene·1-butene copolymer which is
20 Component (B) using the metallocene complex will be described.
[ 0106]
[Synthesis Example] -Synthesis of Metallocene Complex(
1) Preparation of 1-tert- butyl-3-methylcyclopentadiene
In a nitrogen atmosphere, a solution of 3-methylcyclopentenone
25 (43. 7 g, 0.45 mmol) in dried diethyl ether (150 ml) was added dropwise
to a solution obtained by adding dried diethyl ether (350 ml) to a
tert-butylmagnesium chloride/diethyl ether solution (450 ml, 0.90
45
mol, a 2. 0 mol/L solution), while keeping the temperature at 0 °C by
ice cooling. The mixture was further stirred at room temperature
for 15 hours. To the reaction solution, a solution of ammonium
chloride ( 80. 0 g, 1. 50 mol) in water ( 350 ml) was added dropwise while
5 keeping the temperature at 0 °C by ice cooling. Water .(2, 500 ml) was
added to the resultant solution, and the mixture was stirred. The
organic phase was separated and washed with water. A 10% aqueous
hydrochloric acid solution (82 ml) was added to the organic phase
while keeping the temperature at 0°C by ice cooling. The mixture
10 was stirred at room temperature for 6 hours. The organic phase of
the resultant reaction liquid was separated, then washed with water,
a saturated aqueous sodium hydrogen carbonate solution, water and
a saturated saline solution, and then dried over anhydrous magnesium
sulfate. The desiccant was filtered, and the sol vent was distilled
15 away from the filtrate, resulting in a liquid. The liquid was
distilled under reduced pressure ( 45 to 4 7 °C/10 mm Hg) to obtain 14.6
g of a light yellow liquid. The analytical data are shown below.
1H-NMR (270 MHz, in CDC13 , TMS standard) 66.31 + 6.13 + 5.94 +
5.87(s + s + t + d, 2H), 3.04 + 2.95 (s + s, 2H), 2.17 + 2.09 (s +
20 s, 3H), 1. 27 (d, 9H)
[0107]
(2) Preparation of 3-tert-butyl-1,6,6-trimethylfulvene
In a nitrogen atmosphere, dried acetone (55.2 g, 950.4 mmol)
was added dropwise to a solution of
25 1-tert-butyl-3-methylcyclopentadiene (13.0 g, 95.6 mmol) obtained
by the above method (1) in dried methanol (130 ml), while keeping
the temperature at 0 °C by ice cooling, and subsequently pyrrolidine
46
(68.0 g, 956.1 mmo1) was added thereto dropwise. The mixture was
stirred at room temperature for 4 days. The resultant reaction liquid
was diluted with diethyl ether (400 ml), and water (400 ml) was added.
The organic phase was separated, then washed with a 0.5 N aqueous
5 hydrochloric acid solution (150 ml x 4), water (200 ml x 3) and a
saturated saline solution (150 ml), and dried over anhydrous
magnesium sulfate. The desiccant was filtered, and the sol vent was
distilled away from the filtrate, resulting in a liquid. The liquid
was distilled under reduced pressure ( 70 to 80 °C/0. 1 mm Hg) to obtain
10 10.5 g of a yellow liquid. The analytical data are shown below.
1H-NMR (270 MHz, in CDC13 , TMS standard) i56.23 (s, 1H), 6.05 (d,
1H), 2.23 (s, 3H), 2.17 (d, 6H), 1.17 (s, 9H)
[0108]
(3) Preparation of 2-(3-tert-butyl-5-methyl
15 cyclopentadienyl)-2-fluorenylpropane
In a nitrogen atmosphere, a hexane solution of n-butyllithium
( 40 ml, 61. 6 mmol) was added dropwise to a solution of fluorene ( 10. 1
g, 60. 8 mmol) obtained by the above method ( 2) in THF ( 300 m1) with
ice cooling. The mixture was stirred at room temperature for 5 hours
20 (resulting in a dark brown solution). The solution was ice cooled
again, and a solution of 3-tert-butyl-1, 6, 6-trimethylfulvene (11. 7
g, 66.5 mmol) in THF (300 m1) was added thereto dropwise in a nitrogen
atmosphere. The reaction solution was stirred at room temperature
for 14 hours. The resultant brown solution was ice cooled, and water
25 (200 ml) was added. The obtained solution was extracted with diethyl
ether. Then the organic phase was separated therefrom, and dried
over magnesium sulfate. The organic phase was filtered, and the
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47
solvent was removed from the filtrate under reduced pressure,
resulting in an orange brown oil. The oil was purified by silica
gel column chromatography (developing solvent: hexane) to obtain 3.8
g of a yellow oil. The analytical data are shown below.
5 1H-NMR (270 MHz, in CDC13 , TMS standard) 67.70 (d, 4H), 7. 34-7.26
(m, 6H) , 7.18-7.11 (m, 6H) , 6.17 ( s' 1H) , 6.01 (s, 1H) , 4.42 (s, 1H),
4.27 (s, 1H),3.01 ( s' 2H), 2.87 ( s' 2H) , 2.17 ( s' 3H) , 1. 99 (s, 3H),
2.10 (s, 9H) , 1. 99 (s, 9H) , 1.10 (s, 6H), 1. 07 ( s' 6H).
[0109]
10 ( 4) Preparation of
dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluoreny
lzirconium dichloride
In a nitrogen atmosphere, a hexane solution of n-butyllithium
(5.0 ml, 7.7 mmol) was added dropwise to a solution of
15 2-(3-tert-butyl-5-methylcyclopentadienyl)-2-fluorenylpropane
( 1. 14 g, 3. 3 mmol) obtained by the above method ( 3) in diethyl ether
(25 ml) in ice cooling. The mixture was stirred at room temperature
for 14 hours to give a pink slurry. Zirconium tetrachloride (0. 77
g, 3. 3 mmol) was added to the slurry at -78°C. The mixture was stirred
20 at -78°C for several hours and at room temperature for 65 hours. The
resultant dark brown slurry was filtered. The residue was washed
with 10 ml of diethyl ether, and then was extracted with
dichloromethane to obtain a red solution. The solvent of the solution
was distilled away under reduced pressure to obtain 0.53 g of red
25 orange solid metallocene catalyst
dimethylmethylene(3-tert-buty1-5-methylcyclopentadienyl)fluoreny
lzirconium dichloride. The analytical data are shown below.
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48
1H-NMR (270MHz, inCDC13 , TMSstandard) 08.11-8.02 (m, 3H), 7.82
(d, lH), 7.56-7.45 (m, 2H), 7.23-7.17 (m, 2H), 6.08 (d, lH), 5.72
(d, lH), 2.59 (s, 3H), 2.41 (s, 3H), 2.30 (s, 3H), 1.08 (s, 9H).
[0110]
5 [Preparation Example] -Propylene·l-Butene Copolymer (B)-
A 2,000 ml polymerizer that had been thoroughly purged with
nitrogen was charged with nitrogen was charged with 875 ml of dried
hexane, 7 5 g of 1-butene, and triisobutylaluminum ( 1. 0 mmol) at normal
temperature. The temperature inside the polymeiizer was increased
10 to 65 °C, and the polymerizer was pressurized to 0. 7 MPa with propylene.
Subsequently, a toluene solution in which 0.002 mmol of
dimethylmethylene
(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium
dichloride as the metallocene catalyst which had been obtained in
15 the above Synthesis example, 0.6 mmol of rnethylaluminoxane
(manufactured by Tosoh Finechem Corporation) in terms of aluminum
were in contact with each other was added in the polymerizer.
Polymerization was performed for 30 minutes while keeping the
internal temperature of the polymerizer at 65°C and the propylene
20 pressure at 0. 7 MPa, and was terminated by the addition of 20 ml of
methanol. The polymerizer was depressurized, and' then the polymer
was precipitated by adding the polymerization solution to 2 L of
methanol and was dried under vacuum at 130°C for 12 hours.
[0111]
25 The polymer thus obtained weighed 15.2 g. The polymer had a
content of 1-butene (M) of 19.4 mol%, a melt flow rate (MFR) of 6.5
g/10 min, a molecular weight distribution (Mw/Mn) of 2.11, and a
49
melting point (Tm) of 75.3°C; In the following description, the
polymer is abbreviated as PBR in some cases.
[ 0112]
[Example 1]
5 (Production of Unstretched Laminate Film 1)
Two extruders connected to a T-die was used and the resin
composition for a heat sealing layer and the resin composition for
a base layer shown below were supplied to the respective extruders,
and the temperature of the die and resin composi ti6n was set to 230 °C.
10 The amount of extrusion of each extruder was set such that a ratio
between the thickness of the heat sealing layer and the thickness
of the base layer became 2/23, and an unstretched laminate film 1
having a thickness of 1,000 pm was obtained by coextrusion molding.
The resin composition for a heat sealing layer was obtained by
15 blending as component (A), Adsyl5C30F (manufactured by
LyondellBasell Industries) as a propylene random copolymer having
a MFR of 5.5 g/10 min, and a melting point of 138°C, the
propylene·l-butene copolymer (B) obtained in the above preparation
example, and as Component (C), an ethylene·l-butene copolymer
20 (manufactured by Mitsui Chemicals, Inc. ethylene content: 90 mol%,
a-olefin content: 10 mol%, MFR 3.6 g/10 min, density: 870 kg/m3
) at
a weight ratio of 85/7.5/7.5. In the following description,
Adsyl5C30F (manufactured by LyondellBasell Industries) is simply
abbreviated as PP, and ethylene·l-butene copolymer is simply
25 abbreviated as EBR in some cases.
The resin composition or a base layer was Prime Polypro Fll3G
(manufactured by Prime Polymer Co., Ltd.).
I
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[0113]
(Production of Stretched Laminate Film 1)
I j
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The above unstretched laminate film 1 was biaxially stretched
by a batch type biaxial stretching machine at a stretching temperature
5 of 158°C and a stretching rate of 238% such that vertical x horizontal
= 5 times x 8 times (stress relaxation after stretching for 30 seconds)
to obtain a stretched laminate film 1 (the thickness of the base layer:
23 pm, the thickness of the heat sealing layer: 2 pm).
Next, using a moving table type corona treatment apparatus,
10 manufactured by Kasuga electric works Ltd., (effective treatment
width = 430 mm, electrode = wire electrode used, treatment rate =
10 em/sec ( 6 m/min), one-way corona treatment, discharge output: 2.15
A), the surface of the film on the side close to the heat sealing
layer was subjected to a corona treatment.
15 [ 0114]
(Measurement of Heat Sealing Strength)
Next, the stretched laminate films 1 were superposed in such
a manner that the corona-treated heat sealing layers were superposed
and the both surfaces of the superposed films were sandwiched by a
20 Teflon (registered trademark) sheet having a thickness of 50 pm to
prepare a test piece. According to the aforementioned method of
measuring heat sealing strength, the 180° peeling strength between
the films was measured at a rate of 300 mm/min. Each physical property
will be shown in Table 1.
25 [0115]
(Measurement of Wet Tension)
According to ASTM-D-2578-67T, the wet tension was measured in
51
the atmosphere of 23°C and 65% RH. The measurement was repeated five
calculated. The measurement value after 5 to 6 hours had passes from
i
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times by replacing the test piece, and an average value thereof was
the corona treatment and the measurement value after 3 days had passed
5 form the corona treatment were collected.
[0116]
(Evaluation of Antifogging Properties)
100 ml of water was poured into a 300 ml beaker and the temperature
c),
was adjusted to 30°C by a heat stirrer. Then, the laminate film was
10 attached to the beaker such that the surface on. the side close to
the heat sealing layer and the contents in the beaker faced to each
other and sealed with a rubber band. The sealed beaker was allowed
to stand in an environment of l0°C and 50% RH for 20 minutes and the
attachment of water drops was evaluated in two stages. The evaluation
15 result was A.
A: The inner surface of the film was evenly wet and water drops
were not observed and the inner surface was less evenly wet but the
opposite side was clearly seen.
B: The opposite side was not clearly viewed in some portions
20 due to water drops and the opposite side was not completely seen due
to a large number of fine water drops.
Generally, when the film exhibits a wet tension of about 35 to
40 mN/m, the result that the film does not have antifogging properties
is obtained in the evaluation.
25 [0117]
[Example 2]
A film was prepared in the same manner as in Example 1 except
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52
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that instead of using the blend including Component (A), Component
(B), and Component (C) at a weight ratio of 85/7.5/7.5, a blend
including Component (A), Component (B), and Component (C) at weight
ratio of 85/4/11 was used, and evaluation of heat sealing strength,
5 measurement of wet tension, and evaluation of antifogging properties
were performed. The results are shown in Table 1.
[0118]
[Comparative Example 1]
A film was prepared in the same manner as in Example· 1 except
10 that instead of using the blend including Component (A) , Component
(B), and Component (C) at a weight ratio of 85/7.5/7.5, a blend
including Component (A) and Component (B) at a weight ratio of 85/15,
and evaluation of heat sealing strength, measurement of wet tension,
and evaluation of antifogging properties were performed. The results
15 are shown in Table 1.
[0119]
[Comparative Example 2]
A film was prepared in the same manner as in Example 1 except
that instead of using the blend including Component (A), Component
20 (B), and Component (C) at a weight ratio of 85/7.5/7.5, a blend
including Component (A) and Component (C) at a weight ratio of 85/15,
and evaluation of heat sealing strength, measurement of wet tension,
and evaluation of anti fogging properties were performed. The results
are shown in Table 1.
25 [0120]
[Comparative Example 3]
A film was prepared in the same manner as in Example 1 except
53
that instead of using the blend including Component (A), Component
(B), and Component (C) at a weight ratio of 85/7.5/7.5, only Component
(A) was used, and evaluation of heat sealing strength, measurement
of wet tension, and evaluation of antifogging properties were
5 performed. The results are shown in Table 1.
[0121]
[Reference Example 1]
Evaluation of heat sealing strength was performed in Example
1 without a corona treatment. The result is showh in Table 1. When
10 the antifogging properties were measured as in Example 1, the
attachment of a large number of fine water drops to the film on the
side close to the heat sealing layer was recognized and it was
determined that antifogging properties was not sufficient (in Table
1, expressed as "B").
15 [0122]
[Reference Example 2]
Evaluation of heat sealing strength and evaluation of
antifogging properties were performed in Example 2 without a corona
treatment. The result is shown in Table 1.
20 [0123]
[Reference Example 3]
Evaluation of heat sealing strength and evaluation of
antifogging properties were performed in Comparative Example 1
without a corona treatment. The results are shown in Table 1.
25 [0124]
[Reference Example 4]
Evaluation of heat sealing strength and evaluation of
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5
54
antifogging properties were performed in Comparative Example 2
without a corona treatment. The results are shown in Table 1.
[ 0125]
[Reference Example 5]
Evaluation of heat sealing strength and evaluation of
antifogging properties were performed in Comparative Example 3
without a corona treatment. The results are shown in Table 1.
55
[0126]
[Table 1]
Example 1 Example 2
Comparative Comparative Comparative
Example 1 Example 2 Example 3
Reference Reference Reference Reference Reference
Example 1 Example 2 Example 3 Example 4 Example 5
Corona treatment (discharge
output = 2.15 A, mobility = 6 Treated Treated Treated Treated Treated
m/min)
Not Not Not Not Not
treated treated treated treated treated
Composition of heat (A) pp 85 85 85 85 100 85 85 85 85 100
sealing layer (parts (B) PBR 7.5 4 15 0 0 7.5 4 15 0 0
by weight)
(C)EBR 7.5 11 0 15 0 7.5 11 0 15 0
70°C 0.1 0.1 0 0 0 0.1 0 0.1 0 0
80°C 0.1 0.1 0 0.1 0 0.1 0.1 0.8 0.1 0.1
90°C 0.2 0.1 0.1 0.1 0.1 1.9 1.0 3.1 0.1 0.1
100°C 0.5 0.2 0.1 0.2 0.1 3.9 1.7 3.0 0.1 0.1
Heat sealing strengtll
(N/15 mm) 110°C 1.1 0.8 0.2 0.6 0.2 2.8 3.1 2.6 2.0 0.2
120°C 3.1 2.2 1.9 1.8 1.6 3.8 3.8 2.8 3.5 3.6
130°C 3.6 3.5 3.5 3.3 2.4 4.1 3.4 3.8 4.1 3.0
140°C 3.1 3.3 3.2 3.8 3.2 3.2 3.7 3.0 4.1 2.8
150°C 3.2 3.4 3.5 3.4 3.0 3.4 3.5 3.3 4.4 3.8
5 to 6hr 39 39 38 39 40 28 28 28 28 28
wet tension (mN/M)
3 days 38 38 37 38 37 - - - - -
Evaluation of antifogging
A A A A A properties B B B B B
In Table, the symbol " " indicates unmeasured.
56
[0127]
[Example 3]
(Production of Unstretched Laminate Film 2)
An unstretched laminate film 2 was produced in the same manner
5 as in the production of the unstretched laminate film 1 except that
as the resin composition for a heat sealing layer, a resin composition
obtained by blending, as Component (A), Adsyl5C30F (manufactured by
LyondellBasell Industries) as a propylene random copolymer having
a MFR of 5. 5 g/10 min and a melting point of 138oc; as Component (B),
10 the propylene·l-butene copolymer (B) obtained in the above
preparation example, and as Component (D), a 1-butene·propylene
copolymer (manufactured by Mitsui Chemicals, Inc. 1-butene content:
76 mol%, propylene content: 24 mol%, MFR 9.0 g/10 min, density: 885
kg/m3
) at a weight ratio of 70/15/15 was used. In the following
15 description, the 1-butene ·propylene copolymer is simply abbreviated
as BPR in some cases.
[0128]
(Production of Stretched Laminate Film 2)
The above unstretched laminate film 2 was biaxially stretched
20 by a batch type biaxial stretching machine at a stretching temperature
of 158 °C and a stretching rate of 238% such that vertical x horizontal
= 5 times x 8 times (stress relaxation after stretching for 30 seconds)
to obtain a stretched laminate film 2 (the thickness of the base layer:
23 pm, the thickness of the heat sealing layer: 2 pm).
25 Next, using a moving table type corona treatment apparatus,
manufactured by Kasuga electric works Ltd., (effective treatment
width = 430 mm, electrode = wire electrode used, treatment rate =
5
57
6.7 em/sec (4 m/min), one-way corona treatment, discharge output:
1. 95 A) , the surface of the film on the side close to the heat sealing
layer was subjected to a corona treatment.
[0129]
(Measurement of Heat Sealing Strength, Measurement of Wet
Tension, and Evaluation of Antifogging Properties)
Next, the stretched laminate films 2 were superposed in such
a manner that the corona-treated heat sealing layers were superposed
and the both surfaces of the superposed films were sandwiched by a
10 Teflon (registered trademark) sheet having a thickness of 50 pm to
15
prepare a test piece. Measurement of heat sealing strength and
evaluation of antifogging properties were performed by the exactly
same method described in Example 1. The results are shown in table
2.
Incidentally, regarding the unstretched laminate film of
Example 3, and the following Comparative Examples 4 and 5, and
Reference Examples 5 to 8, the wet tension was measured in an
environment of 23°C and 65% RH according to ASTM-D-25'/8-67T. The
measurement was repeated five times by replacing the test piece, and
20 an average value thereof was calculated. The measurement value after
25
5 to 6 hours had passes from the corona treatment and the measurement
value after 3 days had passed form the corona treatment were collected.
[0130]
[Comparative Example 4]
A film was prepared in the same manner as in Example 3 except
that instead of using the blend including Component (A), Component
(B), and Component (D) at a weight ratio of 70/15/15, a blend including
58
Component (A) and Component (B) at a weight ratio of 70/30 was used,
and evaluation of heat sealing strength, measurement of wet tension,
and evaluation of antifogging properties were performed. The results
are shown in Table 2.
5 [0131]
[Comparative Example 5]
A film was prepared in the same manner as in Example 3 except
that instead of using the blend including Component (A), Component
(B), and Component (D) at a weight ratio of 70/15'/15, only Component
10 (A) was used, and evaluation of heat sealing strength, measurement
of wet tension, and evaluation of antifogging properties were
performed. The results are shown in Table 2.
15
[0132]
[Reference Example 6]
Evaluation of heat sealing strength and measurement of wet
tension were performed in Example 3 without a corona treatment. The
results are shown in Table 2. When the antifogging properties were
measured as in Example 3, the attachment of a large number of fine
water drops to the film on the side close to the heat sealing layer
20 was recognized and it was determined that antifogging properties was
not sufficient (in Table 2, expressed as "B") .
[0133]
[Reference Example 7]
Evaluation of heat sealing strength, measurement of wet tension,
25 and evaluation of antifogging properties were performed in
Comparative Example 4 without a corona treatment. The results are
shown in Table 2.
59
[0134]
[Reference Example 8]
Evaluation of heat sealing strength, measurement of wet tension,
and evaluation of antifogging properties were performed in
5 Comparative Example 5 without a corona treatment. The results are
shown in Table 2.
60
[0135]
[Table 2]
Example 3 Comparative Comparative
Example 4 Example 5
Reference Reference Reference
Example 6 Example 7 Example 8
Corona treatment (discharge
output= 1.95 A, mobility= 4 Treated Treated Treated Not treated Not treated Not treated
m/min)
Composition of heat (A) pp 70 70 100 70 70 100
sealing layer (parts (B) PBR 15 30 0 15 30 0
by weight) (C)EBR 15 0 0 15 0 0
70°C 0 0 0 3.7 2.9 0.1
80°C 0.5 0 0 3.6 3.9 0.1
90°C 0.5 0.1 0 3.7 4.2 0.1
Heat sealing strengtt 100°C 3.5 0.1 0.1 3.8 4.2 0.1
(N/15 nun) ll0°C 4.3 0.2 0.1 3.5 4.3 0.4
120°C 3.2 1.9 0.5 3.7 4. 4 3.8
130°C 3.8 3.5 3.4 3.8 3.8 3.7
140°C 3.6 3.2 3.9 3.7 3.8 3.8
Wet tension (mN/m) 5 to 6hr 39 38 40 28 28 28
Evaluation of antifogging
A A A properties B B B
~c..:c..;oc:;.;;;- ---- ---~~------ ~--,- ---"~,~~-----=.;o"~;;",,~»·-c • '"~",.,,, ____ • ' ,.,,,._, _ ,_ __ ,~- -"~~ "~~~- ~- ---" ·-·~-
II
:,,[
~ I
61
I I I
[0136]
As easily understood from the results of Examples, Comparative
Examples, and Reference Examples above, for example, at a heat sealing
temperature of 120°C which is industrially most frequently adopted,
5 in the heat sealing layers composed of a known single polypropylene,
or a blend of two components of polypropylene/propylene·l-butene
copolymer, the heat sealing strength is decreased by about 2. 0 N and
0.9 N each (for example, comparisons of Reference Example 5 and
Comparative Example 3, and Reference Example 3 ·and Comparative
10 Example 1, and the like) by a corona treatment for improving visibility
of contents in a packaging bag (= exhibit antifogging properties)
are recognized, and in the case of using a heat sealing layer composed
of a blend of three components of polypropylene/propylene·l-butene
copolymer/ethylene·a-olefin copolymer, the decrease width is
15 controlled to be 0. 7 N, and a heat sealing strength thereof of more
than 3 N is exhibited (for example, comparison of Reference Example
1 and Example 1).
Similarly, when the heat sealing layer composed of a
polypropylene, a propylene·l-butene copolymer, and a
20 1-butene ·propylene copolymer is subjected to a corona treatment, the
effect of suppressing a decrease in heat sealing strength is exhibited
(refer to Table 2) .
[0137]
The laminate film of the present invention is excellent in
25 antifogging properties and exhibits sufficient strength at a known
heat sealing temperature during heat sealing. Therefore, the film
can be used for various applications including a packaging bag for
--------------- - -- - ---------------
hydrous foods.
[0138]
62
The present application claims priority based on Japanese Patent
Application No. 2014-169835 filed on August 22, 2014, the content
5 of which is incorporated herein by reference.

CLAIMS
1. A laminate film comprising:
a heat sealing layer composed of a resin composition including,
5 with respect to 20 to 95 parts by weight of a propylene-based
polymer (A) having a melting point (Tm) of equal to or higher than
120°C and equal to or lower than 170°C as measured by differential
scanning calorimetry (DSC),
a total of 5 to 80 parts by weight of two 'or more kinds of
10 copolymers selected from the group consisting of
a propylene·l-butene copolymer (B) containing. a unit derived
from propylene in an amount of 51 to 95 mol% and a unit derived from
1-butene in an amount of 5 to 4 9 mol%, wherein the total of the unit
derived from propylene and the unit derived from 1-butene is 100 mol%,
15 a copolymer (C) of ethylene and an ex-olefin having 3 to 20 carbon
atoms, and
a copolymer (D) of 1-butene and an ex-olefin having 3 carbon atoms
or 5 to 20 carbon atoms containing a constitutional unit derived from
1-butene in an amount of 50 to 99 mol% and a constitutional unit derived
20 from an ex-olefin having 3 carbon atoms or 5 to 20 carbon atoms in
an amount of 1 to 50 mol%, wherein the total of the unit derived from
1-butene and the unit derived from the ex-olefin is 100 mol%,
wherein each of Component (B), Component (C), and Component (D)
does not correspond to Component (A) , and the total amount of Component
25 (A), Component (B), Component (C), and Component (D) is 100 parts
by weight; and
a base layer,
I'
II
II
1.1
'!
64
wherein a surface of the heat sealing layer opposite to the base
layer has a wet tension of 32 to 45 mN/m.
2. The laminate film according to claim 1,
5 wherein the surface of the heat sealing layer is modified by
a corona treatment. (
3. The laminate film according to claim 1 or 2,
wherein two or more kinds of copolymers selected from the group
10 consisting of the Component (B), the Component (C), and the Component
(D) include the Component (B) as a required component, and the content
of the Component (B) is 3 to 25 parts by weight, wherein the total
amount of Component (A), Component (B), Component (C), and Component
(D) is 100 parts by weight.
15
4. The laminate film according to any one of claims 1 to 3,
wherein the copolymer (C) of ethylene and an a-olefin having
3 to 20 carbon atoms contains a constitutional unit derived from
ethylene in an amount of 50 to 99 mol% and a constitutional unit derived
20 from an a-olefin having 3 to 20 carbon atoms in an amount of l to
50 mol%, wherein the total of the unit derived from ethylene and the
unit derived from the a-olefin is 100 mol%.
5. The laminate film according to any one of claims 1 to 4 which
25 is not stretched.
6. The laminate film according to any one of claims 1 to 4 which
I
I
:I
,.·.•: ·.'1
,,
\-
11 il :1 ~ I! !I
li
II I
~
5
65
is biaxially stretched.
7. A packaging bag which is formed by fusing the heat sealing layers
of the laminate films according to any one of claims 1 to 6.
8. A laminate film comprising:
a heat sealing layer composed of a resin composition including,
with respect to 20 to 95 parts by weight of a propylene-based
polymer (A) having a melting point (Tm) of equal to or higher than
10 120°C and equal to or lower than 170°C as measured by differential
scanning calorimetry (DSC),
a total of 5 to 80 parts by weight of two or more kinds of
copolymers selected from the group consisting of
a propylene·l-butene copolymer (B) containing a unit derived
15 from propylene in an amount of 51 to 95 mol% and a unit derived from
1-butene in an amount of 5 to 4 9 mol%, wherein the total of the unit
derived from propylene and the unit derived from 1-butene is 100 mol%,
a copolymer (C) of ethylene and an ex-olefin having 3 to 20 carbon
atoms, and
20 a copolymer (D) of 1-butene and an ex-olefin having 3 carbon atoms
or 5 to 20 carbon atoms containing a constitutional unit derived from
1-butene in an amount of 50 to 99 mol% and a constitutional unit derived
from ex-olefin having 3 carbon atoms or 5 to 20 carbon atoms in an
amount of 1 to 50 mol%, wherein the total of the unit derived from
25 1-butene and the unit derived from the ex-olefin is 100 mol%,
wherein each of Component (B), Component (C), and Component (D)
does not correspond to Component (A) , and the total amount of Component
-------________ , __
66
CA), Component ·(B), Component (C), and Component (D) is 100 parts
by weight; aJ;ld
l ~-· '
a base ;f:ayer,
wherein the heat. sealing layer inc)_uded in the LJ.minate ,film
5 is subjected to a modification treatment.
9. The laminate film according to claim 8,
wherein the surface of the heat ,sealing ].ayer opposite to the
base layer has a wet tension of 5 to 30 mN/m ..