U.S. patent application number 13/764603 was filed with the patent office on 2013-06-13 for plastic container having pearl-like appearance and process for producing the same.
The applicant listed for this patent is Kentarou ICHIKAWA, Nobuhisa KOISO. Invention is credited to Kentarou ICHIKAWA, Nobuhisa KOISO.
Application Number | 20130149480 13/764603 |
Document ID | / |
Family ID | 37637243 |
Filed Date | 2013-06-13 |
United States Patent
Application |
20130149480 |
Kind Code |
A1 |
ICHIKAWA; Kentarou ; et
al. |
June 13, 2013 |
PLASTIC CONTAINER HAVING PEARL-LIKE APPEARANCE AND PROCESS FOR
PRODUCING THE SAME
Abstract
This invention provides a plastic container characterized in
that an expanded layer comprising expanded cells having a flat
shape with an average major axis of not more than 400 .mu.m and an
average aspect ratio (L/t) of not less than 6 as viewed in cross
section of the container wall along the maximum stretch direction,
which are oriented in the stretch direction and are distributed so
as to be superimposed on top of each other in the thickness-wise
direction, is formed within the container wall. In this container,
expanded cells having a flat shape are distributed so as to orient
in a given direction and, thus, has light shielding properties and
has a pearl-like appearance, that is, has a very high commercial
value. Further, since any colorant is not contained, the
suitability for recycling is excellent.
Inventors: |
ICHIKAWA; Kentarou;
(Yokohama-shi, JP) ; KOISO; Nobuhisa;
(Yokohama-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ICHIKAWA; Kentarou
KOISO; Nobuhisa |
Yokohama-shi
Yokohama-shi |
|
JP
JP |
|
|
Family ID: |
37637243 |
Appl. No.: |
13/764603 |
Filed: |
February 11, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11994751 |
Jan 31, 2008 |
8397932 |
|
|
PCT/JP2006/314021 |
Jul 7, 2006 |
|
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13764603 |
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Current U.S.
Class: |
428/36.5 |
Current CPC
Class: |
B29B 2911/14332
20150501; B29B 2911/14633 20130101; B29K 2027/08 20130101; B29B
2911/14093 20130101; B29B 2911/1418 20130101; B29K 2995/0041
20130101; B29B 2911/14653 20130101; B29K 2025/00 20130101; B29K
2067/006 20130101; B29L 2031/7158 20130101; B29C 44/0407 20130101;
B29C 44/3453 20130101; B29C 49/0073 20130101; B29B 2911/14328
20150501; B29B 2911/14153 20130101; B29B 2911/14926 20130101; B29B
11/12 20130101; B29B 2911/14466 20130101; B29B 2911/14106 20130101;
B29B 2911/14233 20130101; B65D 1/40 20130101; B29B 2911/14326
20130101; B29B 11/10 20130101; B29B 2911/1444 20130101; B29B
2911/1404 20130101; B29K 2067/00 20130101; B29B 2911/14033
20130101; B29B 2911/14053 20130101; B29B 2911/14213 20130101; Y10T
428/1376 20150115; B29B 2911/14906 20130101; B29K 2077/00 20130101;
B29K 2067/046 20130101; B29B 11/08 20130101; B29B 2911/1494
20130101; B29B 2911/1408 20130101; B29K 2069/00 20130101; B29K
2023/065 20130101; B29B 2911/14913 20130101; B29K 2055/02 20130101;
B29C 49/06 20130101; B29C 44/352 20130101; B29B 2911/14126
20130101; B29K 2027/06 20130101; B29B 2911/1442 20130101; B65D
1/0207 20130101; B29B 2911/14066 20130101; B29B 2911/1402 20130101;
B29B 2911/14646 20130101; B29B 2911/14666 20130101; B29B 2911/14026
20130101; B29K 2105/04 20130101; B29C 49/64 20130101; B29B
2911/1416 20130101; B29B 11/14 20130101; B29B 2911/14333 20130101;
B29K 2023/0633 20130101; B29K 2023/12 20130101; B29B 2911/14133
20130101; B65D 1/0246 20130101; B29D 22/003 20130101; B29K
2995/0067 20130101 |
Class at
Publication: |
428/36.5 |
International
Class: |
B65D 1/40 20060101
B65D001/40 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 13, 2005 |
JP |
2005-203868 |
May 30, 2006 |
JP |
2006-149911 |
May 30, 2006 |
JP |
2006-150228 |
Claims
1.-15. (canceled)
16. A preform for a container formed by integral molding of a
thermoplastic resin, wherein a region corresponding to at least a
body portion and a bottom portion of the container is a foamed
region, said foamed region forming a foamed layer in which foamed
cells are isotropically distributed and a skin layer in which no
foamed cell is distributed.
17. (canceled)
18. The preform for a container according to claim 16, wherein a
portion corresponding to a container mouth portion and the
vicinities thereof are unfoamed regions where no foamed cell is
present.
19. The preform for a container according to claim 18, wherein a
degree of crystallization in said unfoamed region is not smaller
than 13%.
20. The preform for a container according to claim 18, wherein the
preform has a shape of a test tube with its bottom closed, and has,
on an outer surface at an upper portion thereof, a neck portion
comprising a support ring and a threaded portion positioned above
the support ring, said neck portion being the unfoamed region.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of U.S.
application Ser. No. 11/994,751 filed Jan. 31, 2008, which is a 371
of PCT International Application No. PCT/JP2006/314021 filed Jul.
7, 2006, which claims benefit of Japanese Patent Application No.
2005-203868 filed Jul. 13, 2005, Japanese Patent Application No.
2006-150228 filed May 30, 2006 and Japanese Patent Application No.
2006-149911 filed May 30, 2006. The above-noted applications are
incorporated herein by reference to their entirety.
TECHNICAL FIELD
[0002] The present invention relates to a plastic container in
which foamed cells are distributed in the container wall and
pearl-like appearance is imparted thereto due to the foamed cells,
and a process for producing the same.
BACKGROUND ART
[0003] It has heretofore been known that a plastic container
obtained by forming a resin composition containing a scale-like
inorganic pigment (e.g., talc) dispersed therein exhibits
pearl-like (pearl luster) appearance. That is, light is scattered
and reflected in the container wall due to the scale-like pigment.
The plastic container exhibiting the pearl-like appearance has a
very high commercial value.
[0004] In recent years, however, it has been strongly urged to
reutilize the resources and attempts have been made to recover the
used containers such as the above polyester containers to reutilize
them as the recycled resins for a variety of applications. However,
the plastic container having the pearl-like appearance is not
suited for being recycled. This is because the scale-like inorganic
pigment dispersed in the resin for imparting the pearl-like
appearance makes it difficult to maintain transparency in the
recycled resin.
[0005] A patent document 1 is proposing a plastic container
imparted with light shielding property by dispersing bubbles
(foamed cells) in the container wall.
[0006] In the plastic container of the patent document 1, light
scattered by the foamed cells distributed in the container wall
works to impart light shielding property, and the plastic container
is very suited for being recycled since it uses no coloring
component such as pigment. However, the plastic container of the
patent document 1 has not been imparted with such an aesthetic
appearance as pearl-like tone and does not have such an appearance
that may enhance commercial value.
[0007] Further, when the container is formed by using a resinous
foamed material, inconvenience often occurs due to the foaming.
That is, a container as represented by a bottle has a threaded
portion formed in the mouth portion thereof and a cap can be fitted
thereto by screw-fastening. However, if the mouth portion of the
container is formed of the foamed material, the strength decreases
due to the foam and the dimensional stability decreases in the
mouth portion of the container. In particular, a decrease in the
dimensional stability at the threaded portion causes a decrease in
the sealing performance when the cap is fitted.
[0008] To avoid the above problem, patent documents 2 and 3 are
disclosing containers of which the body portions and bottom
portions are formed of a foamed material but of which the mouth
portions are not foamed.
[0009] Patent document 1: JP-A-2003-26137
[0010] Patent document 2: JP-A-61-53021
[0011] Patent document 3: JP-A-10-329203
[0012] The patent document 2 forms a preform (parison) in which is
entirely distributed a foaming agent such as a decomposable foaming
agent like an azo dicarbonimide or sodium bicarbonate, or a
freon-type or hydrocarbon-type organic solvent foaming agent, heats
the preform so as to be foamed except a portion corresponding to
the mouth portion of the container, and stretch blow molds the
preform in this state to obtain a container having the mouth
portion that is not foamed. According to this method, however, the
foaming agent is distributed over the whole preform, and the
foaming cannot be effectively suppressed at the mouth portion of
the container; i.e., the mouth portion of the container is merely a
lowly foamed region where the degree of foaming is low, still
leaving room for improvement from the standpoint of suppressing a
decrease in the strength of the container mouth portion (threaded
portion) and suppressing a decrease in the dimensional
stability.
[0013] The patent document 3 produces a bottle by melt-kneading
various foaming agents and a thermoplastic resin, directly
blow-molding a preform while melt-extruding the kneaded mixture,
forming a foamed preform by cooling the preform, heating the foamed
preform again to a predetermined temperature, and blow-molding the
bottle by blowing the air of a predetermined pressure. This method
is to produce a bottle through a two-step blow which is a
combination of a direct blow and a cold parison blow, and has a
feature in that a portion corresponding to the container mouth
portion is not expanded at the time of forming the foamed preform
and the mouth portion of the finally obtained bottle has not been
foamed. Even with this method, however, the foaming agent has been
distributed over the whole foamed preform which is an intermediate
product like in the patent document 2, and the mouth portion of the
container is merely a region that is lowly foamed as compared to
the body portion or the bottom portion. Namely, the foaming cannot
be completely suppressed in the mouth portion of the container,
which is not satisfactory from the standpoint of suppressing a
decrease in the strength of the container mouth portion (threaded
portion) caused by the foaming and suppressing a decrease in the
dimensional stability.
[0014] There has further been known a method of separately forming
a portion corresponding to the body portion or the bottom portion
and a portion corresponding to the mouth portion, and joining the
two together after having been formed. According to this method,
the body portion and the bottom portion of the container are
selectively foamed yet leaving the mouth portion of the container
unfoamed. With this method, however, the body portion, bottom
portion and mouth portion must be separately formed. Therefore, the
productivity is low and the cost of production becomes high.
Namely, this method cannot be employed from an industrial point of
view.
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0015] It is therefore an object of the present invention to
provide a plastic container which does not use a coloring component
such as a scale-like inorganic pigment, imparted with a pearl-like
appearance due to the distribution of foamed cells, has a high
commercial value, and is excellently suited for being recycled, and
a method of its production.
[0016] Another object of the present invention is to provide a
plastic container in which the body portion and the bottom portion
of the container are the foamed regions where the foamed cells are
selectively formed but no foamed cell is present in the mouth
portion of the container where mechanical properties such as
strength, etc. are required, and a method of its production.
[0017] A further object of the present invention is to provide a
preform used for producing the plastic container.
Means for Solving the Problems
[0018] According to the present invention, there is provided a
plastic container comprising a body portion, a bottom portion and a
mouth portion formed at an upper end of the body portion, wherein a
wall forming at least the body portion and the bottom portion is a
foamed region having a foamed layer and in the foamed region,
foamed cells of a flat shape having an average long diameter of not
larger than 400 .mu.m and an average aspect ratio of not smaller
than 6 as viewed in cross section along a maximum stretching
direction, are oriented in the stretching direction and are
distributed being overlapped one upon the other in a direction of
thickness to thereby form the foamed layer.
[0019] In the plastic container of the present invention, it is
desired that: [0020] (1) An outer surface of the wall in the foamed
region is a smooth surface having a surface roughness Ra of not
larger than 5 .mu.m; [0021] (2) A skin layer in which no foamed
cell is distributed is formed on the outer surface of the wall in
the foamed region; [0022] (3) The wall in the foamed region has a
5-layer structure comprising skin layer/foamed layer/core
layer/foamed layer/skin layer, and the skin layers and the core
layer are unfoamed layers where no foamed cell is present; and
[0023] (4) The mouth portion is an unfoamed region without the
foamed layer.
[0024] According to the present invention, there is further
provided a process for producing a plastic container comprising the
steps of:
[0025] preparing an unfoamed preform formed by integral molding of
a thermoplastic resin and imbibing an inert gas;
[0026] heating the unfoamed preform to effect foaming to obtain a
foamed preform having a foamed layer in a wall, said foamed layer
having formed cells which are isotropically distributed; and
[0027] stretch blow molding the foamed preform so that the foamed
cells assume a flat shape having an average long diameter of not
larger than 400 .mu.m and an average aspect ratio of not smaller
than 6 as viewed in cross section along a maximum stretching
direction.
[0028] In the process for producing a plastic container of the
present invention, it is desired that: [0029] (1) The thermoplastic
resin is, first, formed into an unfoamed preform by integral
molding and then an inert gas is imbibed; [0030] (2) The inert gas
is released from the surface of the unfoamed preform imbibing the
inert gas, and the unfoamed preform is heated to effect the foaming
in order to form a skin layer without foamed cell in the surface
portion of the foamed preform; [0031] (3) The unfoamed preform
imbibing the inert gas is held under normal pressure in a cooled
and solidified state, so that the inert gas is released from the
surface portion of the unfoamed preform; [0032] (4) The unfoamed
preform is held in an inert gas atmosphere of a high pressure, so
that the wall of the unfoamed preform imbibes the inert gas except
a central portion thereof; [0033] (5) The heating of the unfoamed
preform for effecting the foaming is discontinued before the
foaming starts in the central portion of the wall, in order to form
the core layer where no foamed cell is distributed; [0034] (6) A
mouth portion and the vicinity thereof of the unfoamed preform are
selectively heat-treated so as to be crystallized, and the inert
gas is imbibed in the unformed preform; [0035] (7) The selective
heat-treating is effected so that a degree of crystallization in
the surface is not smaller than 13%; [0036] (8) The heating for
effecting the foaming is selectively executed for the regions
corresponding to the container bottom portion and the container
body portion of the unfoamed preform, so will not to form the
foamed cells in the regions corresponding to the mouth portion and
the vicinity thereof of the unfoamed preform; and [0037] (9) The
unfoamed preform has the shape of a test tube with its bottom
closed, and has, on the outer surface at an upper portion thereof,
a neck portion comprising a support ring and a threaded portion
positioned above the support ring.
[0038] According to the present invention, there is further
provided a preform for a container formed by integral molding of a
thermoplastic resin, wherein a region corresponding to at least a
body portion and a bottom portion of the container is a foamed
region, the foamed region forming a foamed layer in which foamed
cells are isotropically distributed and a skin layer in which no
foamed cell is distributed.
[0039] The plastic container is obtained by stretch-forming the
preform.
[0040] In the preform for a container, it is desired that: [0041]
(1) The wall in the foamed region has a 5-layer structure
comprising skin layer/foamed layer/core layer/foamed layer/skin
layer, and the skin layers and the core layer are the unfoamed
layers where no foamed cell is present; [0042] (2) A portion
corresponding to the container mouth portion and the vicinity
thereof are the unfoamed regions where no foamed cell is present;
[0043] (3) The degree of crystallization in the unfoamed region is
not smaller than 13%; and [0044] (4) The preform has the shape of a
test tube with its bottom closed, and has, on the outer surface at
an upper portion thereof, a neck portion comprising a support ring
and a threaded portion positioned above the support ring, the neck
portion being the unfoamed region.
[0045] The plastic container of the present invention contains flat
foamed cells of a predetermined size distributed being overlapped
one upon the other in the container wall, and exhibits pearl-like
appearance offering a very high commercial value. Upon being
imparted with the pearl-like appearance by the foamed cells without
using a coloring agent such as pigment or a filler, further, the
plastic container of the invention is very suited for being
recycled.
[0046] When a skin layer without the foamed cells is formed on the
outer surface side of the container wall, further, smoothness is
imparted to the surface enhancing its luster as well as more
distinct pearl-like appearance contributing to enhancing aesthetic
appearance to the highest degree.
[0047] Further, the core layer without the foamed cell is formed in
the central portion of the container wall to form a 5-layer
structure comprising skin layer/foamed layer/core layer/foamed
layer/skin layer, enhancing the strength and, further, improving
gas-barrier property.
[0048] The plastic container of the present invention is produced
by.forming a foamed preform by utilizing the so-called
microcellular technology, and stretch-forming the foamed preform.
Here, by adjusting the conditions for producing the foamed preform,
the mouth portion and the vicinity thereof of the container can be
selectively formed as an unfoamed region where no foamed layer is
present. In this case, it is allowed to effectively avoid a
decrease in the strength of the neck portion of the container that
is threaded and a decrease in the dimensional stability
thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0049] FIG. 1 is a sectional view showing the container wall of a
plastic container of the invention along the maximum stretching
direction;
[0050] FIG. 2 is a sectional view of a preferred structure of the
container wall of the plastic container of the invention along the
maximum stretching direction;
[0051] FIG. 3 is a side view of a bottle which is a plastic
container of the invention;
[0052] FIG. 4 is a side sectional view of a cup-like container
which is a plastic container of the invention;
[0053] FIG. 5 is a view schematically illustrating representative
steps in a production process according to the invention;
[0054] FIG. 6 is a sectional view showing the structure of a
container wall of a preform (foamed preform) for a container
obtained through the production steps of the invention;
[0055] FIG. 7 is a view illustrating a step of selective
crystallization for selectively forming the neck portion of the
bottle to be an unfoamed region;
[0056] FIG. 8 is a side sectional view showing a foamed preform
(preform for a container) used for forming a bottle of which the
neck portion is selectively formed as an unfoamed region;
[0057] FIG. 9 is a view illustrating a step of foaming by the
selective heating for selectively forming the neck portion of the
bottle to be an unfoamed region; and
[0058] FIG. 10 is a side sectional view showing a sheet-like foamed
preform (preform for a container) used for forming a cup-like
container having a flange that is selectively formed to be an
unfoamed region.
BEST MODE FOR CARRYING OUT THE INVENTION
Plastic Container
[0059] A plastic container of the invention will now be described.
Referring to FIG. 1 showing the container wall in cross section
along the maximum stretching direction, the container wall
generally designated at 10 is forming a foamed layer 5 in which
foamed cells 1 are distributed. The foamed cells 1 have a flat
shape oriented in the maximum stretching direction and are
distributed being overlapped one upon the other in the direction of
thickness. Therefore, light is scattered and reflected in a
multiplexed fashion to exhibit a particular pearl-like appearance.
If, for example, the foamed cells 1 have a spherical shape and are
not flat, then light is scattered but is little reflected
(reflection surfaces are small); i.e., no pearl-like appearance is
obtained but light shielding property is simply imparted.
[0060] In the present invention, it is also important that the
foamed cells 1 have an average long diameter of not larger than 400
.mu.m and, particularly, not larger than 200 .mu.m and an average
aspect ratio (ratio L/t of the long diameter L and the thickness t
as viewed in cross section) in a range of not smaller than 6 and,
particularly, not smaller than 8. That is, if the average long
diameter L is larger than the above range, light is scattered less
deteriorating the appearance. Further, if the average aspect ratio
is smaller than the above range, light reflection surfaces decrease
reflecting light less. In either case, satisfactory pearl-like
appearance is not obtained.
[0061] Further, the foamed cells 1 are overlapped one upon the
other in the direction of thickness, preferably, in a number of
three or more on average to obtain a sufficient degree of
pearl-like appearance.
[0062] In the present invention as shown in FIG. 1, further, it is
desired to form a skin layer 7 without foamed cell 1 on the surface
and, particularly, on the outer surface of the container wall 10.
Formation of the skin layer 7 makes it possible to smooth the outer
surface of the container wall 10, i.e., to form a smooth surface
having an average surface roughness Ra (JIS B 0601) of, for
example, not larger than 5 .mu.m. As a result, it is made possible
to obtain more highly aesthetic pearl-like appearance. Namely, the
luster is enhanced by the surface smoothness and, at the same time,
light reflected by the surface interferes with part of light
reflected by the foamed cells 1 in the inside exhibiting more
distinct pearl-like appearance and the most aesthetic
appearance.
[0063] Further, formation of the skin layer 7 without the foamed
cell 1 is effective in improving the printability of the container
as well as in suppressing a decrease in the strength and in the
gas-barrier property resulting from the formation of foamed cells
1.
[0064] In the present invention, there is no particular limitation
on the thickness of the skin layer 7 formed on the outer surface
side of the container wall 10 so far as the foamed cells 1 are
distributed being overlapped one upon the other at a predetermined
degree in the direction of thickness. Usually, however, it is
desired that the thickness thereof is about 2 to about 200 .mu.m.
If the skin layer 7 is too thin, the thickness becomes irregular
and the skin layer 7 fails to stably express the aesthetic
appearance. If the thickness is too large, on the other hand, it
becomes necessary to increase the thickness of the container wall
10 to obtain a desired pearl-like appearance by maintaining the
degree of overlapping of the foamed cells 1 though there is no
problem from the standpoint of suppressing a decrease in the
strength and in the gas-barrier property.
[0065] As described above, the skin layer 3 maybe formed on the
outer surface side of the container wall 10 but may further be
formed on the inner surface side thereof.
[0066] In the plastic container of the invention as shown in FIG.
2, further, it is also allowable to form the above-mentioned skin
layer 7 on both the outer surface side and the inner surface side
of the container wall 10 and to form a core layer 9 without foamed
cell 1 in the center thereof. In this case, the container wall 10
possesses a 5-layer structure comprising skin layer 7/foamed layer
5/core layer 9/foamed layer 5/skin layer 7. The plastic container
forming the wall of the 5-layer structure features an increased
strength and increased gas-barrier property owing to the core layer
9 without foamed cell 1 formed in the central portion. It is
desired that the skin layers 7 formed on the outer surface side and
on the inner surface side have a thickness in the above-mentioned
range, and the core layer 9, too, must have a thickness in a
suitable range depending upon the thickness of the container wall
10. That is, if the core layer 9 is too thick, the flat foamed
cells 1 are little overlapped one upon the other in the direction
of thickness and the pearl-like appearance is spoiled. Therefore,
the core layer must have a thickness in a range in which it does
not cause the above inconvenience.
[0067] According to the present invention, further, the container
wall 10 as a whole may be the foamed region forming the foamed
layer 5. Generally, however, it is desired that the container mouth
portion and the vicinity thereof selectively have no foamed layer 5
(i.e., are unfoamed regions without foamed cell 1).
[0068] FIG. 3 shows a bottle which is an example of the plastic
container of the invention. The bottle which is generally
designated at 20 in FIG. 3 includes a bottom portion 21 and a body
portion 23. A neck portion 29 including a threaded portion 25 and a
support ring 27 is formed at an upper end of the body portion. That
is, in this bottle 20, the bottom portion 21 and the body portion
23 are constituting a foamed region Y where the foamed layer 5 is
formed, exhibiting light shielding property, luster and pearl-like
appearance. On the other hand, the neck portion 29 corresponding to
the container mouth portion and the vicinity thereof is an unfoamed
region X. That is, the neck portion 29 which is the unfoamed region
X has a high strength without forming the foamed layer 5 and
possesses an excellent dimensional stability. Therefore, the
threaded portion 25 enables a cap to be reliably engaged therewith,
and the support ring 27 can be gripped assuring a reliable
transport.
[0069] FIG. 4 shows a cup-like container which is another example
of the plastic container of the present invention. In FIG. 4, the
cup-like container generally designated at 30 has a bottom portion
31 and a body portion 33. A flange 35 is formed at an upper end of
the body portion 33 extending outward. After the container 30 is
filled with a content, a sealing foil such as an aluminum foil is
adhered and secured to the flange 35 by heat-sealing. In the
cup-like container 30, the bottom portion 31 and the body portion
33 are constituting a foamed region Y where the foamed layer 5 is
formed, exhibiting light shielding property, luster and pearl-like
appearance. Further, the flange 35 corresponding to the container
mouth portion and the vicinity thereof is an unfoamed region X
forming no foamed layer 5. Therefore, the flange 35 has a high
strength, a high dimensional stability, and exhibits excellent
heat-sealing property.
[0070] The above-mentioned plastic container of the present
invention having the foamed layer 5 in which the foamed cells 1 are
distributed in the container wall 10, is produced by a physical
foaming method imbibing an inert gas therein as will be described
later. Therefore, there is no particular limitation on the resin
constituting the container wall 10 so far as it is capable of
imbibing an inert gas, and any known thermoplastic resin can be
used. For example, the container wall 10 can be formed by using
olefin resins such as random or block copolymers of .alpha.-olefins
or cyclic olefin copolymers, like low-density polyethylene,
high-density polyethylene, polypropylene, poly 1-butene, poly
4-methyl-1-pentene or ethylene, propylene, 1-butene and
4-methyl-1-pentene; ethylene/vinyl copolymers such as
ethylene/vinyl acetate copolymer, ethylene/vinyl alcohol copolymer,
and ethylene/vinyl chloride copolymer; styrene resins such as
polystyrene, acrylonitrile/styrene copolymer, ABS, and
.alpha.-methylstyrene/styrene copolymer; vinyl resins such as
polyvinyl chloride, polyvinylidene chloride, vinyl
chloride/vinylidene chloride copolymer, methyl polyacrylate and
methyl polymethacrylate; polyamide resins such as nylon 6, nylon
6-6, nylon 6-10, nylon 11 and nylon 12; polyester resins such as
polyethylene terephthalate, polybutylene terephthalate,
polyethylene naphthalate and copolymerized polyesters thereof;
polycarbonate resin; polyphenylene oxide resin; and a biodegradable
resin such as polylactic acid. The container wall 10 may be formed
by a blend of these thermoplastic resins. It is, particularly,
desired to use an olefin resin or a polyester resin that is
favorably used in the field of containers. Among them, the
polyester resin is most desired from the standpoint of utilizing
the advantage of the present invention to the greatest degree.
[0071] Further, the container wall 10 is not limited to the one of
a single-layer structure but may be of a multi-layer structure
having a gas-barrier layer of, for example, an ethylene/vinyl
alcohol copolymer resin, as well as a polyolefin resin layer or a
polyester resin layer adhered thereon via an adhesive layer of, for
example, a vinyl acetate copolymer resin. If the necessity for
being recycled is neglected, the container wall 10 may have a layer
structure provided with a gas-barrier layer having an
oxygen-absorbing agent such as an iron powder dispersed in the
resin layer.
Production of the Plastic Container
[0072] The plastic container having the pearl-like appearance of
the present invention is produced by preparing an unfoamed preform
imbibing, for example, an inert gas, heating the unfoamed preform
to obtain a foamed preform, and stretch blow molding the foamed
preform. FIG. 5 schematically illustrates a representative example
of the production process.
[0073] Referring to FIG. 5, first, an unfoamed preform 40 is
prepared by using the above-mentioned starting resin and is placed
under a high pressure condition so as to imbibe an inert gas (e.g.,
carbonic acid gas or nitrogen gas) permitting the inert gas to
dissolve therein (step (a)).
[0074] The unfoamed preform 40 can be formed by known forming means
such as extrusion forming, injection forming or compression
forming. Usually, the unfoamed preform 40 has the shape of a test
tube when it is attempted to produce a container of the shape of a
bottle and has the shape of a plate or a cup when it is attempted
to produce a container of the shape of a cup. When it is attempted
to produce a container having a multi-layer structure provided with
a gas-barrier layer, the unfoamed preform 40 is so formed as to
possess a multi-layer structure corresponding thereto by
co-extrusion or co-injection.
[0075] The unfoamed preform 40 imbibes the inert gas through the
above step (a) such that the gas is dissolved therein in amounts
sufficient for forming flat foamed cells 1. to exhibit desired
pearl-like appearance. For example, the unfoamed preform 40 may be
heated to imbibe the inert gas under a high pressure or may not be
heated. If the temperature is high, the gas dissolves in decreased
amounts but is imbibed at a high rate. If the temperature is low,
the gas dissolves in increased amounts but an increased period of
time is needed for the imbibing.
[0076] If the gas is imbibed under the heated condition, attention
should be given so that the temperature of the unfoamed preform 40
(particularly, the temperature of the body portion 2 and bottom
portion 3) does not exceed the thermal crystallization temperature
of the starting resin. If heated higher than the crystallization
temperature, the body portion 2 and the bottom portion 3 are
crystallized imposing limitation on the foaming in the subsequent
step of foaming.
[0077] Next, the unfoamed preform 40 is placed under normal
pressure (atmospheric pressure) in a cooled and solidified state
for a predetermined period of time, letting the inert gas to be
released from the surface of the unfoamed preform 40 to thereby
form a surface layer 43 where no inert gas is dissolved or the
inert gas concentration is low (step (b)). That is, the inert gas
does not almost dissolve under normal pressure and at normal
temperature. Upon holding the cooled and solidified unfoamed
preform 40 under normal pressure, therefore, the inert gas is
gradually released from the surface of the preform 40.
[0078] The surface layer 43 corresponds to the skin layer 7 where
no foamed cell 1 is present. The thickness of the skin layer 7 can
be adjusted by adjusting the time in which the preform is placed
under normal pressure in the state of being cooled and solidified.
That is, the thickness of the surface layer 43 increases with an
increase in the time for placing the preform under normal pressure
and, therefore, the thickness of the skin layer 7 can be increased.
The thickness of the surface layer 43 decreases with a decrease in
the time for placing the preform under normal pressure and,
therefore, the thickness of the skin layer 7 can be decreased.
Attention, however, should be given to that if the time for placing
the preform under normal pressure is too lengthened, the inert gas
is almost released making it difficult to form flat foamed cells 1
in amounts sufficient for exhibiting the pearl-like appearance.
[0079] When the skin layer 7 is not to be formed, the above step is
not necessary, and the process is readily shifted to a step (c)
described below.
[0080] In the example of FIG. 5, the surface layers 43 are formed
on both surfaces (outer surface side and inner surface side) of the
unfoamed preform 20. When the surface layer 43 is formed on one
surface (outer surface side) only to produce the container having
the skin layer 7 formed on the outer surface side only, the
unfoamed preform 40 of the shape of, for example, a test tube is
placed under normal pressure with its mouth portion closed or the
one surface (inner surface side) of the unfoamed preform 40 of the
shape of a plate is closely adhered to a suitable support member
and the outer surface only is exposed to the atmosphere of normal
pressure.
[0081] Next, the unfoamed preform 40 forming the surface layer 43
is heated by using an oil bath or an infrared-ray heater to effect
the foaming (step (c)). Due to this heating, bubbles evolve in the
unfoamed preform 40 in which the inert gas is remaining, and a
foamed preform 50 is obtained having a foamed layer 5 in which the
foamed cells 1a are distributed. Here, no inert gas is present or
its concentration is low in the surface layer 43 of the unfoamed
preform 40. Therefore, even if heated, the surface layer is not
foamed or is formed to a degree that cannot be confirmed unless
carefully observed. Namely, surface layer remains as the unfoamed
region where no foamed cell 1a is present in the foamed preform 50,
and the skin layer 7 is thus formed.
[0082] The heating temperature for foaming is higher than a glass
transition point of the resin forming the unfoamed preform 50. The
heating causes a quick change in the internal energy (free energy)
of the inert gas dissolved in the resin, triggering phase
separation and forming foam that is separated as bubbles from the
resin. The heating temperature should not be higher than a melting
point, desirably, not higher than 200.degree. C. to prevent the
foamed preform 50 from deforming. If the heating temperature is too
high, foaming occurs abruptly after being heated making it
difficult to control cell diameters, deteriorating the appearance,
causing the body portion to be crystallized and lowering the
secondary formability.
[0083] The foamed cells 1a (hereinafter often called spherical
foamed cells) formed as described above in the foamed preform 50
are substantially of a spherical shape and are isotropically
distributed. In this stage, therefore, light shielding property is
exhibited but peal-like appearance is not still exhibited. To
exhibit the pearl-like appearance, therefore, a stretch-forming
(stretch blow molding) becomes necessary as will be described
later.
[0084] Further, the cell density of the spherical foamed cells 1a
(density in the region excluding the skin layer 7) varies depending
upon the amount of the inert gas that is dissolved. If the
dissolved amount is large, the cell density becomes high and the
diameters of the spherical foamed cells become small. If the
dissolved amount is small, the cell density becomes low and the
diameters of the spherical foamed cells 1a become large. Further,
the diameters of the spherical foamed cells 1a can be adjusted
relying upon the heating time. If the heating time for foaming is
long, the diameters of the spherical foamed cells 1a increase. If
the heating time is short, the diameters of the spherical foamed
cells 1a decrease. According to the present invention, the above
conditions are adjusted so that the cell density of the spherical
foamed cells 1a in the foamed layer 5 becomes about 10.sup.6 to
about 10.sup.9 cells/cm.sup.3 and the average diameter becomes
about 5 to 50 .mu.m from the standpoint forming flat foamed cells 1
having the above-mentioned thickness t and average aspect ratio as
well as a suitable degree of overlapping in the direction of
thickness through the stretch-forming that will be described
later.
[0085] In the forming step (c), further, when the heating for
foaming is effected from the side of the one surface (particularly,
from the side of the inner surface) of the unfoamed preform 40, the
spherical foamed cells 1a are successively formed from the side of
the inner surface. By utilizing this, therefore, it is possible to
form the skin layer 7 in which no spherical foamed cell 1a is
present on the outer surface side without releasing the inert gas
(without effecting the above step (b)). That is, if the heating is
discontinued before the spherical foamed cells 1a are formed over
the whole thickness of the unfoamed preform 40, then the foamed
preform 50 is obtained having the skin layer 7 on the outer surface
side only.
[0086] In the above-mentioned embodiment, further, the inert gas is
imbibed after the unfoamed preform 40 is formed (step (a)).
However, the inert gas can also be imbibed by feeding the inert gas
maintaining a predetermined pressure to the resin held in a heated
and molten state in the resin-kneading portion or in the
plasticizing portion in a forming machine such as an extruder, an
injection-forming machine or a compression-forming machine for
forming the unfoamed preform. Or, the foaming by heating can be
executed at one time in the forming machine. However, the foaming
by heating executed at one time in the forming machine is not
suited for forming the skin layer 7 in which no foamed cell 1a is
present. In this case, further, the foamed cells 1a assume a shape
that is slightly flattened in a direction in which the resin flows.
In this case, therefore, it is desired that the foamed cells have
an average diameter in a range the same as the range of the average
diameter described above concerning the spherical foamed cells 1a
in the portion along the surface in the maximum stretching
direction.
[0087] To form the foamed preform 50 of the 5-layer structure
according to the present invention, the atmosphere of a high
pressure may be returned back to normal pressure to discontinue the
imbibing before the gas infiltrates up to the central portion of
the wall of the unfoamed preform 40 in the step (a) of imbibing the
inert gas described above. That is, no inert gas that is a source
of foaming is present in the central portion of the wall of the
unfoamed preform 40. By executing the above-mentioned step (b) of
releasing the inert gas and the step (c) of foaming, therefore, it
is made possible to obtain the foamed preform 50 of the 5-layer
structure shown in FIG. 6. That is, in the foamed preform 50, the
core layer 9 having no spherical foamed cell 1a is formed in the
central portion of the wall, and foamed layers 5 having spherical
foamed cells 1a distributed therein are present among the core
layer 9 and the skin layers 7 formed on the outer surface side and
on the inner surface side.
[0088] In the step (c) of foaming, further, the heating for foaming
is effected by blowing the hot air from both surfaces (outer
surface side and inner surface side) of the unfoamed preform 40.
Here, the heating is discontinued before the spherical foamed cells
1a are formed in all of the internal portion except the surface
layer 43 to thereby form the core layer 9 in the central portion
where no spherical foamed cell 1a is formed. Even by this method,
it is made possible to form the foamed preform 50 having the
5-layer structure as shown in FIG. 6, i.e., having the layer
structure comprising skin layer 7/foamed layer 5/core layer
9/foamed layer 5/skin layer 7.
[0089] Therefore, the foamed preform 50 of the 5-layer structure
shown in FIG. 6 is subjected to the step (d) of stretching to
produce a plastic container having the wall 10 of the 5-layer
structure shown in FIG. 2 forming the body portion and the bottom
portion thereof and exhibiting improved strength and gas-barrier
property.
[0090] In the step (d) of stretch-forming the foamed preform 50,
the draw-forming is effected according to a known method. For
example, the preform is heated at a temperature higher than a glass
transition temperature of the resin but lower than a melting point
thereof, and is stretched by a vacuum-forming as represented by a
blow-molding or a plug-assisted forming to obtain a bottle (see
FIG. 3) or a cup-like container (see FIG. 4) having the foamed
layer 5 in which the foamed cells 1 are distributed as the
spherical foamed cells 1a are deformed into a flat shape as shown
in FIG. 1 (or FIG. 2). It is, further, possible to obtain a
bag-like container by using a film which is obtained by
stretch-forming the foamed preform 50 of the shape of a sheet.
[0091] The stretching is effected to a suitable degree of
stretching ratio depending upon the diameter of the foamed cells la
and the cell density in the foamed preform 50, so that the
thickness t and aspect ratio of the foamed cells lie in the
above-mentioned ranges in cross section in the maximum stretching
direction. For example, in the stretch-forming (stretch blow
molding) effecting the stretching in the two axial directions,
i.e., in the axial direction (direction of height) and in the
circumferential direction, the stretching ratio is, usually, about
2 to about 4 times in these directions. In the plug-assisted
forming effecting the stretching in the monoaxial direction, i.e.,
in the axial direction only, the stretching in this direction is in
the maximum stretching direction effecting the stretching at the
same stretching ratio as above.
[0092] When the plastic container of the present invention is
produced according to the above-mentioned process, the glass
transition point of the resin decreases linearly or exponentially
with an increase in the amount of dissolution of the inert gas.
Further, the gas that is dissolved varies the viscoelasticity. For
instance, the viscosity of the resin decreases with an increase in
the amount of dissolution of the gas. By taking the amount of
dissolution of the inert gas into consideration, therefore, the
conditions should be so set that the flat cells 1 are formed so as
to exhibit pearl-like appearance.
Production of the Plastic Container Having Unfoamed Region
[0093] When the plastic container is produced by the
above-mentioned method, it is desired that the container mouth
portion and the vicinity thereof are forming an unfoamed region
where the foamed layer 5 has not been formed as described with
reference to FIGS. 3 and 4. The container having the unfoamed
region can be produced by two methods. These methods will be
described below with reference to the case of producing a
bottle.
Method 1:
[0094] One method is to execute the selective crystallization prior
to the above-mentioned step (a) of imbibing the gas.
[0095] That is, referring to FIG. 7 showing the step of
crystallization, an unfoamed preform 40 having the shape of a test
tube as a whole is provided. The unfoamed preform 40 has a bottom
portion 21a and a body portion 23a. A neck portion 29 having a
threaded portion 25 and a support ring 27 is formed above the body
portion 23a (the neck portion 29 corresponds to the neck portion 29
of the bottle 20 of FIG. 3). The unfoamed preform 40 is formed by a
known forming method such as the injection forming or the
compression forming as described above.
[0096] In order to form the neck portion 29 as the unfoamed region
according to this method, this portion is, first, selectively
crystallized to suppress the foaming in the step (c) of
foaming.
[0097] The neck portion 29 is selectively crystallized by
selectively heating this portion at a temperature higher than a
crystallization temperature of the crystalline thermoplastic resin
used as the starting material but lower than a melting point
thereof, and gradually cooling it after having been heated. As the
heating means, any means can be employed provided it is capable of
selectively heating the neck portion 29. As shown in FIG. 7, for
example, there can be employed means for heating the neck portion
29 by using such heating means 61 as an infrared-ray heater, a
quartz heater or a heated metal mold while holding the bottom
portion 21a and the body portion 23a by a jig 60 provided with a
cooling water pipe.
[0098] According to the present invention, it is desired to
crystallize the surface of the neck portion 29 to a degree
(laser-Raman method) of not less than 13%, preferably, not less
than 30% and, most preferably, not less than 40% by the
above-mentioned means. The higher the degree of crystallization,
the more reliably the foaming can be avoided in the neck portion 29
in the step (c) of foaming, and the foamed layer 5 can be
selectively formed in the bottom portion 21a and in the body
portion 23a. To increase the degree of crystallization of the neck
portion 29, the time may be lengthened for holding the neck portion
29 in, for example, the region of the crystallizing
temperature.
[0099] The unfoamed preform 40 having the neck portion 29 that is
selectively and thermally crystallized as described above is
subjected to the above-mentioned step (a) of imbibing the gas so as
to imbibe the inert gas. For example, the unfoamed preform is
introduced into a sealed chamber, the inert gas is fed into the
chamber, and the pressure is maintained high in the chamber so that
the inert gas infiltrates into the unfoamed preform 40. In this
case, the neck portion 29 of the unfoamed preform 40 has been
selectively crystallized. In the step of imbibing the gas,
therefore, the inert gas infiltrates into the region (bottom
portion 21a and body portion 23a) excluding the neck portion 29. In
the neck portion 29 that has been crystallized, the resin is very
suppressed from being plasticized due to the crystallization, and
the inert gas is not almost imbibed. In the step (c) of foaming
after the step (b) of releasing the gas, therefore, the bottom
portion 21a and the body portion 23a only are foamed, but the neck
portion 29 is not foamed. In this case, even if the inert gas may
infiltrate in small amounts into the neck portion 29, the resin of
the neck portion 29 is suppressed from being plasticized due to the
crystallization. In this case, too, therefore, the bubbles are
effectively suppressed from growing, and foaming is reliably
prevented.
[0100] After having executed the foaming as described above, the
preform is cooled to discontinue the foaming. As shown in FIG. 8,
therefore, there is obtained a preform for a container (foamed
preform) 50 having the bottom portion 21a and the body portion 23a
forming the foamed region Y containing the foamed layer 5 therein,
and having the neck portion 29 that is forming the unfoamed region
X. Namely, the neck portion 29 forms the unfoamed region X, and the
bottom portion 21a and the body portion 23a form the foamed region
Y, the region Y forming the foamed layer 5 and the skin layer 7 or
the core layer 7. By subjecting the preform to the above-mentioned
step (d) of stretching, there is obtained the bottle 20 shown in
FIG. 3 having the neck portion 29 formed as the unfoamed region X
and having the bottom portion 21 and the body portion 23 formed as
the foamed region Y.
Method 2:
[0101] According to this method, the unfoamed preform 40 is
subjected to the step (a) of imbibing the gas and the step (b) of
releasing the gas followed by the selective and thermal foaming in
the step (c) of foaming according to the above-mentioned process
shown in FIG. 5.
[0102] That is, as shown in FIG. 9(a) or 9(b), the neck portion 29
of the unfoamed preform 40 is held by a holding metal mold 71
equipped with a cooling water pipe 70, and the bottom portion 21a
and the body portion 23a are heated at a predetermined foaming
temperature by using an oil bath or an infrared-ray heater while
cooling the neck portion 29. Through the above selective heating,
the bottom portion 21a and the body portion 23a are selectively
foamed while reliably avoiding the foaming in the neck portion 29
to obtain the preform 50 for the container as shown in FIG. 8 like
the method 1. The preform is subjected to the above-mentioned step
(d) of stretching to obtain the bottle 20 shown in FIG. 3 having
the neck portion 29 forming the unfoamed region X and having the
bottom portion 21 and the body portion 23 forming the foamed region
Y.
[0103] Though the preform in the shape of a test tube was described
above, it is also possible to produce a foamed preform having the
unfoamed region X and the foamed region Y by using a sheet-like
unfoamed preform, as a matter of course. When the sheet-like
unfoamed preform is used, there is obtained a sheet-like preform
for a container (foamed preform) 50 as shown in FIG. 10. In this
preform 50, the circumferential edge corresponding to the container
mouth portion is forming the unfoamed region X, and the central
portion corresponding to the bottom portion and the body portion is
forming the foamed region Y which is forming the foamed layer 5,
skin layer 7 and core layer 9. By draw-forming the preform 50 for a
container, a cup-like container 30 can be obtained as shown in FIG.
4.
[0104] The plastic container of the present invention obtained as
described above exhibits pearl-like appearance and has a very high
commercial value. Particularly, the plastic container forming the
skin layer 7 without foamed cell 1 has a smooth surface, exhibiting
particularly excellent aesthetic peal-like appearance and features
good printability, too. Because of its light shielding property,
further, the plastic container can be effectively used for
containing a content that may undergo degeneration. Without being
blended with any coloring agent, further, the plastic container is
suited for being recycled. Further, formation of the foamed cells
contributes to decreasing the weight and attaining improved
heat-insulating property.
[0105] Moreover, the container having the 5-layer structure forming
the core layer 9 therein features high gas-barrier property and
high strength.
[0106] Further, the bottle has the neck portion corresponding to
the container mouth portion and the vicinity thereof forming the
unfoamed region, and features a high dimensional stability of the
threaded portion and enables a reliable sealing structure to be
formed upon being engaged with the cap. The support ring has a high
mechanical strength and effectively prevents the breakage at the
time of transport or working by gripping the support ring.
Moreover, the cup-like container of which the flange is forming an
unfoamed region features favorable heat-sealing property and makes
it possible to form a reliably sealed structure upon being
heat-sealed with a sealing foil such as aluminum foil.
EXAMPLES
Example 1
[0107] An unfoamed preform having a body wall thickness of 3 mm for
forming a 500-ml bottle was prepared by injection-forming a
homo-PET (polyethylene terephthalate) having an intrinsic viscosity
(IV) of 0.84 dL/g.
[0108] The preform was set in a pressure-resistant container
maintained at 40.degree. C. and was held under a pressure of 15 MPa
for one hour so as to imbibe the carbonic acid gas. Thereafter, the
pressure was decreased down to the atmospheric pressure, the
preform was taken out of the pressure-resistant container and was
held under the atmospheric pressure for 5 minutes. Further, hot
water maintained at 90.degree. C. was sprayed onto the outer
surface of the preform for 10 seconds to effect the foaming, and
there was obtained a foamed preform including a foamed layer having
a cell density of 8.5.times.10.sup.7 cells/cm.sup.3 and a thickness
of 180 .mu.m, and a skin layer of a thickness of 70 .mu.m on the
outer surface thereof.
[0109] From a photograph of cross section, the cell density was
calculated in compliance with the following formula,
[0110] N.sub.f=(n/A).sup.3/2
[0111] N.sub.f: cell density (/cm.sup.3),
[0112] A: sectional area observed,
[0113] n: number of cells in the sectional area A.
[0114] The thus obtained foamed preform was stretch-formed into a
bottle drawn into 2 times longitudinally and 2 times transversely.
There was obtained a foamed PET bottle having an average thickness
of 0.68 mm in the side body portion of the container, an average
surface roughness Ra of 0.5 .mu.m, a skin layer of 17 .mu.m, an
average long diameter of bubbles of 29 .mu.m in the foamed layer,
an average aspect ratio of bubbles of 8.7, and exhibiting favorable
pearl-like luster.
[0115] The average long diameter and the average aspect ratio were
average values of 5 to 50 cells found by processing the images of
bubbles of a photograph of cross section and by using a software
for measuring the shape.
[0116] The surface roughness was an average roughness Ra along the
center line measured in compliance with the JIS B 0601 by using a
surface roughness-measuring instrument.
[0117] The luster was evaluated by eyes and was decided on the
following basis.
[0118] .circleincircle.: Particularly excellent in both appearance
and pearl-like luster.
[0119] .largecircle.: Favorable in both appearance and pearl-like
luster.
[0120] .DELTA.: At least either the appearance or the pearl-like
luster is not desirable.
[0121] X: At least either the appearance or the pearl-like luster
is very poor.
Example 2
[0122] The foamed preform prepared in the same manner as in Example
1 was stretch-formed into a bottle drawn into 3 times
longitudinally and 3 times transversely. There was obtained a
foamed PET bottle having an average thickness of 0.32 mm in the
side body portion, an average surface roughness Ra of 0.3 .mu.m, a
skin layer of 10 .mu.m thick, an average long diameter of bubbles
of 42 .mu.m in the foamed layer, an average aspect ratio of bubbles
of 11.6, and exhibiting favorable appearance and pearl-like
luster.
Example 3
[0123] By using a copolymerized PET containing 5 mol % of
isophthalic acid and having an intrinsic viscosity (IV) of 0.90
dL/g and by using a T-die based on an extrusion foam-forming method
using the carbonic acid gas as a foaming agent, there was obtained
a foamed sheet having an average thickness of 0.58 mm and a cell
density of 4.times.10.sup.6 cells/cm.sup.3. Here, the T-die
temperature was suitably controlled so that the sheet surface
became smooth. The thus obtained foamed sheet was drawn by using a
biaxial stretching machine into 2 times longitudinally and 2 times
transversely, and was heat-sealed to obtain a pouch-like container.
There was obtained a pouch having an average container thickness of
0.16 mm, an average surface roughness Ra of 4.3 .mu.m, an average
long diameter of bubbles of 101 .mu.m in the foamed layer, an
average aspect ratio of bubbles of 8.4, and exhibiting smooth
appearance and favorable pearl-like luster.
Example 4
[0124] The foamed sheet prepared in the same manner as in Example 3
was stretched into 3 times longitudinally and 3 times transversely
by using the biaxial stretching machine, and was heat-sealed to
form a pouch-like container. There was obtained a pouch having an
average container thickness of 0.07 mm, an average surface
roughness Ra of 1.9 .mu.m, an average long diameter of bubbles of
107 .mu.m in the foamed layer, an average aspect ratio of bubbles
of 15.7, and exhibiting smooth appearance and excellent pearl-like
luster.
Example 5
[0125] The foamed sheet prepared in the same manner as in Example 3
was stretched into 4 times longitudinally and 4 times transversely
by using the biaxial stretching machine, and was heat-sealed to
form a pouch-like container. There was obtained a pouch having an
average container thickness of 0.05 mm, an average surface
roughness Ra of 1.4 .mu.m, an average long diameter of bubbles of
102 .mu.m in the foamed layer, an average aspect ratio of bubbles
of 19.8, and exhibiting smooth appearance and excellent pearl-like
luster.
Example 6
[0126] A foamed sheet having a cell diameter larger than that of
Example 3 was obtained by forming a foamed sheet in the same manner
as that of Example 3 but lowering the pressure for feeding the
carbonic acid gas and setting the T-die temperature to be high. An
unfoamed PET sheet was laminated thereon to prepare a two-layer
sheet comprising the foamed layer and the unfoamed layer. The
two-layer sheet was stretched into 3 times longitudinally and 3
times transversely by using the biaxial stretching machine, and was
heat-sealed to form a pouch-like container. There was obtained a
pouch having an average container thickness of 0.12 mm, an average
surface roughness Ra of 0.8 .mu.m, an average long diameter of
bubbles of 240 .mu.m in the foamed layer, an average aspect ratio
of bubbles of 18.5, and exhibiting smooth appearance and favorable
pearl-like luster.
Example 7
[0127] The foamed sheet prepared in the same manner as in Example 3
was stretched into 4 times longitudinally and 1 time transversely
by the plug-assisted forming to form a cup. There was obtained a
cup-like container having an average container thickness of 0.26
mm, an average surface roughness Ra of 2.3 .mu.m, an average long
diameter of bubbles of 103 .mu.m in the foamed layer, an average
aspect ratio of bubbles of 8.2, and exhibiting favorable appearance
and pearl-like luster.
Comparative Example 1
[0128] A foamed preform produced in the same manner as in Example 1
was stretch-formed into a bottle being drawn into 1.5 times
longitudinally and 1.5 times transversely. There was obtained a
foamed PET bottle having an average container thickness of 1.2 mm
in the side body portion, an average surface roughness Ra of 0.5
.mu.m, an average long diameter of bubbles of 22 .mu.m in the
foamed layer, and an average aspect ratio of bubbles of 5.1. The
container exhibited a white color and excellent light shielding
property. However, the pearl-like luster was not favorable due to
the lack of reflected light.
Comparative Example 2
[0129] A foamed preform produced in the same manner as in Example 1
was stretch-formed by using a blow metal mold which has a matt
finish surface, into a bottle being drawn into 3 times
longitudinally and 3 times transversely. There was obtained a
foamed PET bottle having an average container thickness of 0.31 mm
in the side body portion, an average surface roughness Ra of 6.2
.mu.m, an average long diameter of bubbles of 45 .mu.m in the
foamed layer, and an average aspect ratio of bubbles of 12.0.
However, the luster was poor and the appearance was not favorable
due to the lack of reflected light in the surface.
Comparative Example 3
[0130] A foamed sheet prepared in the same manner as in Example 3
was formed into a tray-like container by the compressed air
forming. There was obtained a foamed tray having an average
container thickness of 0.58 mm, an average surface roughness of 3.3
.mu.m, an average long diameter of bubbles of 24 .mu.m in the
foamed layer, and an average aspect ratio of bubbles of 1.3.
However, both the appearance and the pearl-like luster were not
favorable.
Comparative Example 4
[0131] A foamed sheet prepared in the same manner as in Example 3
was stretched by using the biaxial stretching machine into 1.5
times longitudinally and 1.5 times transversely, and was
heat-sealed to obtain a pouch-like container. There was obtained a
pouch having an average container thickness of 0.34 mm, an average
surface roughness Ra of 4.0 .mu.m, an average long diameter of
bubbles of 72 .mu.m in the foamed layer, and an average aspect
ratio of bubbles of 4.3. However, the pearl-like luster was not
favorable.
Comparative Example 5
[0132] A foamed sheet was prepared in the same manner as in Example
6, and was stretched by using the biaxial stretching machine into 3
times longitudinally and 3 times transversely without laminating
the unfoamed PET sheet thereon, and was heat-sealed to obtain a
pouch-like container. There was obtained a pouch having an average
container thickness of 0.10 mm, an average surface roughness Ra of
6.8 .mu.m, an average long diameter of bubbles of 204 in m in the
foamed layer, and an average aspect ratio of bubbles of 17.6.
Without the skin layer, however, the surface was rough, and the
luster was poor and the appearance was defective as compared to
Example 6.
Comparative Example 6
[0133] A foamed sheet having a larger cell diameter was prepared by
decreasing the pressure of the carbonic acid gas to be lower than
that of Example 6. The T-die temperature was set to be low so that
the surface roughness of the sheet was small. The foamed sheet was
stretched by using the biaxial stretching machine into 3 times
longitudinally and 3 times transversely, and was heat-sealed to
obtain a pouch-like container. There was obtained a foamed pouch
having an average container thickness of 0.11 mm, an average
surface roughness Ra of 2.3 .mu.m, an average long diameter of
bubbles of 719 .mu.m in the foamed layer, and an average aspect
ratio of bubbles of 15.6. However, since the container possessed
large bubbles and a small cell density, light was little scattered
or reflected, and the pearl-like luster was poor. Besides, since
the flat bubbles were so large as can be seen by naked eyes, the
appearance was not good.
[0134] Table 1 shows the evaluated results of Examples 1 to 7 and
comparative Examples 1 to 6.
TABLE-US-00001 TABLE 1 Examples Ave. Ave. and Ave. long aspect
surface Comp. Stretching ratio Thickness T dia. L ratio roughness
Exs. Container (Longi. .times. Trans.) (mm) (.mu.m) L/t Ra (.mu.m)
Luster Ex. 1 bottle 2 .times. 2 0.68 29 8.7 0.5 Ex. 2 bottle 3
.times. 3 0.32 42 11.6 0.3 .circleincircle. Ex. 3 pouch 2 .times. 2
0.16 101 8.4 4.3 Ex. 4 pouch 3 .times. 3 0.07 107 15.7 1.9
.circleincircle. Ex. 5 pouch 4 .times. 4 0.05 102 19.8 1.4
.circleincircle. Ex. 6 pouch 3 .times. 3 0.12 240 18.5 0.8 Ex. 7
cup 4 .times. 1 0.26 103 8.2 2.3 Comp. bottle 1.5 .times. 1.5 1.20
22 5.1 0.5 .DELTA. Ex. 1 Comp. bottle 3 .times. 3 0.31 45 12.0 6.2
.DELTA. Ex. 2 Comp. tray undrawn 0.58 24 1.3 3.3 .DELTA. Ex. 3
Comp. pouch 1.5 .times. 1.5 0.34 72 4.3 4.0 .DELTA. Ex. 4 Comp.
pouch 3 .times. 3 0.10 204 17.6 6.8 .DELTA. Ex. 5 Comp. pouch 3
.times. 3 0.11 719 15.6 2.3 .times. Ex. 6 * Three or more cells had
been overlapped in the direction of thickness under all of the
conditions.
[0135] The following experiments deal with the containers of when
the unfoamed region was formed in the mouth portion of the
containers.
Example 8
[0136] A polyethylene terephthalate resin (PET) having an intrinsic
viscosity of 0.84 was injection-formed into an unfoamed preform of
the shape of a test tube having a body portion, a bottom portion
and a neck portion (inner diameter of neck portion:21.6 mm,
thickness of body portion: 3mm, content: 25.4 ml) for forming a
container.
[0137] The neck portion of the unfoamed preform was heated by using
an infrared-ray heating device of a maximum output of 2500 W for 60
seconds so as to be crystallized. Thereafter, the preform was set
in a pressure-resistant container maintained at 30.degree. C. so as
to imbibe the carbonic acid gas being held under a pressure of 15
MPa for 2 hours. Here, the degree of crystallization in cross
section 30 .mu.m deep from the surface of the neck portion was 39%,
measured by using a laser-Raman spectrophotometer NRS-1000
manufactured by JASCO Co.
[0138] The degree of crystallization was close to a degree of
crystllization of a neck portion of a commercially available
heat-resistant bottle. The unfoamed preform was taken out from the
pressure-resistant container and using oil bath, the unfoamed
preform was entirely immersed in hot water at 90.degree. C. for 10
seconds so as to be foamed. After foamed, the preform was cooled
down to room temperature, and the cross section of the threaded
portion was observed by using an X-ray CT scanning apparatus to
find that the neck portion had not been foamed at all but the body
portion had been foamed.
Example 9
[0139] The crystallization by heating and gas imbibition were
executed in the same manner as in Example 8 but effecting the
crystallization by heating for 52 seconds. The degree of
crystallization in cross section 30 .mu.m deep from the surface of
the neck portion was 25%.
[0140] The unfoamed preform was foamed in the same manner as in
Example 1. After foamed, the preform was cooled down to room
temperature, and the cross section of the threaded portion was
observed by using the X-ray CT scanning apparatus to find that the
neck portion had not been foamed at all but the body portion had
been foamed.
Example 10
[0141] The crystallization by heating and gas imbibition were
executed in the same manner as in Example 8 but effecting the
crystallization by heating for 50 seconds. The degree of
crystallization in cross section 30 .mu.m deep from the surface of
the neck portion was 18%.
[0142] The unfoamed preform was foamed in the same manner as in
Example 8. After foamed, the preform was cooled down to room
temperature, and the cross section of the threaded portion was
observed by using the X-ray CT scanning apparatus to find that the
neck portion had not been foamed at all but the body portion had
been foamed.
Example 11
[0143] The crystallization by heating and gas imbibition were
executed in the same manner as in Example 8 but effecting the
crystallization by heating for 47 seconds. The degree of
crystallization in cross section 30 .mu.m deep from the surface of
the neck portion was 13%.
[0144] The unfoamed preform was foamed in the same manner as in
Example 1. After foamed, the preform was cooled down to room
temperature, and the cross section of the threaded portion was
observed by using the X-ray CT scanning apparatus to find that the
neck portion had not been foamed at all but the body portion had
been foamed.
Reference Example 1
[0145] The gas imbibition was executed without effecting the
crystallization by heating. The degree of crystallization in cross
section 30 .mu.m deep from the surface of the neck portion was
9%.
[0146] The unfoamed preform was foamed in the same manner as in
Example 8. After foamed, the preform was cooled down to room
temperature, and the cross section of the threaded portion was
observed by using the X-ray CT scanning apparatus to find that both
the neck portion and the body portion had been foamed.
Reference Example 2
[0147] The crystallization by heating and gas imbibition were
executed in the same manner as in Example 8 but effecting the
crystallization by heating for 40 seconds. The degree of
crystallization in cross section 30 .mu.m deep from the surface of
the neck portion was 10%.
[0148] The unfoamed preform was foamed in the same manner as in
Example 8. After foamed, the preform was cooled down to room
temperature, and the cross section of the threaded portion was
observed by using the X-ray CT scanning apparatus to find that both
the neck portion and the body portion had been foamed.
Reference Example 3
[0149] The crystallization by heating and gas imbibition were
executed in the same manner as in Example 8 but effecting the
crystallization by heating for 45 seconds. The degree of
crystallization in cross section 30 .mu.m deep from the surface of
the neck portion was 12%.
[0150] The unfoamed preform was foamed in the same manner as in
Example 1. After foamed, the preform was cooled down to room
temperature, and the cross section of the threaded portion was
observed by using the X-ray CT scanning apparatus to find that both
the neck portion and the body portion had been foamed.
[0151] Table 2 shows the results and cross sectional photographs of
Examples 8 to 11 and Reference Examples 1 to 3.
Example 12
[0152] A polyethylene terephthalate resin (PET) having an intrinsic
viscosity of 0.84 was injection-formed into an unfoamed preform of
the shape of a test tube having a body portion, a bottom portion
and a neck portion (inner diameter of neck portion: 21.6 mm,
thickness of body portion: 3 mm, content: 25.4 ml) for forming a
container.
[0153] The unfoamed preform was set in a pressure-resistant
container maintained at 30.degree. C. so as to imbibe the carbonic
acid gas being held under a pressure of 15 MPa for 2 hours.
Thereafter, the unfoamed preform was taken out from the
pressure-resistant container and was held at its neck portion by a
metal mold provided with a cooling pipe. While cooling the neck
portion, the body portion and the bottom portion were immersed in
hot water at 90.degree. C. using oil bath for 10 seconds so as to
be foamed. After foamed, the preform was cooled down to room
temperature and was cut in the axial direction. The neck portion
through up to the body portion were observed in cross section to
find that the neck portion had not been foamed at all but the body
portion had been foamed.
[0154] For the purpose of comparison, further, the preform taken
out from the pressure-resistant container was held by a metal mold
without provided with the cooling pipe, and the body portion and
the bottom portion thereof were immersed in the hot water using the
oil bath so as to be foamed but without cooling the neck portion.
After cooled down to room temperature, the preform was cut in the
axial direction. The neck portion through up to the body portion
were observed in cross section to find that the body portion had
been foamed and, at the same time, the neck portion had been foamed
to a slight degree.
* * * * *