U.S. patent application number 10/062719 was filed with the patent office on 2002-08-01 for resin composition and laminated film.
Invention is credited to Imai, Tomoyuki, Matsui, Toshiki, Shimuzu, Toshiaki, Tanaka, Suminori.
Application Number | 20020103284 10/062719 |
Document ID | / |
Family ID | 26548783 |
Filed Date | 2002-08-01 |
United States Patent
Application |
20020103284 |
Kind Code |
A1 |
Tanaka, Suminori ; et
al. |
August 1, 2002 |
Resin composition and laminated film
Abstract
A resin composition comprising (a) 100 parts by weight of a
thermoplastic resin containing nitrogen atom(s) in structural units
thereof; and (b) 0.1 to 20 parts by weight of an iron compound
catalyst comprising at least one iron oxide-based compound selected
from the group consisting of iron oxide hydroxide particles or iron
oxide particles, which has an average particle size of 0.05 to 2.0
.mu.m; and has a specific oxidation activity. Such a resin
composition is inhibited from generating hydrocyanic acid upon the
combustion, though the composition contains nitrogen atom(s) in
structural units thereof.
Inventors: |
Tanaka, Suminori;
(Kagawa-ken, JP) ; Shimuzu, Toshiaki;
(Marugame-shi, JP) ; Matsui, Toshiki;
(Hiroshima-shi, JP) ; Imai, Tomoyuki;
(Hiroshima-shi, JP) |
Correspondence
Address: |
NIXON & VANDERHYE P.C.
8th Floor
1100 North Glebe Road
Arlington
VA
22201-4714
US
|
Family ID: |
26548783 |
Appl. No.: |
10/062719 |
Filed: |
February 5, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10062719 |
Feb 5, 2002 |
|
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09666560 |
Sep 21, 2000 |
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Current U.S.
Class: |
524/431 ;
428/215; 428/220; 428/329; 428/424.4; 428/424.8; 428/475.8;
428/476.3; 428/476.9 |
Current CPC
Class: |
B32B 2333/08 20130101;
B32B 27/32 20130101; Y10T 428/24967 20150115; B32B 2323/10
20130101; B32B 2377/00 20130101; Y10T 428/31757 20150401; B32B
27/08 20130101; B32B 27/26 20130101; Y10T 428/257 20150115; B32B
27/34 20130101; C08K 3/22 20130101; B32B 2331/04 20130101; B32B
27/40 20130101; B32B 2323/04 20130101; Y10T 428/31576 20150401;
Y10T 428/31765 20150401; Y10T 428/3175 20150401; Y10T 428/31743
20150401; B32B 27/306 20130101; Y10T 428/31855 20150401; B32B 27/28
20130101; Y10T 428/31573 20150401; Y10T 428/31587 20150401; B32B
2375/00 20130101 |
Class at
Publication: |
524/431 ;
428/220; 428/215; 428/329; 428/424.4; 428/424.8; 428/475.8;
428/476.9; 428/476.3 |
International
Class: |
C08K 003/18 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 22, 1999 |
JP |
11-269469 |
Sep 22, 1999 |
JP |
11-269470 |
Claims
What is claimed is:
1. A resin composition comprising: 100 parts by weight of a
thermoplastic synthetic resin containing nitrogen atom(s) in
structural units thereof; and 0.1 to 20 parts by weight of an iron
compound catalyst comprising at least one iron oxide-based compound
selected from the group consisting of iron oxide hydroxide
particles or iron oxide particles, which has an average particle
size of 0.05 to 2.0 .mu.m; and has a catalytic activity capable of
converting not less than 15% by mole of carbon monoxide into carbon
dioxide when measured under such test conditions that while passing
an argon gas as a carrier gas, carbon monoxide supplied in a pulse
amount of 6.1.times.10.sup.-7 mole, is contacted with
2.8.times.10.sup.-4 mole of iron oxide-based particles obtained by
heat-treating said iron compound catalyst at 800.degree. C. for 15
minutes in air (pretreatment), at 250.degree. C. at a space
velocity of 42,400 h.sup.-1 using a pulse catalytic reactor.
2. A resin composition according to claim 1, wherein said iron
compound catalyst comprises spindle-shaped iron oxide hydroxide
particles having a major axial diameter of 0.05 to 1.5 .mu.m, an
aspect ratio of 2:1 to 18:1 and a BET specific surface area of 30
to 250 m.sup.2/g.
3. A resin composition according to claim 1, wherein said iron
compound catalyst comprises acicular iron oxide hydroxide particles
having a major axial diameter of 0.05 to 2.0 .mu.m, an aspect ratio
of 2:1 to 20:1 and a BET specific surface area of 10 to 100
m.sup.2/g.
4. A resin composition according to claim 1, wherein said iron
compound catalyst comprises spindle-shaped iron oxide particles or
acicular iron oxide particles having a major axial diameter of 0.05
to 1.0 .mu.m, an aspect ratio of 2:1 to 12:1 and a BET specific
surface area of 30 to 200 m.sup.2/g.
5. A resin composition according to claim 1, wherein said iron
compound catalyst comprises at least one material selected from the
group consisting of goethite particles, akaganeite particles,
lepidocrocite particles, hematite particles, maghemite particles
and magnetite particles.
6. A resin composition according to claim 1, wherein said iron
compound catalyst has a phosphorus content of 0.0001 to 0.02% by
weight, a sulfur content of 0.001 to 0.3% by weight and a sodium
content of 0.001 to 0.3% by weight.
7. A resin composition according to claim 1, wherein said
thermoplastic synthetic resin containing nitrogen atom(s) in
structural units thereof is polyamide resin, aromatic polyamide
resin, polyacrylonitrile resin or polyurethane resin.
8. A laminated film comprising: a synthetic resin layer comprising
a synthetic resin containing nitrogen atom(s) in structural units
thereof; and a layer comprising a polyolefin-based resin, at least
one of the synthetic resin layer comprising a synthetic resin
containing nitrogen atom(s) in structural units thereof and
polyolefin-based resin layer containing an iron compound catalyst
comprising at least one iron oxide-based compound selected from the
group consisting of iron oxide hydroxide particles or iron oxide
particles, which has an average particle size of 0.05 to 2.0 .mu.m;
and has a catalytic activity capable of converting not less than
15% by mole of carbon monoxide into carbon dioxide when measured
under the test conditions as set forth in claim 1.
9. A laminated film according to claim 8 comprising: the synthetic
resin layer comprising a synthetic resin containing nitrogen
atom(s) in structural units thereof; and a layer of a resin
composition comprising 100 parts by weight of the polyolefin-based
resin and 0.2 to 20 parts by weight of the iron compound
catalyst.
10. A laminated film according to claim 8 comprising: a synthetic
resin layer comprising a resin composition comprising 100 parts by
weight of the synthetic resin containing nitrogen atom(s) in
structural units thereof and 0.2 to 20 parts by weight of the iron
compound catalyst; and the layer comprising the polyolefin-based
resin.
11. A laminated film according to claim 8 comprising: a synthetic
resin layer comprising a resin composition comprising 100 parts by
weight of the synthetic resin containing nitrogen atom(s) in
structural units thereof and 0.2 to 20 parts by weight of the iron
compound; and a layer of a resin composition comprising 100 parts
by weight of the polyolefin-based resin and 0.2 to 20 parts by
weight of the iron compound catalyst, wherein the total amount of
the iron compound catalyst is 0.4 to 20.2 parts by weight based on
100 parts by weight of the synthetic resin containing nitrogen
atom(s) in structural units thereof and polyolefin-based resin.
12. A laminated film according to claim 8, wherein said iron
compound catalyst comprises spindle-shaped iron oxide hydroxide
particles having a major axial diameter of 0.05 to 1.5 .mu.m, an
aspect ratio of 2:1 to 18:1 and a BET specific surface area of 30
to 250 m.sup.2/g.
13. A laminated film according to claim 8, wherein said iron
compound catalyst comprises acicular iron oxide hydroxide particles
having a major axial diameter of 0.05 to 2.0 .mu.m, an aspect ratio
of 2:1 to 20:1 and a BET specific surface area of 10 to 100
m.sup.2/g.
14. A laminated film according to claim 8, wherein said iron
compound catalyst comprises spindle-shaped iron oxide particles or
acicular iron oxide particles having a major axial diameter of 0.05
to 1.0 .mu.m, an aspect ratio of 2:1 to 12:1 and a BET specific
surface area of 30 to 200 m.sup.2/g.
15. A laminated film according to claim 8, wherein said iron
compound catalyst comprises at least one material selected from the
group consisting of goethite particles, akaganeite particles,
lepidocrocite particles, hematite particles, maghemite particles
and magnetite particles.
16. A laminated film according to claim 8, wherein said iron
compound catalyst has a phosphorus content of 0.0001 to 0.02% by
weight, a sulfur content of 0.001 to 0.3% by weight and a sodium
content of 0.001 to 0.3% by weight.
17. A laminated film according to claim 8, wherein said
thermoplastic synthetic resin containing nitrogen atom(s) in
structural units thereof is polyamide resin, aromatic polyamide
resin, polyacrylonitrile resin or polyurethane resin.
18. A laminated film according to claim 8, wherein said
polyolefin-based resin is polyethylene, polypropylene,
ethylene-propylene copolymer, polybutene-1,
poly(4-methylpentene-1), ethylene-vinyl acetate copolymer,
ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate
copolymer, ethylene-acrylic acid copolymer or ionic cross-linked
olefin copolymer.
19. A laminated film according to claim 8, wherein the thickness of
said laminated film is 5 to 1000 .mu.m, the thickness of said
synthetic resin layer comprising the synthetic resin containing
nitrogen atom(s) in structural units thereof is 1 to 500 .mu.m, and
the thickness of said polyolefin-based resin layer is 4 to 500
.mu.m.
20. A method of using an iron compound catalyst for inhibiting
percentage of the generation of hydrocyanic acid, which iron
compound catalyst comprising at least one iron oxide-based compound
selected from the group consisting of iron oxide hydroxide
particles or iron oxide particles, which has an average particle
size of 0.05 to 2.0 .mu.m; and has a catalytic activity capable of
converting not less than 15% by mole of carbon monoxide into carbon
dioxide when measured under such test conditions that while passing
an argon gas as a carrier gas, carbon monoxide supplied in a pulse
amount of 6.1.times.10.sup.-7 mole, is contacted with
2.8.times.10.sup.-4 mole of iron oxide-based particles obtained by
heat-treating said iron compound catalyst at 800.degree. C. for 15
minutes in air (pretreatment), at 250.degree. C. at a space
velocity of 42,400 h.sup.-1 using a pulse catalytic reactor.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a resin composition and a
laminated film, and more particularly, to a resin composition and a
laminated film (or sheet) comprising the resin composition, which
is inhibited from generating hydrocyanic acid upon the
combustion.
[0002] With the recent rise in levels of living and income, many
new goods have been marketed, so that rich material civilization
has been realized. On the other hand, the amount of domestic wastes
discharged has been rapidly increased. As a result, waste disposal
treatments have caused significant social problems.
[0003] A considerable part of these wastes is occupied by those
derived from synthetic resins. In particular, it has been reported
that vinyl chloride resin wastes have a risk of generating dioxins
upon incineration thereof. In addition, it has been recognized that
synthetic resins containing nitrogen atom(s) in structural units
thereof such as polyamide resins or polyurethane resins generate
hydrocyanic acid as combustion product gas upon the combustion or
incineration as described in Morimoto, "Composition of High-Polymer
Combustion Product Gas", HIGH POLYMER, Vol. 22, No. 253, p. 192
(1973). Further, it is also known that laminated films (or sheets)
having a constituent layer composed of polyamide resin, which have
been extensively used as wrapping materials, also generate
hydrocyanic acid upon the combustion or incineration.
[0004] Such synthetic resins containing nitrogen atom(s) in
structural units thereof have been widely used in ordinary domestic
applications such as interior materials, e.g., carpets, curtains,
wall papers or decorative papers for decorative sheets. However,
hydrocyanic acid generated from these resins upon firing tend to
sometimes endanger human life.
[0005] As a result of the present inventors' earnest studies for
solving the above problems, it has been found that by incorporating
an iron compound catalyst comprising iron oxide hydroxide particles
or iron oxide particles, which has an average particle size of 0.01
to 2.0 .mu.m, into a synthetic resin, the obtained resin
composition can be inhibited from generating hydrocyanic acid upon
the combustion or incineration even though the synthetic resins
contain nitrogen atom(s) in structural units thereof. The present
invention has been attained on the basis of this finding.
SUMMARY OF THE INVENTION
[0006] It is an object of the present invention to provide a resin
composition which is free from the generation of hydrocyanic acid
upon the combustion or incineration notwithstanding synthetic
resins containing nitrogen atom(s) in structural units thereof are
used.
[0007] It is another object of the present invention to provide a
laminated film (or sheet) which is free from the generation of
hydrocyanic acid upon the combustion or incineration
notwithstanding synthetic resins containing nitrogen atom(s) in
structural units thereof are used, and exhibits a sufficient
transparency and a good coloring property required for interior
materials or wrapping materials.
[0008] In a first aspect of the present invention, there is
provided a resin composition comprising:
[0009] 100 parts by weight of a thermoplastic synthetic resin
containing nitrogen atom(s) in structural units thereof; and
[0010] 0.1 to 20 parts by weight of an iron compound catalyst
comprising at least one iron oxide-based compound selected from the
group consisting of iron oxide hydroxide particles or iron oxide
particles, which has an average particle size of 0.05 to 2.0 .mu.m;
and has a catalytic activity capable of converting not less than
15% by mole of carbon monoxide into carbon dioxide when measured
under such test conditions that while passing an argon gas as a
carrier gas, carbon monoxide supplied in a pulse amount of
6.1.times.10.sup.-7 mole, is contacted with 2.8.times.10.sup.-4
mole of iron oxide-based particles obtained by heat-treating said
iron compound catalyst at 800.degree. C. for 15 minutes in air
(pretreatment), at 250.degree. C. at a space velocity of 42,400
h.sup.-1 using a pulse catalytic reactor.
[0011] In a second aspect of the present invention, there is
provided a laminated film comprising:
[0012] a synthetic resin layer comprising a synthetic resin
containing nitrogen atom(s) in structural units thereof; and
[0013] a layer comprising a polyolefin-based resin,
[0014] at least one of the synthetic resin layer comprising a
synthetic resin containing nitrogen atom(s) in structural units
thereof and polyolefin-based resin layer, which contain an iron
compound catalyst comprising at least one iron oxide-based compound
selected from the group consisting of iron oxide hydroxide
particles or iron oxide particles, which has an average particle
size of 0.05 to 2.0 .mu.m; and has a catalytic activity capable of
converting not less than 15% by mole of carbon monoxide into carbon
dioxide when measured under the test conditions as set forth
above.
[0015] In a third aspect of the present invention, there is
provided a laminated film comprising:
[0016] a synthetic resin layer comprising a synthetic resin
containing nitrogen atom(s) in structural units thereof; and
[0017] a layer of a resin composition comprising 100 parts by
weight of a polyolefin-based resin and 0.2 to 20 parts by weight of
an iron compound catalyst,
[0018] which iron compound catalyst comprises at least one iron
oxide-based compound selected from the group consisting of iron
oxide hydroxide particles or iron oxide particles, which has an
average particle size of 0.05 to 2.0 .mu.m; and has a catalytic
activity capable of converting not less than 15% by mole of carbon
monoxide into carbon dioxide when measured under the test
conditions as set forth above.
[0019] In a fourth aspect of the present invention, there is
provided a laminated film comprising:
[0020] a synthetic resin layer comprising a resin composition
comprising 100 parts by weight of a synthetic resin containing
nitrogen atom(s) in structural units thereof and 0.2 to 20 parts by
weight of an iron compound; and
[0021] a layer comprising a polyolefin-based resin
[0022] which iron compound catalyst comprises at least one iron
oxide-based compound selected from the group consisting of iron
oxide hydroxide particles or iron oxide particles, which has an
average particle size of 0.05 to 2.0 .mu.m; and has a catalytic
activity capable of converting not less than 15% by mole of carbon
monoxide into carbon dioxide when measured under the test
conditions as set forth above.
[0023] In a fifth aspect of the present invention, there is
provided a laminated film comprising:
[0024] a synthetic resin layer comprising a resin composition
comprising 100 parts by weight of a synthetic resin containing
nitrogen atom(s) in structural units thereof and 0.2 to 20 parts by
weight of an iron compound; and
[0025] a layer of a resin composition comprising 100 parts by
weight of a polyolefin-based resin and 0.2 to 20 parts by weight of
an iron compound catalyst.
[0026] which iron compound catalyst comprises at least one iron
oxide-based compound selected from the group consisting of iron
oxide hydroxide particles or iron oxide particles, which has an
average particle size of 0.05 to 2.0 .mu.m; and has a catalytic
activity capable of converting not less than 15% by mole of carbon
monoxide into carbon dioxide when measured under the test
conditions as set forth above,
[0027] the total amount of the iron compound catalyst being 0.4 to
20.2 parts by weight based on 100 parts by weight of the synthetic
resin containing nitrogen atom(s) in structural units thereof and
polyolefin-based resin.
[0028] In a sixth aspect of the present invention, there is
provided a method of using an iron compound catalyst for inhibiting
percentage of the generation of hydrocyanic acid, which iron
compound catalyst comprising at least one iron oxide-based compound
selected from the group consisting of iron oxide hydroxide
particles or iron oxide particles, which has an average particle
size of 0.05 to 2.0 .mu.m; and has a catalytic activity capable of
converting not less than 15% by mole of carbon monoxide into carbon
dioxide when measured under such test conditions that while passing
an argon gas as a carrier gas, carbon monoxide supplied in a pulse
amount of 6.1.times.10.sup.-7 mole, is contacted with
2.8.times.10.sup.-4 mole of iron oxide-based particles obtained by
heat-treating said iron compound catalyst at 800.degree. C. for 15
minutes in air (pretreatment), at 250.degree. C. at a space
velocity of 42,400 h.sup.-1 using a pulse catalytic reactor.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The resin composition of the present invention is inhibited
from generating hydrocyanic acid upon the combustion or
incineration notwithstanding the composition comprises a
thermoplastic resin containing nitrogen atom(s) in structural units
thereof. As the thermoplastic resins containing nitrogen atom(s) in
structural units thereof, there may be exemplified polyamides,
aromatic polyamides, polyacrylonitrile, polyurethane resins or the
like. Meanwhile, the effects of the present invention can be
remarkably exhibited when applied to resin compositions comprising
such a thermoplastic resin containing nitrogen atom(s) in
structural units thereof. However, in the resin composition of the
present invention, there may also be contained thermoplastic resins
other than those containing nitrogen atom(s) in structural units
thereof.
[0030] In addition, a laminated film (or sheet) of the present
invention comprises:
[0031] a synthetic resin layer comprising a synthetic resin
containing nitrogen atom(s) in structural units thereof; and
[0032] a layer comprising a polyolefin-based resin,
[0033] at least one of the synthetic resin layer comprising a
synthetic resin containing nitrogen atom(s) in structural units
thereof and polyolefin-based resin layer containing an iron
compound catalyst blended therein.
[0034] That is, a laminated film (or sheet) of the present
invention comprises:
[0035] (1) a synthetic resin layer comprising a synthetic resin
containing nitrogen atom(s) in structural units thereof, and
[0036] a layer of a resin composition comprising 100 parts by
weight of a polyolefin-based resin and usually 0.2 to 20 parts by
weight of an iron compound catalyst;
[0037] (2) a synthetic resin layer comprising a resin composition
comprising 100 parts by weight of a synthetic resin containing
nitrogen atom(s) in structural units thereof and usually 0.2 to 20
parts by weight of an iron compound, and
[0038] a layer comprising a polyolefin-based resin; or
[0039] (3) a synthetic resin layer comprising a resin composition
comprising 100 parts by weight of a synthetic resin containing
nitrogen atom(s) in structural units thereof and usually 0.2 to 20
parts by weight of an iron compound, and
[0040] a layer of a resin composition comprising 100 parts by
weight of a polyolefin-based resin and usually 0.2 to 20 parts by
weight of an iron compound catalyst,
[0041] wherein the total amount of the iron compound catalyst is
usually 0.4 to 20.2 parts by weight, preferably 0.4 to 10 parts by
weight, more preferably 0.5 to 7 parts by weight based on 100 parts
by weight of the sum of the synthetic resin containing nitrogen
atom(s) in structural units thereof and polyolefin-based resin.
[0042] Further, in the laminated film of the present invention, the
iron compound catalyst having the effect of inhibiting the
generation of hydrocyanic acid as explained hereinafter is
incorporated in the synthetic resin layer containing nitrogen
atom(s) in structural units thereof, or in the layer composed
mainly of polyolefin-based resins capable of being processed at a
relatively low temperature.
[0043] In case of the laminated film (or sheet) of the present
invention, it is preferred that the iron compound catalyst having
the effect of inhibiting the generation of hydrocyanic acid is
incorporated in the polyolefin-based resin which can be processed
at a relatively low temperature, rather than the synthetic resin
containing nitrogen atom(s) in structural units thereof. As
compared with the case of using the resin composition comprising a
synthetic resin containing nitrogen atom(s) in structural units
thereof, and the iron oxide hydroxide particles or iron oxide
particles such as magnetite particles, which is required to be
processed at a relatively high temperature, such laminated film
having the polyolefin-based resin layer containing the iron
compound catalyst, can be prevented from being deteriorated in
transparency as a whole due to the discoloration of the iron
compound catalyst.
[0044] The laminated film of the present invention, which is
multilayered film having at least two layers, has a total thickness
of usually 5 to 1000 .mu.m, preferably 10 to 400 .mu.m. With
respect to the respective layers of the laminated film, the
synthetic resin layer containing nitrogen atom(s) in structural
units thereof has a thickness of usually 1 to 500 .mu.m, preferably
5 to 200 .mu.m, and the polyolefin-based resin layer has a
thickness of usually 4 to 500 .mu.m, preferably 5 to 200 .mu.m.
[0045] As the synthetic resins containing nitrogen atom(s) in
structural units thereof which are usable in the laminated film of
the present invention, there may be exemplified polyamide resins
such as nylon 6, nylon 66, nylon 6/nylon 66 copolymer, nylon
6/nylon 12 copolymer and nylon 6/nylon 66/nylon 12 copolymer;
polyacrylonitrile; (thermoplastic) polyurethane resins; or the
like.
[0046] As the polyolefin-based resins used in the laminated film of
the present invention, there may be exemplified various
polyethylenes such as low-density, medium-density or high-density
polyethylenes, polypropylene, ethylene-propylene copolymer,
polybutene-1, poly(4-methylpentene-1), ethylene-vinyl acetate
copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl
acrylate copolymer, ethylene-acrylic acid copolymer, ionic
cross-linked olefin copolymer (ionomer) or the like. Among these
polyolefin-based resins, the use of those capable of being
processed at a relatively low temperature, such as low-density
polyethylene, ethylene-vinyl acetate copolymer, is preferred from
the standpoint of preventing the discoloration of the iron compound
catalyst upon processing.
[0047] The iron compound catalyst of the present invention
comprises at least one iron oxide-based compound selected from the
group consisting of iron oxide particles and iron oxide hydroxide
particles having an average particle size (which means a major
axial diameter for spindle-shaped or acicular particles; and the
average of particle sizes for granular particles) of usually 0.05
to 2.0 .mu.m. Further, the iron compound catalyst of the present
invention has such a catalytic activity capable of converting not
less than 15% by mole of carbon monoxide into carbon dioxide when
measured under the following test conditions.
[0048] That is, the catalytic activity (oxidation activity) of the
iron compound catalyst is determined as follows. The iron compound
catalyst is heat-treated at 800.degree. C. for 15 minutes and then
arranged and classified into a particle size of 150 to 200 .mu.m.
2.8.times.10.sup.-4 mole of the thus obtained particles are charged
into a quartz column (diameter: 3 mm.phi.) of a pulse catalytic
reactor used in ordinary catalytic activity tests. While passing an
argon gas as a carrier gas through the reactor, 6.1.times.10.sup.-7
mole of carbon monoxide is introduced from a sample feed port of
the reactor and contacted with the iron compound catalyst at a
column temperature of 250.degree. C. at a space velocity (SV) of
42,400 h.sup.-1. The amount of carbon dioxide produced by the
oxidation of carbon monoxide and discharged from the column is
measured by gas chromatography. The catalytic activity of the iron
compound catalyst is evaluated by the conversion percentage of
carbon monoxide into carbon dioxide according to the following
formula. Incidentally, the space velocity (SV) represents the value
obtained by dividing a flow rate of the reaction gas by a volume of
the catalyst, and is expressed by a unit of an inverse number of
time (h.sup.-1).
Conversion (%)=[Carbon dioxide produced (mol)]/[Carbon monoxide
initially charged (mol)].times.100
[0049] The reason why the iron compound catalyst is preliminarily
heat-treated at 800.degree. C. for 15 minutes before the catalytic
activity test, is as follows. That is, wastes are usually
incinerated at a temperature of not less than 800.degree. C., so
that the iron oxide particles such as magnetite particles and the
iron oxide hydroxide particles are expected to undergo phase change
at such a high temperature. Therefore, the above heat-treatment is
conducted to reproduce the combustion conditions in an actually
used incinerator. In addition, the reason why the measuring
temperature is set to 250.degree. C., is as follows. That is, when
the measuring temperature is as high as more than 300.degree. C.,
the conversion of carbon monoxide by the iron compound catalyst is
increased, so that it becomes difficult to recognize the difference
in catalytic activity between the respective catalysts. Meanwhile,
it has been confirmed that carbon monoxide cannot be converted into
carbon dioxide at 250.degree. C. even in the presence of oxygen
unless any oxidation catalyst is used.
[0050] As a result of studies concerning interrelation between the
carbon monoxide conversion percentage measured by the above method
and the generation of hydrocyanic acid when actually combustion or
incineration the composition or laminated film of the present
invention, it has been found that the amount of hydrocyanic acid
generated can be reduced by using the iron compound catalyst
showing a carbon monoxide conversion percentage of not less than
15% by mole in a predetermined amount. More specifically, the iron
compound catalyst used in the present invention is required to have
a catalytic activity capable of converting usually not less than
15% by mole, preferably not less than 18% by mole, more preferably
not less than 20% by mole of carbon monoxide into carbon dioxide.
Even though a large amount of the iron compound catalyst showing a
carbon monoxide conversion percentage of less than 15% by mole, is
used, a sufficient combustion-promoting effect may not be obtained,
thereby failing to accomplish the objects of the present
invention.
[0051] Specific examples of the iron oxide particles or iron oxide
hydroxide particles usable in the present invention may include the
following compounds. As the iron oxide hydroxide particles, there
may be used any of goethite (.alpha.-FeOOH) particles,
lepidocrocite (.gamma.-FeOOH) particles or .delta.-FeOOH particles.
The iron oxide hydroxide particles may have any particle shape such
as a spindle shape, an acicular shape, or the like. Among them, the
use of spindle-shaped iron oxide hydroxide particles is preferred
in view of combustion efficiency.
[0052] The spindle-shaped iron oxide hydroxide particles have an
appearance of bundles of many superfine fibers when observed by
electron microscope. The spindle-shaped iron oxide hydroxide
particles have a major axial diameter of usually 0.05 to 1.5 .mu.m,
preferably 0.1 to 1.0 .mu.m; an aspect ratio (major axial
diameter/minor axial diameter; hereinafter referred to merely as
"aspect ratio") of usually 2:1 to 12:1, preferably 3:1 to 10:1; and
a BET specific surface area of usually 30 to 250 m.sup.2/g,
preferably 50 to 150 m.sup.2/g.
[0053] The acicular iron oxide hydroxide particles may have an
acicular shape in appearance, and may further include those
acicular particles having dendritic projections on the surface
thereof. The acicular iron oxide hydroxide particles have a major
axial diameter (corresponding to the average particle size) of
usually 0.05 to 2.0 .mu.m, preferably 0.1 to 0.8 .mu.m; an aspect
ratio of usually 2:1 to 20:1, preferably 5:1 to 15:1; and a BET
specific surface area of usually 10 to 200 m.sup.2/g, preferably 15
to 100 m.sup.2/g.
[0054] These iron oxide hydroxide particles having various shapes
may be produced from an aqueous solution prepared by passing an
oxygen-containing gas such as air through a suspension containing a
precipitate obtained by the neutralization reaction between an
aqueous ferrous salt solution and an aqueous alkali solution such
as an aqueous alkali hydroxide solution or an aqueous alkali
carbonate solution in the presence or absence of additives.
[0055] As the iron oxide particles, there may be used any of
hematite (.alpha.-Fe.sub.2O.sub.3) particles, magnetite
(FeO.sub.x.Fe.sub.2O.sub.3- , 0<x.ltoreq.1) particles and
maghemite (.gamma.-Fe.sub.2O.sub.3) particles. The iron oxide
particles may have a spindle shape, an acicular shape, or a
substantially isotropic shape, i.e., a so-called granular shape
such as a spherical shape, an octahedral shape, a polyhedral shape
or an ununiform shape. Among these particles, the use of
spindle-shaped iron oxide particles is preferred in view of
combustion efficiency.
[0056] In general, the spindle-shaped iron oxide particles or
acicular iron oxide particles may have a major axial diameter of
usually 0.05 to 1.0 .mu.m, preferably 0.05 to 0.3 .mu.m; an aspect
ratio of usually 2:1 to 12:1, preferably 3:1 to 10:1; and a BET
specific surface area of usually 5 to 200 m.sup.2/g, preferably 20
to 100 m.sup.2/g.
[0057] The ordinary granular iron oxide particles may have an
average particle size of usually 0.03 to 1.0 .mu.m, preferably 0.05
to 0.5 .mu.m; and a BET specific surface area of usually 2 to 30
m.sup.2/g, preferably 4 to 25 m.sup.2/g.
[0058] The spindle-shaped or acicular iron oxide particles may be
produced by heat-treating the above spindle-shaped or acicular iron
oxide hydroxide particles obtained from the above aqueous solution,
at a temperature of usually 250 to 700.degree. C. in air while
maintaining the particle shape, to form spindle-shaped or acicular
hematite particles; heat-reducing the obtained spindle-shaped or
acicular hematite particles at a temperature of usually 300 to
500.degree. C. in a reducing atmosphere such as under hydrogen gas
flow while maintaining the particle shape, to form spindle-shaped
or acicular magnetite particles; and then heat-oxidizing the thus
obtained spindle-shaped or acicular magnetite particles at a
temperature of usually 200 to 500.degree. C. in air while
maintaining the particle shape, thereby forming spindle-shaped or
acicular maghemite particles.
[0059] The granular iron oxide particles may be produced by passing
an oxygen-containing gas such as air through a suspension
containing a precipitate obtained by the neutralization reaction
between an aqueous ferrous salt solution and an aqueous alkali
solution such as an aqueous alkali hydroxide solution or an aqueous
alkali carbonate solution to form granular magnetite particles;
heat-treating the obtained granular magnetite particles at a
temperature of 200 to 500.degree. C. in air while maintaining the
particle shape to form granular maghemite particles; and then
heat-treating the thus obtained maghemite particles or the
previously obtained granular magnetite particles at a temperature
of 500 to 900.degree. C. while maintaining the particle shape,
thereby forming granular hematite particles.
[0060] The iron compound catalyst used in the present invention has
a phosphorus content of usually 0.0001 to 0.02% by weight,
preferably 0.0001 to 0.01% by weight, more preferably 0.0001 to
0.005% by weight. When the phosphorus content is more than 0.02% by
weight, the catalyst poison ability of the phosphorus may become
large, so that the oxidation activity for converting carbon
monoxide into carbon dioxide may be deteriorated, thereby failing
to obtain the aimed effect of inhibiting the generation of
hydrocyanic acid upon the combustion or incineration. Meanwhile,
although the phosphorus content is preferably as low as possible,
it is difficult to industrially produce such an iron compound
catalyst having a phosphorus content of less than 0.0001% by
weight.
[0061] The iron compound catalyst used in the present invention has
a sulfur content of usually 0.001 to 0.3% by weight, preferably
0.001 to 0.1% by weight, more preferably 0.001 to 0.07% by weight.
When the sulfur content is more than 0.3% by weight, the catalyst
poison ability of the sulfur may become large, so that the
oxidation activity for converting carbon monoxide into carbon
dioxide may be deteriorated, thereby failing to obtain the aimed
effect of inhibiting the generation of hydrocyanic acid upon the
combustion or incineration. Meanwhile, although the sulfur content
is preferably as low as possible, it is difficult to industrially
produce such an iron compound catalyst having a sulfur content of
less than 0.001% by weight.
[0062] The iron compound catalyst used in the present invention has
a sodium content of usually 0.001 to 0.3% by weight, preferably
0.001 to 0.2% by weight, more preferably 0.001 to 0.15% by weight.
When the sulfur content is more than 0.3% by weight, the catalyst
poison ability of the sodium may become large, so that the
oxidation activity for converting carbon monoxide into carbon
dioxide may be deteriorated, thereby failing to obtain the aimed
effect of inhibiting the generation of hydrocyanic acid upon the
combustion or incineration. Meanwhile, although the sodium content
is preferably as low as possible, it is difficult to industrially
produce such an iron compound catalyst having a sodium content of
less than 0.001% by weight.
[0063] In the production of the iron compound catalyst used in the
present invention, it is necessary to restrict the contents of
phosphorus, sulfur and sodium as catalyst poisons to not more than
predetermined amounts. More specifically, the contents of
phosphorus, sulfur and sodium should be reduced by avoiding the use
of sodium hexametaphosphate usually added as a sintering preventive
upon heat-calcination step, and by removing sulfur ions derived
from the raw ferrous materials or sodium ions derived from alkali
hydroxides or the alkali carbonates by means of purification
treatments such as washing with water or the like.
[0064] In the present invention, the iron compound catalyst
comprising at least one material appropriately selected from the
above iron oxide hydroxide particles or iron oxide particles, which
are capable of exhibiting an activity as the above oxidation
catalyst.
[0065] Also, the iron compound catalyst used in the present
invention may be surface-treated with various agents in order to
improve a dispersibility in synthetic resins.
[0066] The amount of the iron compound catalyst blended in the
resin composition of the present invention is usually 0.1 to 20
parts by weight, preferably 0.5 to 10 parts by weight, more
preferably 1.0 to 10 parts by weight based on 100 parts by weight
of the thermoplastic synthetic resin containing nitrogen atom(s) in
structural units thereof. When the content of the iron compound
catalyst is less than 0.1 part by weight, it may be difficult to
sufficiently accomplish the aimed objects of the present invention.
On the contrary, even when the content of the iron compound
catalyst is more than 20 parts by weight, the aimed effect cannot
be enhanced correspondingly, and there rather arises such a
tendency that the obtained resin composition or molded products
thereof may suffer from coloring.
[0067] The resin composition of the present invention may contain,
in addition to the above components, various additives, e.g.,
anti-blocking agents such as silica or calcium carbonate,
lubricants, ultra-violet light absorbers, light stabilizers,
anti-oxidants, colorants and plasticizers in ordinary amounts.
[0068] The lower limit of the amount of the iron compound catalyst
contained in the laminated film of the present invention is usually
0.2% by weight, preferably 0.4% by weight, more preferably 0.5% by
weight, still more preferably 1.0% by weight based on the weight of
the laminated film. The upper limit of the amount of the iron
compound catalyst contained in the laminated film of the present
invention is usually 20.2% by weight, preferably 20% by weight,
more preferably 10% by weight, still more preferably 7% by weight
based on the weight of the laminated film. When the content of the
iron compound catalyst is less than 0.2% by weight, it may be
difficult to sufficiently accomplish the aimed objects of the
present invention. On the contrary, even when the content of the
iron compound catalyst is more than 20.2% by weight, the aimed
effect may not be enhanced correspondingly, and there rather arises
such a tendency that the obtained laminated film suffers from
coloring.
[0069] Further, the laminated film of the present invention may
optionally has a synthetic resin layer having a gas-barrier
property which is composed of polyvinyl alcohol or a saponified
product of ethylene-vinyl alcohol copolymer; a metal foil layer; a
metal-deposited layer or the like. The total thickness of these
additional layers is preferably 0.005 to 100 .mu.m.
[0070] The respective layers of the laminated film according to the
present invention may contain, in addition to the above-described
components, various additives, e.g., anti-blocking agents such as
silica or calcium carbonate, lubricants, ultra-violet light
absorbers, light stabilizers, anti-oxidants, colorants and
plasticizers in ordinary amounts, according to requirements. The
amount of the additives added is preferably 0.01 to 30 parts by
weight based on 100 parts by weight of the synthetic resins to be
added.
[0071] The inhibiting percentage of the generation of hydrocyanic
acid of the resin composition of the present invention is usually
not less than 35%, preferably not less than 40%, more preferably
not less than 50%, still more preferably not less than 60%. In
addition, the inhibiting percentage of the generation of
hydrocyanic acid of the laminated film (or sheet) of the present
invention is usually not less than 10%, preferably not less than
12%, more preferably not less than 15%.
[0072] The iron compound catalyst used in the present invention can
exhibit a specific combustion-promoting effect, resulting in
inhibiting the generation of hydrocyanic acid upon the combustion
or incineration. The mechanism is suggested as follows though not
exactly known.
[0073] That is, iron atoms present on the surface of each iron
compound catalyst particle are initially kept stable by surface
hydroxyl groups capable of dissociating and adsorbing water. When
these hydroxyl groups undergo dehydration by the heating in the
combustion process, coordination-unsaturated iron ions and oxygen
ions are produced. Then, the thus produced coordination-unsaturated
active sites can activate oxygen due to the oxygen adsorption
thereto caused during the combustion process, and show a good
catalytic activity in a series of reaction steps such as
dehydrogenation reaction from organic substances or the like,
thereby exhibiting a good combustion-promoting effect. By this
effect, the synthetic resins containing nitrogen atom(s) in
structural units thereof can be decomposed while inhibiting the
generation of hydrocyanic acid upon the combustion or
incineration.
[0074] As described above, the resin composition of the present
invention can be inhibited from generating hydrocyanic acid upon
the combustion or incineration notwithstanding the composition
contains nitrogen atom(s) in structural units thereof. Further,
when the resin composition of the present invention are combusted
together with other wastes in an incinerator, there can also be
obtained such an effect of reducing the amount of dioxins
discharged from the incinerator due to the combustion-promoting
effect of the iron compound catalyst. Furthermore, the iron
compound catalyst can be reacted with heavy metals such as zinc,
copper or cadmium which are present in the incinerator, thereby
forming ferrite. The thus formed ferrite exhibits a good magnetic
property and, therefore, can be easily separated and recovered. The
thus recovered material can be recycled and reused in useful
applications. As a result, the heavy metals remaining in the
incinerator can be prevented from being discharged in the form of
water-soluble salts together with residual ashes into environments.
The resin composition of the present invention having the
above-described advantages can be processed into various molded
products, fibers, sheets or the like which are not only free from
environmental pollution, but also inhibited from generating
hydrocyanic acid upon fire, whereby the risk of endangering human
life can be avoided.
[0075] The laminated film of the present invention can be inhibited
from generating hydrocyanic acid upon the combustion or
incineration notwithstanding the resin of the film contains
nitrogen atom(s) in structural units thereof. In addition, the
laminated film of the present invention can exhibit a sufficient
transparency, in case of comprising the synthetic resin containing
nitrogen atom(s) in structural units thereof, and the layer of the
resin composition comprising the polyolefin-based resin and the
iron compound catalyst. Further, since the base material of the
laminated film has a sufficient transparency, the obtained
laminated film can be suitably colored with pigments or in
subsequent printing steps without damaging the aimed effects of the
present invention.
[0076] Also, when the laminated film of the present invention is
combusted together with other wastes in an incinerator, there can
be obtained such an effect of reducing the amount of dioxins
discharged from the incinerator due to the combustion-promoting
effect of the iron compound catalyst contained therein. Upon the
incineration, the iron compound catalyst can be reacted with heavy
metals such as zinc, copper or cadmium which are present in the
incinerator to form ferrite. The thus formed ferrite exhibits a
magnetic property and, therefore, can be readily separated and
recovered from the incinerator, thereby enabling the recovered
material to be recycled for useful applications. Thus, there can
also be obtained the effect of inhibiting the heavy metals
remaining in the incinerator from being discharged in the form of
water-soluble salts together with residual ashes into
environments.
[0077] Further, when the laminated film (or sheet) of the present
invention is used as interior materials such as wall papers and
decorative papers for decorative plywood, it is also expected to
obtain such an effect of avoiding a risk of endangering human life
even upon fire since the generation of hydrocyanic acid is
inhibited.
[0078] The laminated film (or sheet) having these advantages
according to the present invention can be used in various useful
applications such as wrapping materials, wall papers or decorative
papers for decorative plywood.
EXAMPLES
[0079] The present invention is described in more detail by
Examples and Comparative Examples, but the Examples are only
illustrative and, therefore, not intended to limit the scope of the
present invention.
[0080] Various properties were measured by the following
methods.
[0081] <Analysis for Hydrocyanic Acid Generated>
[0082] Twenty milligrams of a sample was charged into a quartz
tube-shaped furnace (22 mm.phi..times.300 mm) having a peripheral
portion whose temperature was controlled to 700.degree. C. Further,
air was fed into the quartz tube from one end thereof at a flow
rate of 100 ml/minute. The gas discharged from the other end of the
quartz tube was collected into a Tedler bag for 5 minutes. The thus
collected gas was measured using a detector (No. 12M, manufactured
by GASTEC Co., Ltd.) to determine a concentration of hydrocyanic
acid contained therein.
[0083] <Evaluation of Activity of Iron Compound Catalyst>
[0084] The iron compound catalyst was heat-treated at 800.degree.
C. for 15 minutes, and then granulated and classified into a
particle size of 150 to 200 .mu.m. 2.8.times.10.sup.-4 mole of the
thus obtained particles were filled into a quartz column (diameter:
3 mm.phi.) of a pulse catalytic reactor. While flowing an argon gas
as a carrier gas through the reactor, 6.1.times.10.sup.-7 mole of
carbon monoxide was introduced from a sample feed port of the
reactor and contacted with the iron compound catalyst within the
column at 250.degree. C. at a space velocity (SV) of 42,400
h.sup.-1. The amount of carbon dioxide produced by the oxidation of
carbon monoxide and discharged from the column was measured by gas
chromatography. The catalytic activity of the iron compound
catalyst was evaluated by the conversion percentage represented by
the above formula.
[0085] As the synthetic resins containing nitrogen atom(s) in
structural units thereof, there were used the following resins:
[0086] Synthetic resin 1: Polyamide (Nylon 6; "ARAMINE CM6041"
produced by Toray Co. Ltd.);
[0087] Synthetic resin 2: Polyacrylonitrile ("BALEX 1000" produced
by Mitsui Kagaku Co., Ltd.);
[0088] Synthetic resin 3: Thermoplastic polyurethane elastomer
("MIRACTORANE E885" produced by Nippon Miractorane Co., Ltd.);
[0089] Further, as the synthetic resin constituting the laminated
film containing nitrogen atom(s) in structural units thereof, there
was used Polyamide (Nylon 6, "ARAMINE CM6041" produced by Toray
Co., Ltd.).
[0090] As the polyolefin-based resin constituting the
polyolefin-based resin layer, there was used the following
material:
[0091] Polyolefin-based resin: low-density polyethylene ("SUMIKASEN
L705" produced by Sumitomo Kagaku Co., Ltd.).
[0092] As the iron compound catalyst, there was used the following
material:
[0093] Iron compound catalyst: spindle-shaped goethite (produced by
Toda Kogyo Co., Ltd., average particle size: 0.25 .mu.m; BET
specific surface area: 86 m.sup.2/g; aspect ratio: 8:1; conversion
percentage: 23%; phosphorus content: 0.0004% by weight; sulfur
content: 0.01% by weight; sodium content: 0.05% by weight).
Comparative Examples 1 to 3
[0094] The synthetic resins 1 to 3 was respectively supplied into
an extrusion-molding machine equipped with a T-die and
extrusion-molded into a film having a thickness of 100 .mu.m. The
thus obtained respective films were measured by the above-described
method to determine the amount of hydrocyanic acid generated
therefrom upon the combustion. The results are shown in Table
1.
Examples 1 to 6
[0095] Using a pressure-kneader, the synthetic resins 1 to 3 and
the iron compound catalyst were mixed together in amounts as shown
in Table 1, heat-melted and then granulated. The thus obtained
material was charged into an extrusion-molding machine equipped
with a T-die and molded into a film having a thickness of 100
.mu.m. Each of the thus obtained films was measured by the
above-described method to determine the amount of hydrocyanic acid
generated therefrom upon the combustion. The measurement results of
the films were respectively compared with corresponding ones
obtained in Comparative Examples 1 to 3 for each kind of synthetic
resin used, thereby calculating the efficiency (%) of suppressing
the generation of hydrocyanic acid. The results are shown in Table
1.
[0096] As is apparent from Table 1, upon the combustion of the
films produced from the resin composition of the present invention,
the amount of hydrocyanic acid contained in the combustion gas was
considerably reduced as compared to those of Comparative Examples
using no iron oxide particles.
Comparative Example 4
[0097] The same procedure as defined in Example 1 was conducted
except that granular hematite (produced by Toda Kogyo Co., Ltd.,
average particle size: 0.55 .mu.m; BET specific surface area: 2.1
m.sup.2/g; phosphorus content: 0.01% by weight; sulfur content:
0.04% by weight; sodium content: 0.18% by weight) having an
activity capable of converting 5.3% of carbon monoxide into carbon
dioxide, were kneaded with polyamide, and the kneaded material was
molded into a film. The obtained film was measured by the same
method as defined above to determine the percentage of hydrocyanic
acid generated. As a result, it was confirmed that the amount of
hydrocyanic acid generated upon the combustion was 1,200 ppm, and
the efficiency of suppressing the generation of hydrocyanic acid
when compared with Comparative Example 1, was only 8%.
Examples 7 to 10
[0098] Using a pressure-kneader, 80 parts by weight of a
polyolefin-based rein and 20 parts by weight of the iron compound
catalyst were melt-kneaded together and then granulated, thereby
obtaining an iron compound catalyst-containing master batch.
[0099] The thus obtained iron compound catalyst-containing master
batch and a polyolefin-based rein were mixed together, and then
charged into a hopper of an extruder. Then, using a
extrusion-coating machine, the obtained mixture was extruded over a
polyamide film anchor-coated with polyisocyanate-based resin,
thereby obtaining a laminated film comprising a polyamide layer and
polyolefin-based rein layer containing the iron compound
catalyst.
[0100] The thickness of the extruded polyolefin-based rein layer
formed on the polyamide film and the weight percentage of the iron
compound catalyst based on the total weight of the laminated film
are shown in Table 2. Meanwhile, it was confirmed that all of the
obtained laminated films had a sufficient transparency for
practical use.
Comparative Example 5
[0101] Low-density polyethylene was extruded over a polyamide film
anchor-coated with polyisocyanate-based resin, thereby obtaining a
laminated film. The percentage of hydrocyanic acid generated from
the thus obtained laminated film upon the combustion was measured
by the same method as defined above. The results are shown in Table
2.
[0102] As is apparent from Table 2, it was confirmed that when the
film was combusted, the amount of hydrocyanic acid contained in the
combustion gas was considerably reduced as compared to that of
Comparative Example 5 using no iron compound catalyst.
Comparative Example 6
[0103] Granular hematite (produced by Toda Kogyo Co., Ltd., average
particle size: 0.55 .mu.m; BET specific surface area: 2.1
m.sup.2/g; phosphorus content: 0.01% by weight; sulfur content:
0.04% by weight; sodium content: 0.18% by weight) having a
catalytic activity capable of converting 5.3% of carbon monoxide
into carbon dioxide, and low-density polyethylene were melt-kneaded
together and then granulated by the same method as defined above,
thereby obtaining a master batch. Then, using the thus obtained
master batch, there was produced a laminated film which was
identical in layer structure, layer thickness and amount of iron
compound catalyst blended to those of the film obtained in Example
9. The obtained laminated film was measured by the same method as
defined above to determine the percentage of hydrocyanic acid
generated upon the combustion. As a result, it was confirmed that
the amount of hydrocyanic acid generated upon the combustion was
300 ppm and, therefore, the efficiency of suppressing the
generation of hydrocyanic acid was insufficient.
Example 11
[0104] Using a pressure-kneader, 80 parts by weight of a polyamide
rein and 20 parts by weight of the iron compound catalyst were
melt-kneaded together and then granulated, thereby obtaining an
iron compound catalyst-containing master batch.
[0105] The thus obtained iron compound catalyst-containing master
batch and polyamide were mixed together (the amount of the iron
compound catalyst is 10 parts by weight based on 100 parts by
weight of polyamide resin), and then charged into a hopper of an
extruder. Then, using a extrusion-coating machine, the obtained
mixture was extruded over a polyolefin-based rein anchor-coated
with polyisocyanate-based resin, thereby obtaining a laminated film
comprising polyamide containing the iron compound catalyst and
polyisocyanate-based resin layer.
[0106] The thickness of the polyolefin-based rein layer and the
polyamide resin layer were 50 .mu.m and 15 .mu.m, respectively. The
weight percentage of the iron compound catalyst based on the total
weight of the laminated film was 1.5% by weight. The amount of
hydrocyanic acid generated was 140 ppm. The inhibiting percentage
of the generation of hydrocyanic acid was 58%.
Example 12
[0107] Using a pressure-kneader, 80 parts by weight of a
polyolefin-based rein and 20 parts by weight of the iron compound
catalyst were melt-kneaded together and then granulated, thereby
obtaining an iron compound catalyst-containing master batch. The
thus obtained iron compound catalyst-containing master batch and
polyisocyanate-based resin were mixed together (the amount of the
iron compound catalyst is 5 parts by weight based on 100 parts by
weight of polyisocyanate-based resin), and then charged into a
hopper of an extruder.
[0108] Alternatively, using a pressure-kneader, 80 parts by weight
of a polyamide rein and 20 parts by weight of the iron compound
catalyst were melt-kneaded together and then granulated, thereby
obtaining an iron compound catalyst-containing master batch. The
thus obtained iron compound catalyst-containing master batch and
polyamide were mixed together (the amount of the iron compound
catalyst is 5 parts by weight based on 100 parts by weight of
polyamide resin), and then charged into a hopper of an
extruder.
[0109] Then, using a extrusion-coating machine, the obtained
polyisocyanate-based resin mixture and polyamide rein mixture were
coextruded, thereby obtaining a laminated film comprising polyamide
containing the iron compound catalyst and polyisocyanate-based
resin layer containing the iron compound catalyst.
[0110] The thickness of the polyolefin-based rein layer and the
polyamide resin layer were 15 .mu.m and 50 .mu.m, respectively. The
weight percentage of the iron compound catalyst based on the total
weight of the laminated film was 4.8% by weight. The amount of
hydrocyanic acid generated was 60 ppm. The inhibiting percentage of
the generation of hydrocyanic acid was 82%.
1 TABLE 1 Amount blended (wt. part) Examples and Iron Comparative
Synthetic Synthetic Synthetic compound Examples resin 1 resin 2
resin 3 catalyst Example 1 100 -- -- 1 Example 2 100 -- -- 2
Example 3 100 -- -- 5 Example 4 100 -- -- 10 Example 5 -- 100 -- 2
Example 6 -- -- 100 2 Comparative 100 -- -- -- Example 1
Comparative -- 100 -- -- Example 2 Comparative -- -- 100 -- Example
3 Examples and Efficiency of Comparative Amount of hydrocyanic
suppressing generation Examples acid generated (ppm) of hydrocyanic
acid (%) Example 1 800 38 Example 2 500 62 Example 3 200 85 Example
4 100 92 Example 5 900 61 Example 6 50 62 Comparative 1,300 --
Example 1 Comparative 2,300 -- Example 2 Comparative 130 -- Example
3
[0111]
2 TABLE 2 Polyolefin-based rein layer Polyamide Iron Examples and
resin Polyolefin- compound Comparative layer based resin catalyst
Thickness Examples (.mu.m) (wt. part) (wt. part) (.mu.m) Example 7
15 100 1 50 Example 8 15 100 2 50 Example 9 15 100 5 50 Example 10
15 100 10 50 Comparative 15 100 0 50 Example 5 Percentage of
inhibiting iron compound Amount of percentage of Examples and
catalyst based on hydrocyanic the generation Comparative total
weight of acid generated of hydrocyanic Examples film (wt. %) (ppm)
acid (%) Example 7 0.7 280 15 Example 8 1.4 180 45 Example 9 3.5 80
76 Example 10 6.6 40 88 Comparative 0 330 -- Example 5
* * * * *