U.S. patent number 3,862,070 [Application Number 05/405,319] was granted by the patent office on 1975-01-21 for acrylic synthetic fibers having increased flame retardance and method of producing same.
This patent grant is currently assigned to Kanegafuchi Kagaku Kogyo Kabushiki Kaisha. Invention is credited to Toshihiko Fukushima, Shunichiro Kurioka, Masahiko Morimoto.
United States Patent |
3,862,070 |
Fukushima , et al. |
January 21, 1975 |
ACRYLIC SYNTHETIC FIBERS HAVING INCREASED FLAME RETARDANCE AND
METHOD OF PRODUCING SAME
Abstract
An acrylic synthetic fiber having increased flame retardance,
consisting essentially of 20 to 90 weight percent acrylonitrile, 80
to 10 weight percent vinyl chloride, 0 to 30 weight percent other
ethylenically unsaturated compounds copolymerizable with
acrylonitrile or vinyl chloride and 0.5 to 30 weight percent flame
retardant additive comprising a magnesium compound selected from
the group consisting essentially of MgO, Mg(OH).sub.2, MgCO.sub.3
and mixtures thereof, and method of producing same.
Inventors: |
Fukushima; Toshihiko (Akashi,
JA), Kurioka; Shunichiro (Kobe, JA),
Morimoto; Masahiko (Nishiwaki, JA) |
Assignee: |
Kanegafuchi Kagaku Kogyo Kabushiki
Kaisha (Kita-ku, Osaka, JA)
|
Family
ID: |
14386774 |
Appl.
No.: |
05/405,319 |
Filed: |
October 11, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Oct 18, 1972 [JA] |
|
|
47-104666 |
|
Current U.S.
Class: |
524/140; 524/436;
524/433; 264/206; 524/145; 524/233; 524/365; 524/424; 264/182;
524/144; 524/205; 524/409 |
Current CPC
Class: |
C08K
3/26 (20130101); D01F 1/07 (20130101); C08K
3/22 (20130101); C08K 3/22 (20130101); C08L
33/20 (20130101); C08K 3/26 (20130101); C08L
33/20 (20130101) |
Current International
Class: |
D01F
1/02 (20060101); D01F 1/07 (20060101); C08K
3/00 (20060101); C08K 3/26 (20060101); C08K
3/22 (20060101); C08c 011/70 () |
Field of
Search: |
;260/45.7R,28.5A,45.75B,45.9NP ;264/182,206 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Marquis; Melvyn I.
Attorney, Agent or Firm: Kojima; Moonray
Claims
What is claimed is:
1. An acrylic synthetic fiber having an increased flame retardance
consisting essentially of
A. fiber forming copolymer consisting essentially of 20 to 90
weight percent acrylonitrile, 80 to 10 weight percent vinyl
chloride and 0 to 30 weight percent ethylenically unsaturated
compound copolymerizable with acrylonitrile or vinyl chloride,
and
B. 0.5 to 30 weight percent, based on the weight of said fiber
forming copolymer, of a flame retarding additive comprising a
magnesium compound selected from the group consisting of magnesium
monoxide, magnesium hydroxide, magnesium carbonate and mixtures
thereof.
2. The fiber of claim 1, wherein said magnesium compound is in an
amount of from 1.0 to 10 weight percent, based on the weight of
said fiber forming copolymer.
3. The fiber of claim 1, wherein said flame retarding additive
further comprises in combination with said magnesium compound at
least one compound selected from the group consisting of antimony
trioxide, hexabromobenzene, chlorinated paraffin, tris
(2,3-dibromopropyl)phosphate, dibutylamine phosphate and ammonium
polyphosphate and mixtures thereof.
4. The fiber of claim 1, wherein said fiber forming copolymer
comprises 40 to 70 weight percent acrylonitrile, 60 to 30 weight
percent vinyl chloride and 0 to 30 weight percent of ethylenically
unsaturated compound copolymerizable with acrylonitrile or vinyl
chloride.
5. The fiber of claim 1, wherein said ethylenically unsaturated
compound is selected from the group consisting of acrylic acid,
methacrylic acid or esters thereof; acrylamide, methacrylamide or
N-mono- or dialkyl substitutes thereof; vinyl and vinylidene
halides; vinyl carboxylates; vinyl pyridines; styrene or
.alpha.-substitutes of styrene, .beta.-substitutes of styrene or
aromatic nucleous -substitutes of styrene; allyl-or
methallylsulfonic acid or salts thereof and mixtures thereof.
6. A method of producing an acrylic synthetic fiber having an
increased flame retardance, comprising the steps of preparing and
spinning a spinning solution comprising an organic solvent and the
following components
A. a fiber forming copolymer consisting essentially of 20 to 90
weight % acrylonitrile, 80 to 10 weight % vinyl chloride and 0 to
30 weight % ethylenically unsaturated compound copolymerizable with
acrylonitrile or vinyl chloride, and
B. 0.5 to 30% based on the weight of said fiber forming copolymer,
of a flame retardant additive comprising a magnesium compound
selected from the group consisting of magnesium monoxide, magnesium
hydroxide, magnesium carbonate and mixtures thereof.
7. The method of claim 6, wherein said magnesium is 1.0 to 10.0
weight % based on the weight of said fiber forming copolymer.
8. The method of claim 6, wherein said flame retardant additive
further comprises in combination with said magnesium compound at
least one compound selected from the group consisting of antimony
trioxide, hexabromobenzene, chlorinated paraffin, tris
(2,3-dibromopropyl) phosphate, dibutylamine phosphate, ammonium
polyphosphate and mixtures thereof.
9. The method of claim 6, wherein addition of said magnesium
compound to said fiber forming copolymer is carried out either in
the polymerization stage or in the spinning stage.
10. The method of claim 6, wherein said fiber forming copolymer
consists essentially of 40 to 70 wt.% acrylonitrile, 60 to 30 wt.%
vinyl chloride and 0 to 30 wt% ethylenically unsaturate compound
copolymerizable with acrylonitrile or vinyl chloride.
11. The method of claim 6, wherein said ethylenically unsaturated
compound is selected from the group consisting of acrylic acid,
methacrylic acid or esters therof; acrylamide, methacrylamide or
N-mono- or dialkyl substitutes thereof; vinyl or vinylidene
halides; vinyl carboxylates; vinyl pyridines; styrene or
.alpha.-substitutes of styrene, .beta.-substitutes of styrene or
aromatic nucleous substitutes of styrene; allyl- or methallyl
sulfonic acid or salts thereof, and mixtures thereof.
12. The method of claim 6, wherein said copolymer is produced by
emulsion polymerization, solution polymerization or suspension
polymerization.
13. The method of claim 6, wherein said spinning is carried out by
dry spinning process or wet spinning process.
14. The method of claim 6, wherein said organic solvent is selected
from the group consisting of acetone, acetonitrile,
dimethylformamide, dimethylacetoamide, and mixtures thereof.
Description
BACKGROUND OF THE INVENTION
This invention relates to acrylic synthetic fibres having increased
flame retardance and method of producing same.
Among the various known acrylic synthetic fibers, the so-called
modified acrylic type which contains a comparatively large portion
of flame resistant monomer units, such as vinyl chloride or
vinylidene chloride, in the fiber forming polymer, is known to have
not only the same or similar texture and touch or feel as other
types of acrylic fibers, but also markedly increased flame
retardance thereover.
Recently, because of increased consumer and governmental concern
for loss of human life and human injuries and because of the
desirability of preventing large fires, the social need for flame
retardance of textile goods has increased substantially. Moreover,
increasingly severe legal regulations are necessitating flame
retardance of textile goods.
There are a number of known ways for enhancing flame retardance of
textile fibers, namely (1) copolymerization of flame retardant
monomers, (2) addition of flame retardant additives in a spinning
solution, and (3) application of flame retardant additives by
post-processing of fibers or textile materials.
Each of these methods has its merits and demerits, but the second
(2) method is thought to be advantageous because of its simplicity
and production of long term lasting effects.
Heretofore, there were known to exist as flame retardant additives,
such compounds as those of antimony, zinc, boron, bromine, chlorine
and phosphorus. Among these, only a few are known to be effective
with acrylic fibers. Others are known to be effective only when
used in considerably large quantities. For example, chlorine
compounds such as chlorinated paraffin or tetrabromoethane,
chlorine-phosphorus compounds such as tris-(2,3-dibromopropyl)
phosphate or tris-(2,3-dichloropropyl) phosphate show no
substantial effect unless more than 25 % by weight (based on the
polymer weight; hereinafter similar notation will be used) is
added.
SUMMARY OF THE INVENTION
Through a series of studies and experiments, we have discovered a
class of additives which shows specific and surprising flame
retarding effect with synthetic fibers made only of copolymers of
acrylonitrile and vinyl chloride as discussed more specifically
hereinbelow.
This invention contains acrylic fibers having increased flame
retardance, obtained from a spinning composition containing from
0.5 to 30 weight percent (based on the weight of the polymer) of at
least one compound selected from the group of magnesium compounds
consisting of magnesium monoxide (MgO), magnesium hydroxide
(Mg(OH).sub.2) magnesium carbonate (MgCO.sub.3) and mixtures
thereof.
Acrylic synthetic fibers which may be used in this invention are
those made of copolymers of 20 to 90 weight percent of
acrylonitrile, 80 to 10 weight percent of vinyl chloride,
preferably of 40 to 70 weight percent acrylonitrile and 60 to 30
weight percent vinyl chloride, and from 0 to 30 weight percent of
other ethylenically unsaturated compounds copolymerizable with
acrylonitrile or vinyl chloride.
Ethylenically unsaturated compounds which may be used in this
invention can be any compound which is ethylenically unsaturated
and copolymerizable with acrylonitrile or vinyl chloride. For
example, such compounds may be, although not limited thereto,
acrylic acid, methacrylic acid or esters thereof; acrylamide,
methacrylamide or N-mono- or dialkyl substitutes thereof;
halogenated olefinic compounds such as vinylidene chloride, vinyl
bromide, or vinylidene bromide; vinyl carboxylates such as vinyl
acetate or vinyl chloroacetate; vinyl pyridines such as 2-vinyl
pyridine or 2-methyl-5-vinyl pyridine; styrene, .alpha.-,
substitutes of styrene; allyl- or methallylsulfonic acid or salts
thereof. Appropriate mixtures of the foregoing may be employed.
The copolymerization process can be selected from any of emulsion
polymerization, solution polymerization and suspension
polymerization.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The magnesium compounds which may be used in this invention are
magnesium monoxide (MgO), magnesium hydroxide (Mg(OH).sub.2),
magnesium carbonate (MgCO.sub.3) and mixtures thereof.
From a result of the studies, the inventors have discovered and
made the following novel observations, such as
1. Magnesium monoxide, magnesium hydroxide and magnesium carbonate
show specific, surprising and outstanding flame retarding effect
only for the above-mentioned acrylonitrile-vinyl chloride
copolymers and copolymers of acrylonitrile and vinyl chloride and
ethylenically unsaturated compounds, while no such effect was
produced when the mentioned magnesium compounds were used with
polyacrylonitrile or polyvinyl chloride themselves, or for
polyacrylonitrile-polyvinyl chloride blends having the same
composition percentages as the corresponding acrylonitrile-vinyl
chloride copolymers.
2. Magnesium compounds other than magnesium monoxide, magnesium
hydroxide and magnesium carbonate, for example magnesium phosphate,
magnesium silicate, show only poor flame retarding effect.
3. The burning behavior of acrylic synthetic fibers containing
magnesium monoxide, magnesium hydroxide or magnesium carbonate, is
apparently different from that of acrylic synthetic fibers which do
not contain such magnesium compounds in some respect. First, fibers
containing the above-mentioned magnesium compounds leave markedly
increased amounts of carbonaceous residue (ca.) after burning. When
the carbonaceous residue after burning was measured using twisted
and doubled specimen of filaments resulting from different spinning
compositions and percentage recovery was calculated from the
weights of specimen before and after burning, the results were ca.
17% for the control specimen (without addition of the
above-mentioned magnesium compounds), while the percentage recovery
reached up to ca. 40% for the instant invention when for example
10% by weight of magnesium monoxide was added. This observation was
confirmed by experiments using a thermobalance. Second, fibers
containing the above-mentioned magnesium compounds swell
considerably at the moment of ignition. This is probably due, it is
thought, to surface enclosure of blow-out gas emerging from inside
of the specimen, which may also, to a certain degree, lead to flame
retardance effect. Such a phenomena was never observed at the
moment of ignition of the control specimen.
Hence, the inventive additives magnesium monoxide, magnesium
hydroxide and magnesium carbonate impart flame-retardance
specifically to acrylic synthetic fibers of certain polymer
compositions as herein discussed and the flame retardant effect is
surprising, marked and substantial.
When compared with antimony trioxide (which is reputed to exert
comparatively marked flame retardant effect on acrylic synthetic
fibers) in measurement of limiting oxygen indices, using specimen
forms described later, this invention showed surprising and
outstanding results. For example, the limiting oxygen index for
specimen using 10 weight % addition of magnesium monoxide, for
example, was 42.0, while those for control specimen using 10 weight
percent addition of antimony trioxde was 34.5 and for a second
control specimen not employing any additive was 27.0. These results
showed clearly the marked and surprising effect of use of of the
inventive magnesium compounds.
The amount of magnesium compounds to be added to this invention is
from 0.5 to 30 weight percent, preferably from 1 to 10 weight
percent, based on the weight of the acrylic fiber forming polymer.
No substantial effect can be expected when the magnesium compound
is added in less than 0.5%, while addition of more than 30% impairs
mechanical properties, for example tensile strength and elongation
of the obtained fibers and also leads to economical
disadvantages.
The amounts of acrylonitrile, vinyl chloride, and other
ethylenically unsaturated compounds, to be used in this invention
have been set forth above. Amounts outside of those ranges produce
various disadvantages, and hence should not be used.
Furthermore, these above mentioned magnesium compounds can be used
in combination with compounds which are known to have flame
retardance effect. For example, such compounds may include
inorganic compounds such as antimony trioxide; aromatic halogen
compounds such as hexabromobenzene; aliphatic halogen compounds
such as chlorinated paraffin; halogen and phosphorus containing
compounds such as tris (2,3-dibromoprophyl) phosphate; organic
phosphorus compounds such as dibutylamine phosphate; inorganic
phosphorus compounds such as polyphosphoric acid, ammonium
polyphosphate and combinations thereof. Among the foregoing, a
marked synergistic effect was observed when the inventive magnesium
compounds were used in combination with antimony trioxide.
The addition of magnesium monoxide, magnesium hydroxide, magnesium
carbonate or their mixtures to acrylic fiber forming polymers can
be carried out either in the polymerization stage or in the
spinning stage.
The spinning process used to spin the spinning solution containing
the above-mentioned magnesium compound can be either a dry spinning
process or a wet spinning process.
A solvent can be used in the spinning solution in both cases; such
solvent can be any compound which dissolves acrylonitrile
copolymers in use, for example acetone, acetonitrile,
dimethylformamide, dimethylacetamide, and mixtures thereof.
The method used for evaluating flame retardance of fibers obtained
by this invention was as follows.
Evaluation was made by limiting oxygen indices test (see "Modern
Plastics," Vo. 44., No. 3, Page 141 (Nov. 1966)). This test
determines minimal volumne fraction of oxygen in a slowly rising
gaseous atmosphere that will sustain a candle like burning of a
stick-formed specimen. Therefore, the higher the value of the
index, the greater is the flame retardance of the specimen. The
method was originally devloped for molded plastic materials, and
cannot directly be applied to textile goods, where the evaluation
of flame retardance is generally carried out for specimen in the
form of textile fabric. There are a number of factors which exert
effects on the test results, which do not appear in the case of
molded plastic materials, for example, density and uniformity of
structure, twisting density and count of component yarns. Thus, to
evaluate the flame retardance of the fiber itself as accurately as
possible, a standarized specimen form was established by using
double twisting filaments and measurements were carried out for
specimen in that form. To illustrate, 12 bundles of twisted fibers
each comprising 300 of 3 denier acrylic fiber was doubled and
heat-set, and was erected on a specimen holder of a limiting oxygen
indices tester. Then, the minimal volume fraction of oxygen was
determined, that will sustain the burning of the specimen for 5 cm
of its length.
The invention is further illustrated by, but not limited to, the
following example.
EXAMPLE 1
A fiber forming copolymer composed of 50.0 weight percent
acrylonitrile, 46.0 weight percent vinyl chloride, 3.0 weight %
methyl methacrylate, and 1.0 weight percent sodium
p-styrenesulfonate was dissolved into acetone to a polymer
concentration of 20.0%, and a variety of additives were added to
give spinning compositions. The spinning compositions were spun
into acetone-water coagulation bath through nozzles of 0.1 mm
diameter, followed by drying at 120.degree.C, hot stretching to
300% and heat treatment at 140.degree.C for 5 minutes. The thusly
obtained samples were subjected to measurement of the flame
retardance properties by the above discussed testing method.
As is evident from Table 1, specimen containing magnesium monoxide,
magnesium hydroxide or magnesium carbonate showed marked and
surprisingly superior flame retardance.
Table 1. ______________________________________ Compounds Percent
Added Limiting (Based on Wt. Oxygen of polymer) Index
______________________________________ Magnesium oxide (MgO) 10
41.0 Magnesium hydroxide (Mg(OH).sub.2) 10 42.0 Magnesium carbonate
(MgCO.sub.3) 10 41.0 Tetrabromobutane 10 30.0 Tris
(2,3-dibromopropyl)phosphate 10 29.5 Antimony trioxide 10 34.5
Chlorinated paraffin 10 30.0 Control none 27.5
______________________________________
EXAMPLE 2
A fiber forming copolymer composed of 47.5 weight percent
acrylonitrile, 42.5 weight percent vinyl chloride and 10% by weight
vinylidene chloride, was dissolved in dimethylformamide to a
polymer concentration of 24.0%, and a variety of amounts of
magnesium monoxide, magnesium hydroxide and magnesium carbonates
were respectively added in the range of 0.2 to 30 weight percent,
based on the weight of the polymer. Fibers spun from these
compositions were measured for their flame retardance, which
results are shown in Table 2. The measurement tests were as in
Example 1.
Table 2.
__________________________________________________________________________
% added (Based on Magnesium Magnesium Magnesium Carbo- wt. of
polymer) oxide (MgO) hydroxide (Mg(OH).sub.2) nate (MgCO.sub.3)
__________________________________________________________________________
Control 28.8 28.8 28.8 0.2 29.0 29.0 29.0 0.5 31.5 32.0 32.0 1 33.5
34.5 34.0 5 39.0 40.0 40.0 10 43.5 44.5 43.5 20 48.5 49.0 47.0 30
Over 50 over 50 Over 50
__________________________________________________________________________
EXAMPLE 3
A fiber forming copolymer composed of 65 weight % acrylonitrile,
34.0 weight % vinyl chloride and 1.0% by weight sodium
p-styrenesulfonate, was dissolved into acetonitrile to a polymer
concentration of 20%, and a variety of magnesium compounds were
added respectively in amounts of 10% by weight. The compositions
were spun into acetonitrile-water coagulation bath and then flame
retardance of which was measured an in Example 1. The results are
shown in Table 3.
Table 3 ______________________________________ % added Compound
(Based on Limiting wt. of oxygen polymer index control none 26.0
______________________________________ Magnesium oxide (MgO) 10
40.0 Magnesium hydroxide (Mg(OH).sub.2) 10 41.0 Magnesium carbonate
(MgCO.sub.3) 10 40.0 Magnesium phosphate (Octahydrate) 10 27.2
Magnesium pyrophosphate 10 27.3 Magnesium aluminate 10 31.3
Magnesium trisilicate 10 31.2 Magnesium fluoride 10 29.0
______________________________________
EXAMPLE 4
A fiber forming copolymer composed of 39.0 wt% acrylonitrile, and
61.0 wt.% vinyl chloride, was dissolved into acetone to a polymer
concentration of 23%. To the solution, a variety of flame retardant
additives were added in combination with magnesium monoxide, and
spun in the manner of Example 1 to evaluate flame retardance. The
results are shown in Table 4.
Table 4 ______________________________________ Compound Percent
added Limiting (Based on wt. Oxygen of polymer) index
______________________________________ Control None 30.0 Magnesium
oxide (MgO) 5 45.0 Antimony Trioxide 5 Magnesium oxide (MgO) 5 44.0
Zirconium oxide 5 Magnesium oxide (MgO) 5 43.5 Hexabromobenzene 5
Magnesium oxide (MgO) 5 41.0 1,2,3,4-tetrabromobutane 5 Magnesium
oxide (MgO) 5 42.0 Tris-(2,3-dibromopropyl)Phosphate 5 Magnesium
oxide (MgO) 5 44.0 Ammonium polyphosphate 5 Magnesium oxide (MgO) 5
42.0 Chlorinated paraffin 5
______________________________________
EXAMPLE 5
A fiber forming copolymer composed of 90 wt.% acrylonitrile, and 10
Wt.% vinyl chloride, was dissolved into dimethylformamide to a
polymer concentration of 16%, and after addition of 10% by weight
magnesium carbonate, spun into filaments to measure flame
retardance as in Example 1. The results are shown in Table 5.
Table 5 ______________________________________ Compound Limiting
Oxygen Index ______________________________________ Control 19.5
10% by wt. magnesium carbonate(MgCO.sub.3) 24.0
______________________________________
EXAMPLE 6
A fiber forming copolymer composed of 20 wt.% acrylonitrile and 80%
by wt. vinyl chloride, was dissolved into dimethylformamide to a
polymer concentration of 18%, and after addition of 10 wt.%
magnesium hydroxide, spun into filaments which were then subjected
to measurement for flame retardance by measurement of limiting
oxygen indices as in Example 1. The results are shown in Table
6.
Table 6 ______________________________________ Compound Limiting
Oxygen Index ______________________________________ Control 45 10%
by wt. magnesium hydroxide Over 50 (Mg(OH).sub.2)
______________________________________
EXAMPLE 7
In order to test the flame retarding effects of magnesium monoxide,
magnesium hydroxide and magnesium carbonate on fibers based on
polymers other than acrylontrile-vinyl chloride copolymer, tests
were carried out on the following polymer substrates. Because some
of the substrates were unspinnable into fiber form, limiting oxygen
indices were measured for specimen in the form of pressed strips in
this example. Thus, strips of 1 mm thickness, 10 mm width and 80 mm
length were cut out from pressed sheets which had been prepared
under pressure of 150 kg/cm.sup.2 at a temperature of 140.degree.
to 165.degree.C, from mixtures of finely granulated polymer
substrates and additives, on which flame retardance was evaluated.
As a comparative example, there are also shown data for specimen
containing antimony trioxide, which was previously stated to be
reputed to exert comparatively marked flame retardance effect on
acrylic fibers.
From the results shown in below Table 7, it is evident that the
three above-mentioned magnesium compounds show a specific,
surprising and marked flame retardant effect only to acrylic
copolymers, as above discussed, while no such effect was observed
in the cases or other polymer compositions.
EXAMPLE 8
Fiber strength properties were measured on magnesium oxide
containing specimen prepared in Example 1. As can be clearly seen
in Table 8, no substantial degredation of fiber strength properties
took place by addition of magnesium oxide. The results of light
exposure resistance by Fade-o-meter, also gave no substantial
difference with control specimen wherein no additive were
added.
Table 8 ______________________________________ 10% MgO added
Control ______________________________________ Tensile Strength
g/denier 2.88 2.89 Elongation % 31.6 32.2 Young's modulus kg/mm
428.9 440.8 Knot Strength g/denier 2.42 2.33
______________________________________
Table 7
__________________________________________________________________________
Substitute Polymer Control 10% Mag- 10% Magne- 10% Magne- 10%
Antimony (% by weight) nesium sium hydro- sium carbo- Trioxide
oxid(MgO) xide(Mg(OH).sub.2) nate(MgCO.sub.3)
__________________________________________________________________________
Copolymer of Acrylonitrile-40.2% 30.8 49.2 49.0 49.2 35.0 Vinyl
Chloride-60.8% Blend of Polyacrylonitrile-40% 30.3 32.0 --* -- 38.0
Poly(vinyl chloride)-60% Polyacrylonitrile 100% 20.7 21.3 21.4 21.6
22.5 Poly(vinyl chloride)-100% 43.2 44.8 -- -- 51.8 Blend of
Poly(vinyl chloride)-50% 29.2 29.0 -- -- 36.8 Poly(vinyl
alcohol)-50% Blend of Poly(vinylidene chloride)-10% 28.0 26.2 -- --
37.2 Poly(vinyl alcohol)-90% Blend of Poly(vinyl chloride)-50% 22.8
25.2 25.2 -- 29.8 Poly(methyl metacylate)-50% Blend of Poly(vinyl
chloride)-50% 21.4 25.8 -- 25.2 -- MBS** -50%
__________________________________________________________________________
* no experiment ** graft polymer of methyl methacrylate, butadiene,
and styrene
The foregoing description is for purposes of illustration of the
invention. Numerous other variations and modifications thereof
would be apparent to the worker skilled in the art. All such
variations and modifications are to be considered to be within the
spirit and scope of the invention.
* * * * *