Note: Descriptions are shown in the official language in which they were submitted.
6~
1 BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for preparing
a compounding ingredient for vinyl chloride resins and, more
particularly, it relates to a process for preparing a granulated
compounding ingredient for vinyl chloxide resins by compounding
a liquid or tacky additive into emulsion-polymerized polyvinyl
chloride.
2. Description of the Prior Art
-
- 10 Using conventional techniques, it is necessary to add a
lubricant to a vinyl chloride resin Eor us~ as a moldlng to
improve the workability of the resin during working and also
it is necessary to add a stabilizer such as an oryanotin
stabili2er, etc., to a moulding vinyl chloride resin to prevent
heat deterioration of the resin from occurring. However, slnce
conventionally used additives such as a lubricant and an
organotin stabilizer have a comparatively low melting point
and such additives are mostly liquid or tacky at room ternpera-
ture, (e.g., about 20-30C) such an additive is difficult to use.
More specifically, when a large amount of the additive is
compounded in a vinyl chloride resin as it is, it is dlfficult
to disperse the additive uniformly in the resin simply using
agitation because a localized adhesion of the resin occurs.
This results in reducing the transportability of the product,
hindering production, and decreasing the effects of stabilization
of the resin.
In order to overcome the above described difficulty, a
process ha~ been proposed in which a liquid additive such as an
organotin stabilizer is mixed with a part of the resin using a
mixer having a large shearing stress to form a master powder and
,,~,
1 then the master powder is blended with the remainder of the resin
in a ribbon blender as described in, for example, Plastic
Zairyo Koza (Plastic Mate_ al Course), 14, Vinyl Chlorid Resins;
pages 110-112, published hy Nikkan Koyyo Shinbun Sha on
October 15 r 1961.
However, the above-described process has the following
disadvantage. That is, in producing a master powder in a
granulated condition which is non-tacky and which can be easily
handled by compounding a liquid and tacky compounding ingredient
in a portion of an ordinary moulding suspension-polymeri~ed
vinyl chloride resin merely using the above-described process,
only a master powder having a very low content of the com-
pounding ingredient can be obtained and thus the advantage of
forming the master powder cannot sufficiently be utilized. In
c~mpounding a liquld ingredlent, the ratio of an amount of
resin to that of a liquid ingredient is at most 85/15 by weight,
in compounding a tacky ingredient, the ratio of an amount of
resin to that of a tacky ingredient is at ~ost 70~30 by weight.
SUMMARY OF THE INVENTION
A primary object of this invention is, therefore, to
provide a process for preparing a compounding ingredient for
vinyl chloride resins containing therein a high conten-t of an
additive or additives such as a stabilizer, etc., which is not
tacky, and which is granulated for handling convenience.
That is, according to this invention, there is provided
a process of preparing a compounding ingredient for vinyl
chloride resins which comprises compounding a liquid or tacky
additive or two or more additives comprising a par-tially or
completely liquid or tacky additive or additives into an emulsion-
3~ polymerized polyvinyl chloride powder under hesting.
`" ~ 6~
1 To this end, in one of its aspects, the invention
provides a process for preparing a granulated and non-tacky
: compounding ingredient for vinyl chloride resins which com~
prises compounding a liquid or tacky additive or two or more
additives comprising a partially or completely liquid or tacky
additive or additi~es with an emulsion-polymerized polyvinyl
chloride powder under heating at a temperature of about 100
to 110C, wherein the compounding ratio of the polyvinyl chloride
powder is 0.5 to 2 times the weight of the l.iquid or tacky
additive or additives, wherein said additive or additives
~ comprise an organotin stabilizer or a mixture of an organotin
- stabilizer with another additive or additives.
.: .
~' ' .
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1 DETAILED DESCRIPTION OF THE INVENTION
The emulsion-polymerized polyvinyl chloride powder which
is used in this invention is a so-called resin for paste and the
particles of the resin powder are compact spheres having a smooth
surface. Particle size for the resin powder ranges 0.2 to
60 ~. The compounding ratio of the resin powder is generally
0.5 to 5 times by weight to the weight of the liquid or tacky
additive or additives, preferably 1 to 2 times by weight.
The average degree of polymerization (Pn) of the polyvinyl
chloride ~hich is useful in this invention ranges from 900 to
1700, preferably from 1200 to 1400. The molecular weight (Mw)
calculated based on the average degree of polymerization
ranges from 56250 to 106250, preferably from 75000 to 87500.
The copolymers used in this invention are those
usually used as resins -Eor paste, for example, copolymers which
are disclosed in Japanese Patent Publication 2338/74 (column 7,
lines 7 to 19), i.e., a copolymer of vinyl chloride and a
monomex other than vinyl chloride which is copolymerizable with
vinyl chloride, such as an olefin, e.g., ethylene, propylene,
n-butene and the like; a vinyl ester, e.g., vinyl acetake,
vinyl propionate, vinyl laurate, vinyl stearate and the like;
an unsaturated acid and an ester thereof, e.g., acrylic acid,
methacrylic acid, itaconic acid and the like; a vinyl ether,
e.g., methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether,
lauryl vinyl ether and the like; maleic acid and anhydride
thereof; fumaric acid and anhydride thereof; an aromatic vinyl;
an unsaturated carbonitrile or a mixture thereof.
The amount of monomer capable of copolymeri~lng with
vinyl chloride is preferably below 50~ by weight based on the
weight of the whole monomer.
A straight polymer of vinyl chloride is generally
most preferred.
Examples of liquid or tacky additives to which this
invention is applicable incl~de almost all organotin stabili~ers,
for example, as a liquid additive octyltin mercaptide, octyltin
maleate, dibutyltin malea~e, dioctyltin maleate, dibutyltin laurate,
dibutyltin maleate laurate, dioctyltin laurate, dimethyltin
carboxylic acid aster, dibu~yltin mercapto carboxylia acid
ester, dibutyltin sulfide, dioctyltin mercaptida, dioctyltin
sulfide and the like, and as a tacky additive, dibutyltin maleate
polymer, dicotyltin ma~eate polymer and the like; other stabil-
izers such as certain kinds of metal soaps, for example, as the
liquid additive, calcium chlorostearate, barium chlorostearate
and the like, and, as the tack~ additive, cadmium soap-epoxide
and the like; and hydrocarbo~ type lubricants, for example, as
the liquid additive, liquid paraffin and the lik~, and, as the
tacky additive, polyethylene wax (low molecular weight poly-
ethylene).
Examples of suitable mixers which can be used in
compounding the additive and the polyvinyl chloride resin powder
under heati.ng in this invention include a Henschel mixer, a
super mixer, etc., with which mixing at high speed under heating
can be achieved. It is preferred to compound the materials at
about 100 to abou~ 110C. If the compounding is carried out at
temperatures below about 100C., a tacky powder is obtained and
if the compounding is carried out at temperature above about
110C., a block product which is not applicable for practical
use unless it is applied to a grinding process is obtained.
Since the compounding ingredient prepared by the
process of this invention has a high content of the additive or
--4--.
29~
t additives such as a stabili~er, a lubricant, etc., is not tacky,
and is comple~ely grallula~ed to obtain particles having a
particle size distribution of 75 to 300 ,u, even in compounding
the compounding ingreaient which is prepared using emulsion-
polymerized pol~vinyl chloride according to this invention in
a large amount of suspension-polymerized polyvinyl chloride
usually employed in the ar~, the ingredient can be uniformly
dispersed in the resin and hence no difficulties with respect
to transportabili~y as well as production occur.
The invention is explained in greater detail by
reference to the following examples.
In addition, emulsion-polymerized polyvinyl chloride
having a mean polymerization degree of 1,300, a mean particle
size of 50-60 microns, and an apparent specific gravity of
0.18 g/.ml. and suspension-polymerized polyvinyl chloride having
a mean polymerixation degree of 800, a mean particle size of
- 170 microns, and an apparent specific gravity of 0.54 g./ml.
were used in the examples.
EXAMPLE 1
2Q To 55 parts by weight of an emulsion-polymerized
polyvinyl chloride powder was compounded 45 parts by weight of
liguid octyltin mercaptide us~ng a Henschel mixer under heating
employing the conditions as shown in Table lo The results
obtained are also shown in Table 1 below.
In addition, for the sake of comparison, to 55 parts
by weight of a suspension-polymerized polyvin~l chloride powder
was compounded 45 parts by weight of liquid octyltin mercaptide
under heating employing the same conditions as above and the
results obtained are also shown in Table 1 below.
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1 As iS clear from the results shown in Table l abo~e,
.~ in Example l, a desirable granulated product which was not
tacky was ohtained in each case, while i~ the comparison example,
only a tacky block product was obtained in each case.
EXAMPLE 2
To 55 parts by weight of an emulsion-polymerized poIy-
vinyl chloride powder were compounded 15 parts by weiyht o~
liquid octyltin mercaptide, 15 parts by weight of octyltin
maleate as a tacky powder, and 15 parts by waight of a liquid
hydrocargon lubricant (polyethylene wax of a molecular weight
of 3000) using a Henschel mixer under heating employing the
compounding conditions as shown in Table 2 below. The results
obtained are shown in Table 2 below.
In addition, for the sake of comparison~ to 55 parts
by weight of a suspension-polymerized polyvinyl chloride powder
were compounded the sa~e additives as in the above example~
under heating employing the same compounding conditions as
above and the results obtained are also shown in Table 2 below
as Comparison Example 2. Moreover, to 85 parts by weight of
2~ a suspension-polymerized polyvinyl chloride powder were
compounded 5 parts by weight of liquid octyltîn mercaptide, 5
parts by weight of octyltin maleate as a tacky powder, and 5
parts by weight of a liquid hydrocarbon lubricant under heating
under the same compounding conditions as above and the results
obtained are also shown in Table 2 below as Comparison Example 3.
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--8--
1 As is clear from the results shown in Table 2 above,
when 45 parts by weight oE the liquid and tacky additives were
compounded with 55 parts by weight of the emulsion-polymerized
polyvinyl chloride powder under the compoundiny temperature
conditions of 100 110C as in Example 1, a desirable granulated
product which was not tacky was obtained in each case. On the
other hand, when the same additives as in Example 2 were
compounded with 55 parts by weight of suspension-polymerixed
polyvinyl chloride under -~he same conditions as above as in
Comparison Example 2, only a tacky block product was obtained
in each case. When a comparatively small amount, i.e., 15 parts
by weight of the same liquid and tacky additives were compounded
with 85 parts by weight of suspension-polymerized polyvinyl
chloride under the same conditions as above in Comparison
Example 3, a granular non-tacky product was obtained in each
case but the granular condition of the products was poor and
the products were all inconvenient to handle.
As described above, by compounding liquid and tacky
additives with the emulsion polymerized polyvinyl chloride powder
under heating at 100-110C according to this invention desirable
granulated compounding ingredients having a high additive content
and which are not tacky can be obtained.
EXAMPLES 3 and 4
To 35 parts hy wei.ght of an emulsion-polymerized
polyvinyl chloride powder were compounded 10 parts by weight
of liquid octyltin mercaptide/ 10 parts by weight oE octyltin
maleate as a tacky powder, 10 parts by weight of a liquid
- hydrocarbon lubricant (polyethylene wax of a molecular weight
of 3000), and 35 parts by weight of calcium carbonate powder
using a Henschel mixer under heating employing the compounding
.. . .
conditions as shown in Table 3 below. Furthermore, to 30 parts
by weigh-t of an emulsion-polymeri~ed polyvinyl chloride powder
were compounded 15 parts by weight of liquid octyltin mercaptide,
15 parts by weight of octyltin maleate as a tacky powder, 15
parts by weight of a liquid hydrocarbon lubricant ~polyethylene
wax of a molecular weight of 3000), and ~5 parts by we.ight o:E
a silicic acid powder under the same conditions as above. The
resul.ts obtained were shown in Table 3 below.
o
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1 As is c.lear from the results shown in Table 3 above,
when a powdery filler such as calcium carbonate powder and
silicic acid powder was compounded with the emulsion-polymerized
polyvinyl chloride powder together wi~h other liquid and tacky
additives according to the process of this invention, desirable
granulated compounding inyredients having a high additive
content such as the above described liquid and tacky stabilizers,
lubricant, etc., and which are not tacky can be obtained.
While the invention has been described in detail and
1~ with reference to specific emboidments thereof~ it will be
apparent to one skilled in the art that various changes and
modifications can be made therein without departing from the
spirit and scope thereof.
