Note: Descriptions are shown in the official language in which they were submitted.
206559~
~nthetic resin hased mater~al. ~rocess for manufacturing
same and its uses, particularlv in the manufacture of fine
leather-like ~oods. articles of stationery~ boxes and similar
items.
____________
The invention relates to a new. synthetic resin based
material intended. amon~ other thin~s. for the manufacture of
fine leather-like oods, articles of stationery, boxes and
similar items, to a process for manufacturing same and to its
applications.
At the present time. the synthetic material based
articles available on the fine leather-like goods, stationery
and box markets manufactured from panels of material, are
~enerally made of polypropylene, polyethylene, and sometimes
polyvinyl chloride (PVC). Their thicknesses ~enerally ran~e
between 0.3 and 2 mm.
These products, which are widely used, present certain
drawbacks, however, in particular:
- in the case of polypropylene and polyethylene panels,
or those obtained by mixing these two polymers, a relativelv
large thickness has to be used in order to ensure the
satisfactory riidity of the finished articles;
- these products have an elastic memory, that is to say
they tend to regain an initial position;
- in order to print on them it is usually necessarY to
apply surface treatments, such as the one known by the
process name of CORONA, prior to printing;
- it is not easy to hot mark them or to bond to~ether
similar qualities, and this necessitates the use of specially
designed machines.
In addition, the tactile qualities of these products,
which are of a paraffinic type, are not always appreciated.
In the case of rigid PVC, which is little used, the
drawbacks are associated rather with folding resistance, cold
resistance and the drv. brittle tactile qualities.
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Ttlere iS tilUS A need t`or a s~nthetic material that can
be used in smaller thic~nesses, while offerin~ the same
rigiditv, very good impact strength, no elastic memorY, good
foldin~ resistance, in particular by means of appropriate
groovin~, and excellent printability, and that can be
transformed, notably into a finished product, usin~ press
type equipment. and most particularly using hi~h frequency
weldin~ machines which, with a suitable process, permit
welding, welding and cutting, and grooving.
Accordin~ to the invention, there is provided a
synthetic material composed. for the most part, of polyvinyl
chloride (PVC), which surprisin~ly and unexpectedlv satisfies
the above-mentioned requirements.
This material is characterized in that it is essentiallv
composed of:
A. A system of resins including:
- 0 to 95% by weight of suspension PVC,
- 0 to 95% by weight of emulsion PVC,
- 5 to 25% by wei~ht of a system formed by one or more
modifying resins, suitable for improving the folding
resistance, and
- 0 to 3% bv wei~ht of acrylic resin,
and
B. Per 100 ~ of resin system A:
- 0 to 15 ~ of plasticizer,
- 0 to 3 g of thermal costabilizer.
- 1 to 3 Y of thermal stabilizer,
- 0.5 to 4 ~ of a lubricating system.
- 0 to 20 g of a mineral filler.
- 0 to 5 g of a colouring system,
- 0 to 1 ~ of anti-ultraviolet radiation (anti-UV)
agent, and
- 0 to 1 ~ of antioxidant.
The expression "susPension P~C " means that the
polvvinyl chloride used has been obtained usin~ a suspension
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process. well known to a man of the art.
~ uspension PVC's that can be used accordin~ to the
invention include, for example, the one bearin~ the reference
S 5703 marketed by the LVM company~ the one bearinY the
reference S5715 marketed by BASF or the one bearin~ the
reference S 071 marketed by ATOCHEM.
Advantaeeously, it has a K value (also referred to as a
"K-Wert") of from 57 to 70. determined accordin~ to the
DIN 53 726 standard.
The expression "emulsion PVC" means that the polyvinvl
chloride used has been obtained usin~ an emulsion process,
well known to a man of the art.
Emulsion PVC's that can be used accordine to the
invention include, for example, the one bearin~ the name of
SOLVIC~R~ 357 NC, marketed by SOLVAY. the one bearin~ the
reference E 600 marketed by ATOCHEM or the one bearin~ the
reference E 6007 marketed b~ HULS.
Accordin~ to the invention. it has been found that
certain modifiyin~ resins are capable, even when added in
relatively small proportions to PVC based compositions, of
considerably improving the foldin~ resistance of the
materials obtained from these compositions.
In particular, the system formed by one or more
modifyin~ resins. suitable for improvin~ foldine resistance.
used accordin~ to the invention is advanta~eously composed of
one to three resins chosen from amon the resins of the
acrylonitrile-butadiene tYpe such as, for example, the resin
marketed under the name of CHEMIGUM(R~ P83, P90 or P8BlA b~-
GOODYEAR, from amon~ the resins of the chlorinated
polyethylene type such as, for example, the resin marketed
under the name of TYRINIR) 3615 or TYRIN~R) 6000 by the DO~
company, and from amon~ the polyester type elastomeric resins
such as, for example, the resin marketed under the name of
HYTREL~R) 55D or 63D bY the DU PONT compan~.
Acrylic resins that can be used accordine to the
2065595
in~-ention include~ for e~amPle. the one marketed under the
name of PA~AL0ID(R)~ 12() ND. ~ 130 or ~ ll5 by the ROHM AND
HAAS compar.~.
The plasticizer used accordin~ to the invention is
5 advanta~eouslv formed bY a phthalic acid, adipic acid.
sebacic acid or trimellitic acid ester .
The phthalic acid ester can be. in particular, the one
marketed under the name of JAYFLEX~R~ DIUP by the EXXON
company. The trimellitic acid ester can be, in particular.
the one marketed under the name of REOMO~R)LTM by CIBA-GEIGY.
The thermal costabilizer used accordinP to the invention
is advantaeeously composed of epoxidized soybean oil or
heptahydrated tetraaluminium and nonama~nesium hexacosa-
hydroxydicarbonate, or a mixture of these compounds.
The epoxidized sovbean oil can be, in particular, that
marketed under the name of REOPLAST IR) 39 by CIBA-GEIG~- or
the one marketed under the name of EDENOL~R) D 81 by the
HENKEL company.
The heptahydrated tetraaluminium and nonama~nesium
hexacosa-hydroxydicarbonate is, for example, that marketed
under the name of ALCAMITZER(R) 42 by MITSUI TOATSU CHEMICALS.
The thermal stabilizer is advanta~eously formed bY an
octyl-tin mercaptide type compound or mixture, in particular
a mixture of monooctyl-tin tri-~2-ethylhexYlmercapto-acetate)
and di-n-octyl-tin bis-(2-ethylhexylmercapto-acetate), such
as that marketed under the name of 17 MOKS~R) by CIBA-GEIG~-.
the one marketed under the name of STANOFIX(R~ A 363 by the
POLYTITAN company or the one marketed under the reference
OT 650 by the HARCROS companY.
The lubricatin~ system can be formed bY an internal
lubricant, an external lubricant or an internal-external
lubricant, or bY mixtures thereof.
Internal lubricants that can be used accordin~ to the
invention include, for example, pentaerythritol and lon~-
chain fatty acid esters, such as the one marketed under the
206559~
name of CIRE B ~16 by the BARLOCHER comPan~-. or fatty acid
and ~lycerol partial esters. such as LOXIOL~R) G 16 marketed
bv the HENKEL company.
External lubricants that can be used accordin~ to the
invention include, for example, low molecular wei~ht
polyethylene waxes such as CIRE AC 316 marketed bY ALLIED
CHEMICAL.
Internal-external lubricants that can be used according
to the invention include, for example, montanic acidsand
ethylene 1ycol esters such as CIRE E marketed by the HOECHST
company.
The mineral filler used according to the invention can
be of the calcium carbonate, talc or silica type.
The calcium carbonate can be that marketed under the
name of OMYALITHEIR) 90 by the OMYA company. The talc can be
that marketed under the name of TALC 10 MO by the DUCANCEL
company. The silica can be that marketed under the name FK
310 by the DEGUSSA company.
The colourin~ system used according to the invention can
be a colourin~ a~ent or a pi~ment, such as, for exemple,
titanium oxide, anatase or rutile, carbon black, for example
PVU 85 black marketed by CIBA-GEIGY, or a metallic oxide commonly
used in the manufacture of panels of PVC, or possibly a
mixture of colouring a~ents and/or pigments.
Anti-UV agents that can be used according to the
invention include, for example, N-/2-ethoxyphenyl)-N'-~2-
ethylphenyl)-ethane diamide, such as TINUVIN~R) 312 or
CHIMASSORB(R) H, both marketed by CIBA-GEIGY, and N,N'-(2-
ethoxyphenyl)-oxonilide.
Antioxidants that can be used accordin~ to the invention
include, for example. sterically "hidden" or hindered
phenols, such as those marketed under the names
IRGANOX~R) 245, 1070 and 1076 bv CIgA-GEIGY.
The material according to the invention can be obtained
by calendering or the cast-film (extrusion and calendering)
2~6559~
process from mixtures of the compounds of types A and B
obtained using the dry mixing processes well known to a man
of the art and widel~ used in the PVC transformation
industry.
This material generallv takes the form of a sheet
having, for example, a thickness of between 0.2 and 1.5 mm.
It can be grained by means of a process commonly used in
the sheet PVC industry, for example by hot stamping between
a metal roller bearin~ a pattern in relief, or an en~raved
pattern, and a second, counter-pressure roller.
Accordin~ to an advantageous form of embodiment, the
components of the system of resins A and the additives B are
mixed in a turbo-mixing device of the tYpe habituallY used
for dry mixing PVC and its additives, the mixture thus
obtained is subiected to a calendering or cast-film
(calenderin~ and extrusion) process to obtain a sheet of a
desired thickness, advanta~eously a thickness of between 0.2
and 1.5 mm, it is grained, if applicable, at a temperature
previously established at approximately 200C, and then it is
~radually cooled down to ambient temperature by bein~ passed
over coolin~ cylinders.
This ~radual cooling ensures its dimensional stability.
The material thus obtained is stored, for example in the
form of spools or formatted sheets or panels.
Whatever the process used to manufacture it and the
method used to store it. the material accordin~ to the
invention has. for smaller thicknesses, a eroup of properties
that confer upon it overall superiority over the known prior
art materials, desi~ned for the same applications.
It can be pointed out, in this connection, that. by
comparison with polyprop~lene and/or polyethylene based
materials, it has, in particular, better stren~th and oreater
ri~idity, it has no elastic memory las defined earlier),
there is no need to apply thereto surface preparation
processes such as the so-called CORONA process prior to
2065~9~
printin~ and it is very easy to hot mark it, for example
usin~ a marking press.
B~ comparison with the known PVC based materials. when
it undergoes grooving and folding, it displays ~ood
resistance permitting its use, in particular, in binding and
in the manufacture of articles such as boxes designed to be
opened and closed frequently.
In addition. unlike the prior art materials. it is
a reeable to the touch, that is to say it is non-paraffinic,
is not dry and is not brittle.
The material according to the invention can be printed
on without anY difficulty, by means of the processes used for
PVC, even after prolon~ed stora~e.
This material can not onlv be cut and arooved using a
platen press but can also under~o high frequency welding and
cutting and welding.
Finally, while offerin the numerous advantages
mentioned above, as well as others, the material accordin~ to
the invention can be obtained at a cost price of the same
order of magnitude as that for materials known hitherto and
designed for similar uses.
This material can be used, in particular, to manufacture
items of stationery or fine leather-like articles such as,
for example, bindin~s, briefcases, dust covers, display
means, bags carrying advertising, boxes, etc., particularly
when it comes in the form of spools or formatted sheets or
panels.
It should be noted, however, that it is also possible to
manufacture articles based on the material according to the
invention usin~ processes other than those described above,
for example by heat forming the sheets or panels obtained,
for example, by calendering or calendering and extruding
mixtures of components A and B, or again by injection
moulding such mixtures.
The following examples are intended to illustrate the
2Q65595
invention, without limitin~ its scope.
EXAMPLE 1:
In a turbo-mixing device, the followin are intimately
mixed:
- 58% by weight of S 5703 t~pe suspension PVC,
- 27% by weight of SOLVIC(R)357 NC type emulsion PVC,
- 1~% by weight of CHEMIGUM(R~ P 83, and
- 1% by weiyht of PARALOID~Rl K 175 type acrylic resin,
with, per 100 g of this mixture:
- 2.0 ~ of REOPLAST(R) 39 type epoxidized soybean oil,
- 0.275 g of ALCAMITZER (R) 42 type heptahydrated
tetraaluminiumandnonamagnesiumhexacosa-hydroxydicarbonate,
- 1.500 g of MOKS(R) 17 type octyl-tin mercaptide,
- 0.700 ~ of CIRE B 216 type pentaerYthritol ester,
- 0.100 g of AC 316 type polyethYlene wax,
- 3.000 ~ of PVQ 85 type black pi~ment,
- 0.410 g of N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)-
ethane diamide or N,N'-(2-ethoxyphenyl)-oxonilide, and
~ 0.700 g of IRGA~O~(R) 1076 as a sterically "hidden"
phenol.
This mixture is sub~ected to a calendering process,
using a four-cYlinder calender, to obtain a sheet with a
thickness of 0.5 mm, ~rained on the calender line.
The material thus obtained is stored in the form of
formatted sheets with a view to its subsequent transformation
into files, after grooving and weldin~, and possibly
printing.
EXAMPLE 2:
In a turbo-mixing device, the followin~ are intimatelY
mixed:
- 55% by wei~ht of S 5715 type suspension PVC,
- 30% by weight of E 600 type emulsion PVC,
- 13% by weiaht of CHEMIGUM~R~ P 90,
- 2% bv weight of PARALOID~l~ K 120 ND with, per 100 ~ of
this mixture:
206559~
~o
~ g of EDE~OL~R~ D 81 type epoxidized soybean oil,
- 1.8 ~ of octyl-tin mercaptide,
- 1.0 ~ of LOXIOL~Rl G 16.
- 0.5 ~ of CIRE E,
- 3.5 ~ of anatase type titanium ATl.
- 0.3 of anti-UV agent, and
- 0.5 ~ of antioxidant.
This mixture is then processed as in Example 1.
EXAMPLE 3:
In a turbo-mixing device, the following are intimately
mixed:
- 63% by weight of S 071 type suspension PVC,
- 27% by weight of E 6007 type emulsion PVC,
- 9% by weight of TYRIN(R) 6000,
- 1% by weight of K 130 type acrylic resin with, per lO0
g of this mixture:
- 10 g of JAYFLEX(R~ DIUP type diisoundecyl phthalate,
- 3.0 g of EDENOL(R) D 81 type epoxidized soybean oil,
- 2.2 . of MOKS(R) 17 type octyl-tin mercaptide,
- 10 g of OMYALITHE(R) 90 type mineral filler,
- 3.5 g of anatase type titanium ATl,
- 0.3 g of anti-UV agent, and
- 0.5 g of antioxidant.
This mixture is then processed as in Example 1.
EXAMPLE 4:
In a turbo-mixing device, the following are intimately
mixed:
- 85% by weight of E 600 type emulsion PVC,
- 8% by weight of CHEMIGUM(R) P 90 type acrylonitrile-
butadiene resin,
- 4% by weight of HYTREL(R~ 63 D type pol~ester
elastomer, and
- 3% by weight of PARALOID(R) K 120 ND type acrylic
resin, with, per 100 g of this mixture:
- 7 g of REOMO~R)LTM type trimellitic acid ester,
20~a~95
- 1.5 ~ of REnPlASI`~39 tvpe epoxidized sovbean oil,
- 1.8 of STANO~IY'~ 363 tvpe octvl-tin mercaptide,
- 1.0 ~ of LOXIOL(~)G16.
- 0.5 of GIRE E.
- 0.8 of TALC 10 MO tvpe talc.
- 3.2 of a mixture of pi~ments~ and
- 0.4 ~ of IRGANOX(~)1070 t~pe antioxidant.
This mixture is then processed as in Example l.
The sheets of synthetic material accordin~ to the
invention. obtained in examples l to 4. can be used, for
instance, to manufacture b~ cuttin and ~roovin~ boxes that
are li~ht and ri~id, and that possess oood resistance and
stren~th.
