Note: Descriptions are shown in the official language in which they were submitted.
W~ 91/1x571 i 1'C.'TItJ~91/01~75
MA'fd.KF;'l~~F'~~:~' ilk Ph I~~1NDIC;IA
This invention relates to an article having permanent andicia
thereon and to the use of such articles for marking electrical equipment,
such as housirags, wires and cables. In a preferred exnbodixnent, the
article is in the form of a heat stable mFarker suitable for use in marking
cable.
Substrates such as wires, cables, equipment housing and the like
are sometimes labeled with marker assemblies comprising a polymeric
article marked with indicia, such as letters, nugnbers, or combinations
thereof. To identify large diameter cables, electrical equipment or the
like,.relatively flat polymeric articles, frequently referred to as cable
markers and panel markers, may be used. To identify individual wires,
a marker:assembly naay copnprise a sleeve, preferably heat recoverable,
of a polymeric material such as a polyolefin, e.g. polyethylene, polyvinyl
chloride, nylon or polyvinylidene fluoride. The indicia are generally
typed or painted onto the article using a typewriter or computer printer.
For many uses, the indicia need to be permanent (i.e. durable), e.g.
resistant to smearing, to being rubbed off' (i.e. abrasion resistant) and
resistant to solvents which may contact the marker, as discussed more
fully below. This lattex req~xirement is generally specified for aircraft
cable, which may come into contact with hydraulic fluid, liquid fuel, de-
icang solvents or the Like. The mark is generally rendered permanent by
a heat treatment. This heat treatment, referred to as °'penmatization",
may take place by placing the sleeve in an oven, subjecting it to infrared
radiation or, in the case of heat-recoverable sleeves, by the heat applied
during the heat-recovery step. See for e~arnple U.S. Patent No. 3,894,731
to Evans where infrared radiation is used to "permatize" the mark and
U.K: Patent Application hTo. 2,18I,~42 where the mark is rendered
permanent by application of heat duxqng a heat shrinking step. An
alternate teclaniq~xe of pea~aanently eking wires, cables or the like is
the relatively expensive "hot stamping" technique which requires
special, expensive sqofpmseat to mark the wire or cable with heated foil.
CA 02077334 2000-06-12
2
Approaches for the production of articles with permanent indicia
or marks without the need for "permatization" by heat treatment are
disclosed in PCT Patent Applications WO 88/06520 and WO 89/09137. The
former application describes a multilayer article comprising a first
substantially
nonporous polymeric layer bonded to a second porous absorbent, polymeric
layer.
The porous layer is capable of being marked with indicia which are resistant
to
organic solvents, smearing or abrasion. The multilayer article is relatively
compli-
cated to manufacture. One method of manufacturing the article is to bond a
first
layer of polymeric material to a second layer of polymeric material
containing a leachable particulate material and then leaching the
particulate material from the second layer to render it porous. The latter
application describes an article in which the surface has a specified
roughness found to be essential for obtaining permanent indicia without
the need to heat treat or "permatize". Articles of the same composition
but without the specified surface roughness could not be marked with
permanent indicia without a "permatizing" treatment.
We have now discovered that an article having a surface made of
a polymeric composition containing specified additives, as defined more
fully below, is capable of receiving permanent indicia, i.e. indicia
resistant to organic solvents, smearing and abrasion, without the need
for a "permatizing" treatment.
One aspect of this invention comprises a marker device
comprising: an article having having on at least a portion of a surface
thereof a permanent mark, said portion of the surface comprising a
composition comprising:
a) about 35 to about 759'0 of a polymeric component having dispersed
therein about 25 to about 65°!0 of a filler component comprising:
i) about 2 to about 65°!0 of an insoluble, infusible, particulate,
active filler having a mean particle size less than about
2.5 micron and a surface area greater than about 10
m 2/g: and
WO 91/1d571 3 P~'r/vS91/o1~75
ii) up to about 60% of an insoluble, ia~.fusible, particulate, inert
filler;
with the proviso that if the polymeric component is nonpolar, said
composition further contains about 0.11to about 10% of low molecular
weight polar compound, all percentages being by weight based on the
weight of the composition.
The terms "permanent" and "pe~rananent indicia" or "permanent
mark" as used herein mean that the amdicaa, or marks, are resistant to
organic solvents, smearing and abrasion, as discussed more fully below
without having been subjected to a "permati.zing" step. The degree of
permanence required varies depending on the particular application.
The term "active filler' means an insoluble, infusible,
particulate filler having a mean particle size less than about 2.5
micron and a surface area greater than about 10 m2/g, such fillers
having been found to be actave in improving the mark permanence of
pOlymeTlC CompOSltlOn6 contSlnlIlg such actl't~e filler.
The term "insoluble, anfu.sible, particulate filler°° means
a filler
in particle form that does not melt or substantially dissolve in the
polymer of the polymeric component under processing and use
conditions.
The term "inert filler" means a filler which does not have a
mean particle size less than about 2.5 micron and a surface area
greater than about 10 m2/g, such fillers having been found to have no
effect on the mark permanence of a marked polymeric composition
containing such inert filler.
Another aspect of this invention compx°ises a method for
producing axe article having permanent indicia thereon, which
method comprises:
(A) selecting an article having on at least a portion of a surface thereof
a permanent ana~rk, said portion of tlae surface comprising a
~'V~ ~1/a~4571
~'CT/~1~91 /Oi $7~
composition comprising:
a) about 35 to about 75% of a polymeric component having dispersed
therein about 25 to about f5%a of a filler component comprising:
i) about 2 to about 65% of an insoluble, infusible particulate,
active filler having a mean particle size less than about
~.5 micron and a surface area greater than abaut 1.0
m2/g: and
ii) up to about 63% of an insoluble, infusible, particulate, inert
fuller;
with tho proviso that if the polymeric component is nonpolar, said
composition further contains about ~.1 to about 1U% of low
molecular weight polar compound, all percentages being by weight
based on the weight of the composition; and
(B) applying ink to said portion of the surface to obtain permanent
indicia thereon.
FIG. 1 illustrates a cable marker having permanent indicia
thereon an accordance with this invention.
FIG. 2 illustrates heat recoverable marker sleeves on a bandolier
and having permanent indicia thereon in accordance with this
. inventioxa.
FIG. 3 illustrates another arrangement of heat recoverable maker
sleeves having permanent indicia thereon in accordance with this .
invention.
In accordance with this invention the composition of the surface,
or the poavtaon ther~o~ to be rrnarked, comprises a polymeric component
and a filler component compra~ing an active filler and, optionally, an
inert filler. The composition contaiaas about 35 to about 'T5% of the
polymeric component, preferable about 35 to about 6~1% and more
preferable aibout 5th to about 6~% of the polymeric component. The
~~~~~'~3~
WO 91/14571 5 F°C:1'1U:~91/01875
composition also contains about 25 to about 65% of a taller component
(defined more fully below), preferably about 30 to about 55% and more
preferable about 40 to about 50% of a filler component. In this patent
application including the claims thereof, all percentages are by weight,
based on the weight of the composition, unless ~therwlse specified.
The polyaneric component preferably comprises a polar polymer
such as polar olefin copolymers, for example, ethylene-alkyl acrylate
copolymers, such as ethylene-methyl acrylate and ethylene-ethyl
acrylate copolymers, ethylene methacrylic acid copolymers, ethylene-
vinyl acetate and blends of these polymers with each other or with other
polymers. Preferably,such blends contain at least about 50% polar
polymer so that the major phase of the polymeric component is polar.
Nonpolar polymers can be used in the polymeric component in blends
with a polar polymer in which the polar polymer predoraianates or a low
molecular weight polar compound can be added to the nonpolar
polymer. Nonpolar polymers include polyethylene, ethylene-propylene
co- or terpolymers and the like.
The insoluble, infusible, particulate, active filler has a mean
particle size less than about 2.5 microns, preferably between about 0.01 to
about 2.5 microns and a surface area greater than about 10 an2/g
preferably between about 10 and about 300 mz/g, more preferable between
about ~5 and about 200 m2/g. The composition contains about 2 to about
65%of the active taller, preferably about 5 to about 45% and more
preferable about 10 to about 20% active f~lller. The active filler, in
addition
to having the specified mean particle size and a surface area, preferably
has an irregular configuration, for example, it can be in the for$u of
flakes, platelets, or the like. Fixtures of active fillers can be used to
obtain the desired degree of mark permanence. The active Taller also
preferably has an oil absorption of greater than about 30, more
preferably greater than about 40 and most preferable greater than about
200 grams per 100 grams of filler. Illustrative active fillers are talc, clay,
fumed or precipitated silica, aluminosilicates, and the like, having the
specified particle size and surface area. fro or more active fullers can be
used if desired.
The composition optionally contains up to about fi3% of the inert
WO 91/1~i57t ~' P~C'T/YJ~91/01875
filler, preferable about 5 to about 60%a, more preferable about 10 to about
50% and most preferably about 20 to about 40% of the inert filler. The
particle size and surface area of the inert filler is not critical.
Illustrative inert fillers are calcium ca bonate (having a particle size
and/or surface area such that it is not an active filler) powdered P"1"FFE,
flame retardants such as decabromodiphenyl ether,
perchloropentacyclodecane, 2,2-bis (tetrabromophthalimido) ethylene,
inorganic fillers such as titanium dioxide, antimony trioxide, zinc
hydroxide, zinc borate, zinc oxide, zinc; sulf-ade, magnesium hydroxide,
basic magnesium carbonate, iron oxide, and the like. Two or more inert
fillers can be used if desired.
The polymer composition can contain soluble, fusible additives in
addition to the active and inert insoluble fillers, if desired. Such
additives include for example, antioxidants such as alkylated phenols,
e.g. those commercially available as ~oodrite 3125, Irganox 1010,
Ixganox 1024, Irganox 1035, Irganox 10'TS, Irganox 1093, 'Vulkanox BI~Ta',
organic phosphite or phosphates, e.g dilauryl phosphate, Mark 1178,
organic sulfides, such as, dilauryl thio-dipropionate, e.g. Carstab
DLTDP, dimyristyl thiodipropionate, e.g. Caratab DMT13'P, distearyl
thiodiproporionate, e.g Cyanox STDI?, amines, e.g. ~Vingstay 29 etc; I~
stabilizers such as (2,2'-thio-bis(4-t-octylphenolato)] n-butyla~anine nickel,
Cyasorb W 1034, 3, 5-ditertiarybutyl-p-hydroxybenzoic acid, ~V Chec
Am-240; processing aids, e.g. zinc stearate, silicone oilsJresin;
crosslinking agents as promoters, such as organic peroxides, e.g.
dicumyl peroxide, triallyl cyanurate, triallyl trimellitate, trimethylol
propane trimethacrylate, triallyl isocyanurate and the like. Mixtures of
such additives can be used if desired.
It has further been found that if the major phase of the polymeric
component is nonpolar, for example if the polymeric component
contains more than 50% high density polyethylene, the composition
should also contaixi a low molecaalar weight polar compound The low
molecular weight paler compound is present in an amount of about 0.1
to about 10 % , preiferably about 1 ~ about 5% and more preferably about
2, to about 4%. Illustrative low molecular weight polar compound which
may be used include hindered phenols, e.g. phenolic antioxidants,
acrylates, such as trimethyl~1 propane trimethacrylate, phthalates,
CA 02077334 2000-06-12
7
such as dioctyl phthalate, cyanurates, such as triallyl cyanurate, and
isocyanurates, such as triallyl isocyanurate, and other compounds
containing one or more polar groups.
The surface roughness of the surface to be marked is not critical.
The surface can be relatively smooth or can have the degree of
roughness specified in WO 89/09137, or can have an intermediate degree of
roughness. In general, however, the rougher the surface the higher the degree
of
mark permanence.
The marked device of this invention need not be subjected to a heat
treatment (i.e. "permatizatiori') to render the mark (or indicia)
permanent (as defined herein). In general, however, if the marked
article is subjected to a heat treatment the mark will have a higher
degree of permanence.
The marker device can be in the shape desired for the intended
use. It can be in the form of a package or label for use on a package or
other substrate to be marked. For application to large diameter
cable,equipment housings and the like, the marker device is generally a
substantially flat sheet, as shown in Fig. 1 discussed more fully below.
For application to individual wires and relatively small diameter cables,
the article is preferably in the form of a tubular article, preferably heat-
recoverable, as shown in ~5igs 2 and 3 (discussed more fully below)
Heat-recoverable articles are articles, the dimensional
configuration of which may be made substantially to change when
subjected to heat treatment. Usually these articles recover, on heating,
towards an original shape from which they have previously been
deformed but the term "heat-recoverable", as used herein, also includes
an article which, on heating, adopts a new configuration, even if it has
not been previously deformed.
In their most common form, such articles comprise a heat-
shrinkable sleeve made from a polymeric material exhibiting the
property of elastic or plastic memory as described, for example, in U.S.
Patents 2,027,962, 3,086,242 and 3,597,372.
CA 02077334 2000-06-12
8
In the production of heat-recoverable articles, the polymeric
material may be crosslinked at any stage in the production of the article
that will enhance the desired dimensional recoverability. One manner of
producing a heat-recoverable article comprises shaping the polymeric
material into the desired heat-stable form, subsequently crosslinking the
polymeric material, heating the article to a temperature above the
crystalline point or, for amorphous materials the softening point, as the
case may be, of the polymer, deforming the article and cooling the article
whilst in the deformed state so that the deformed state of the article is
heat-unstable, application of heat will cause the article to assume its
original heat-stable shape.
The crosslinking can be efi'ected by chemical means, e.g. with
peroxides, or by irradiation or a combination of the two. Radiation
employed can be of various types including charged particles, e.g. alpha
particles or high energy electrons and electromagnetic radiation, e.g.
gamma or ultraviolet radiation. Radiation doses of any desired amount
can be used, although generally a dosage of from 1 to 50, preferably 2 to
20 Mrads will be su~cient.
Illustrative processes for the preparation and use of marker
devices can be found, for example, in U.S. Patents Nos. 3,894,731,
4,349,404, 4,365,400 and 4,865,895. Typical marker devices of this invention
are
shown in the accompanying drawings.
Fig. 1 illustrates an embodiment of a marker device which is an
assembly of cable markers 11 detachable secured to support structure 12.
In the illustrated embodiment the cable markers and support strip have
been formed from an extruded sheet of a polymeric composition in
accordance with this invention and stamping the desired shape.
Perforations 14 are provided where the cable markers join the support
for easy separation of the markers. Typically. the assembly is fed
through a typewriter or printer and the indicia are applied. The
individual cable markers are the removed when needed and secured to
the cable to be identified with a cable tie inserted through holes 16
provided in each marker. The cable marker is not heat shrinkable and
2a~1'~~3~~
WHO 91 / 14571 g 1'CT/U591 /U1 X75
in accordance with this invention no heating step is required to render
the mark permanent, Cable marker assemblies of this type can also
readily be formed from a molded plaque of a polymeric composition
containing an active filler as taught herein.
FIG. 2 shows a marker device wlhach is an assembly comprising a
bandolier or comb like support structuxE; 21 having a spine 22 that is
provided with a number of sprocket holes 23, and an array of bars 24 that
extend from one side of the spine 22. Each bar 2~ has a heat recoverable
sleeve 25 partially recovered thereon.
The assembly can be fed into a conventional typewriter or pz inter,
with suitable modification to the typewriter on printer platten, and a Ilat
surface of each heat-shrinkable sleeve will be presented to the printer
head in correct register for printing indicia on the assembly. After
printing the sleeve is slipped onto a wire or other object to be marked and
heated to recover the sleeve onto the substrate.
FIG. 3 illustrates another embodiment of the marker device of the
present invention wherein cax~ier strips 31, 32 are separate strips and
the adhesive means as provided by opposing tapes 33, 34 having adhesive
surfaces to engage carrier strip 31 and the end portions of marker
sleeves 36. Opposing adhesive tapes 33, 34 bond to each other in regions
37 and bond to the opposite sides of the end portions of iQattened tubular
marker sleeves in regions 39. Tapes 33, 34 engage the carrier strip 31
along the inner portion of carrier strip 31 and along its entire length.
Adhesive straps 33, 34 can b~ segmented or perforated or discontinuous
which in some cases will aid in the ease of removal of the marker
sleeves from the marker sleeve assembly pxovided that su~cient
bonding in regions 37, 3~ are achieved by the lengths of tapes 33, 3~
which are used.
In normal configuration the inner edge of carrier strips 31, 32 axe
._ adjacent to the ends of the #lattened tubular marker sleeves and the
adhesive tapes 33, 3~ cover the area of ez~ch as explained above.
However, in some c;oaafigurations it may be desirable to leave a space in
region 38 between the inner edge of carrier strip 31 and the end of
marker sleeve 36 to allow the opposing adhesive surfaces of opposing
2~'~~J~i~
t'VO 91/1~i571 ~ PCf/iJ~91/11187~
tapes, 33, 34 to bond to each other along and adja<;ent to the ends of
marker sleeves 36 to further aid in holding the flattened tubular marker
sleeves 36 in the desired position and aid in holding the flattened marker
sleeves in the desired flattened configuration.
The indicia are applied to the surface using conventional inks.
Conventional inks typically contain a vehicle comprising a solvent and
optionally a binder, pigment particles, for example carbon black,
together with a dye soluble in the ink vehicle. Such dyes ixiclude, for
example, nagrosine and 9ndulane dyes. The indiaa can be in the form of
alpha-numeric characters, bar codes or the like and can be applied by
any printer typically used for applying such indicia.
Indicia, or marks applied to the surface in accordance with this
invention are permanent without the need for a heat treatment step. For
certain uses, for example to mark wire and harnessing for military use,
resistance to organic solvents and abrasion is of paramount importance.
In this regard, it as neeessaa~ for the marked article to meet the
requirements of ll~alitary Specification 1VITL-Ni-81581 and ll~ilitary
Standard MIL-STD-202, both of which are incorporated by reference
herein. With respect to abrasion, Malitaxy Specification MIL-M-81531
requires that the markings or indicia be readable after being rubbed
with an eraser 20 times.
With respect to resistance to organic soleents, Military Standard
MIL-STD-202 requires that the marks or indicia be readable after being
immersed in a variety of organic solvents and then brushed with a
toothbrush. These organic solvents include: mixtures of isopropyl
alcohol and mineral spirits; an azeotrope mixture of
trichlorotrifluroethane (FR,E~N TF, a registered trademarks of 1! . I.
DuPont de Nemours) and methylene chloride; 1,1,1-trichloroethane; and
an aqueous solution of butyl cellosolve and monoethanolamine.
In addition to meeting the requirements of R~ilitary Standard
MIL-STD-202, it is preferred that the markings or indicia be resistant to
removal during proloraged immersion in the following organic solvents:
JP-4 fuel (kerosene), Skydrol (a phosphate ester hydraulic fluid available
from Monsanto Co~aapany), hydraulic fluid (petroleum based), aviation
~~~~~~e~~~
~'~ 91 / 1 X4571 W 1'CT/US91 /01$75
gasoline, lubricating oil (ester based) and anti_it;iaag fluid (an aqueous
mixture of glycols). These organic solvents are further specified in the
Raychem Corporation Specification ftT-1800/2, which is incoa-porated by
reference herein.
It is, of course, anticipated that the n~arl~ed article according to
the invention vrill be resistant to many other organic solvents as well as
many inorganic solvents.
It should be understood, then, that whenever throughout this
specification the markings or indicla are stated to be permanent or
durable they are resistant to organic solvents, smearing and abrasion,
such resistance to organic solvents, smearing and abrasion shall be
defined as indicated above.
The following examples illustrate the preparation of articles in
accordance with this invention.
Formulations were prepared containing 51% of an ethylene-
methyl acrylate copolymer, 8% of a mixture of a crosslinking promoter,
stabilizer and processing aid, 41% of insoluble, infusible fullers
including an inert filler x~iacture (IF) of decabromodiphenyl ether,
antimony trioxide and other flame retardants and an active filler. Table
I gives the identity of active ~llers used and Table 2 gives the amount of
active fuller used in each example. (Some of the fillers in Table 1 were
found not to be active fillers and do not have the required partials size
and surface area). The formulations were compounded in a Eanbury,
pelletized and extruded into 2" wide tapes. The control formulation
contained 4I% inert filler. rComp. 1, a comparative forqnulation
contained 15% of filler L, an aluminosilicate having a mean particle
size greater that that found to be necessary for obtaining marl
permanence, together with the inert filler.This can be compared to
Example ~ which contains 15% of an aluminosalicate having a particle
size less than aboL~t 2 micron.
The extruded tapes were marked using standard I~1V! printer and ink.
~VU 91/11571
P~r/usy ~ /a i g7s
The permanence of the mark was tested according to Mil 81531,
mentioned above, using Skydrol (after 24 hour immersion in room
temperature Skydrol), Solvent A (mixture of isopropyl alcohol and
mineral spirits), and solvent B (1,1,1-trichloroethane) as defined in Mil.
Std. 202. The results of this testing is shown in Table 2, where the mark
after testing is rated on a scale of 1 - 5, where
1 ~ No evidence of IVIark
2 ~ Some Mark but completely unreadable
3 = Marginal fail
3 = IVIarginal pass
4 = Strong pass
= Retention of original mark quality.
The times indicated in Table refer to the time elapsed between printing
and solvent or fluid immersion.
~O 91/14571 ~ PC.'1'/i1S91/01875
ABLE 1
Filler TYPE PAP,TICLE OIL ABS.SURFACE
SIZE
. Number (macron) y/100
g
m2/g
A Fumed Silica 0.01 ~ x
50
B Fumed Silica 0,02 ,
110
C Fumed Silica 0.01 170
D Silica 1.80 29 6.3
E Ppt. Silica O.U2 app L5p
F Clay 1.80 ~ 5.1
G Clay 1.00 46 13.9
H Clay ' 0.40 43 18-26
I Clay 0.40 43 18-26
J Talc 2.20 ~ 17
K Aluminosilicate1.00
L AJuminoeilice~te3.50 1W
M Mica 2.00
N Wollastonite ?.00 ~ 1.9
O CaC03 2.00 16 2.5
'
. y ~f on ~)
Filler SHAPE
Number
A spherical surface treated
B spherical surface treated
C spherical surface treated
D rnicrocrystallinemicronized
E spherical synth. amorphous
F calcined
G plate 11:1 delaminated
kaolin
H water fractionated
I surface treated
J Plate magnesium silicate
K porous,irreguiartreated
diatomaceous
earth
L porous,irregularcrushed
diatomaceous
earth
M rhombohedral dry ground
N Acircular 5:1 aspect
ratio
O rhombohedral surface treated
yvo 9ria~s~a 14 ~~rius9aioa~7s
E~cample Active filer, Skydrol' Solvent Solvent
% B E
1hr 1 hr 1 hr
4hr
24hr
Control none 1 2 2 . 2
Comp. 1 L, 15% 1 g 2
~, 5% 1 4 _ 3
5 4
4
2 K, 15%~ 5 5 5.5 4.5 5
0
A, 15% 1 ~ 4 5,5* 5
4
C, 15% 1 3. 3.5 5.5* 5
B, 15% 1 $.5 4.5 5* 4
5
JD, 15% 1 3.5 4 3.5 .
3
5
E, 15% 2 4* 4 5.5* .
5 4
5
G, 2% 3 4 5 4 .
4
0 ~C"a'r, 10% 4 4.5 5 4
5
. 4
G, 15% 2 5 5 4
5 5
. . 4.5
11 ~3, 2% 2 ,~ 5 4
4
12 bI, 10l0 4 5 5.5 4.5 4
5
7E~, 15% 2 5 5.5 5* .
14 5
5
T, 15% 1 5 5 5* .
4
5
F, 15% 4 .
5
16 F, 20% . 2 2
2-3 4
4
2
J, 15% 4.5 5 5.5 4.5
J, 20% 4 4 4.5 4.5 4
~, 20% 2-3 - 2 2
-
~, 10% 1 3 4 3 2
5
1~T, 10% 1 3 3.5 . 3
' 4 5
21 Ia 1 3 3.5 3.5 .
22 , 15% 3.5
*Slightly print dace to
blurred ink bleeding
**Blurring
dxae to
surface
roughness
W~ 91/14571 ~ P~T'/U~91/01$75
Formulations were prepared on a Brabender and pressed into
slabs using various base resans, the sanne inert filler {IF) maxture as in
the previous examples and additives as indicated in Table 4. The
following abbreviations were used for the resins:
Resin 1 = low density polyethylene having a melt flow index of 2.2
and a density of .920.
Resin 2 = ethylene/vinyl acetate copolymer containing 18% vinyl
acetate and a melt flow index of 2.5.
Resin 3 = high density polyethylene having a melt flow index of
0.15 and a density of .946.
Resin 4 = very low density polyethylene having a melt flow index of
1.0 and a density of .905.
Resin 5 = ethyIene/vinyl acetato copolymer containing 25% vinyl
acetate and a melt flow index of 2Ø
Resin 6 = ethylene/methyl acrylate copolymer containing 15a/o
methyl acrylate and having a melt flow index of 0.7.
The slabs were irradiated in an electron beam accelerator to a
dose of 10 Mrad. The slabs were then printed with an IBM Proprinter
dot matrax printer. The samples were tested for mark permanence in
Solvent A according to Mil- STD-202 and in Skydrol according to Mil-M-
81531. .
~~~~'~~3~
WO 91/14571
fC.T/IUS97 /01875
TABLE 3
~I J.QB ~
~X ~T ~ ~' sl~ rn~,oL sozw
E~~'r A
~
. VGT T %Q
. IF
.25
1!2
blend**
45 3.5 4.5 2
IF/J/.E 30/7
5/7
5
2? ~ . 2
F .
~
3
28 YP2 O
45 3.5 5 1
29 3 IF 45 1
1 1
30 3 IF/J/E 30/7 1
5/7
5
. 1 1
.
31 1 IF 45 2
1
1 IF/J/~; 30/7.5/7.5 3
5
. 1
33 4 IF 45 4
1
4 IF/J/E 30/7.5/7.5 5
1
35 5 ,IF 45 4
2
IF/J/E 30/7.5/7.5 5
5
37 2 IF 45 5
5 3.5
2 IF/JiE 30/7.5/7.5 5 5
5 5
, . . 5
39 S IF 45 5
5 3
IF/J!E 30!7.5/7.5 5 5
5 5
. . 5
41 6 IF/J/E 35/5/5 5 5
5 5
. . 5
42 6 IFIJ/E 25J10/10 5 5
5
. 5
43 6 IF/J 35/10 5 5
5 5
. . 5
'~ 6 IF/J 25120 5 5
5 5
. . 5
IFlE 35/IO 5
5.5 5
IF/E 25/20 4
5
. 5 5
47 5 K 25 4
5 3.5
48 6
49 8 E ~ ~ 4
50 6 4 3
2
51 6 G 5
2,5 4.5 5 4
53 6 ~ 4.5 5
J
~ 4.5 5 3
55 6 ~ 4.5 4
56 6
4.5 4.5 2
57 6 ~ 4~5 4
D
25 3 4.5 2
58 6
45 3 2
*inert fillers are designated IF, the active fillers are as identified in
Table 1
**the blea~d coaitaind more t5~°l0 of 1, a nonpolar resin.
wo ~~nasm 17 ~trc/US9~ra~s75
Formulations were prepared using the nonpolar resins 3 and ~,
defined above, or a blend of nonpolar resin 3 with a minor amount of
polar resin 6, the same inert filler (TF) mixture as in the previous
examples and polar additives (f'A1 w p:henolic antio~idant,1'.A2 r tria11y1
isocyanurate and 1'A3 = trimethylol propane trimethacrylate) in
amounts specified in Table 4. Each formulation contained active fullers J
and E (see Table 1). Samples were prepared and tasted for mark
permanence in Salvent .A, as described above. The results are shown in
Table 4. The results show that the mark permanence of a nonpolar resin
is improved by the addition of a polar compound.
V1'O 91/14571 1$
~~r/us~i/0~s7s
r~
Ex. Resin ResinResinIF J E PA1
PA2 PA3 Solv A
IVo.3 4 6
59 36.0 19.0 - 28.4 8.3 8.3 -
- - 1
60 34.9 18.5 - 27.5 8.0 8.0 3
0 -
.
61 35.0 18.5 - 2?.6 .8 8 - 4
1 1
. . - 2.7 - 3.5
GZ 34.9 18.4 - 27.5 8.1 8
1
. - - 3.0 5
36.0 - 19.0 28.4* 8.3 8 -
3
. - - 1
64 34.9 - 18.4 27.8' X9.1 8 3
1 0
. .
- - 3.5
