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Патент USA US2406705

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Aug- 27› 1945'
Fiied Sept. so, 1944
//// /
, W *Mach
Patented Aug. 27, 1946
› V_
Joseph Mrazek, Woodside, Long Island, N. Y'..
Application September 30, 1944, Serial No. 556573
forming mass includes* a solvent which can- dis
This?'inventioni relates- to a new* and improved
method of marking bodies.
solve said' ink, save possibly' for>the insoluble-pig--V
ment coloring'matter thereof. The coloringmat
The inventionl relatesparticularly to the mark
't'er of said ink can be a dye or dyes which are
ing_ of self-supporting thin transparent ?lms.
„ soluble in said solvent.
such ?lms may be made of any material; which
can con'?pri'se a single ingredient, or a plurality
of ingredi'ents.
The pre-formed marking
cant be, mono-color _or multi-colo?u said. pre
formed› marking can be printed on the, clay coat
ing by any suitable'method or machine.
When the ?lm-forming mass is thus applied to
Without li'mitihg the ir'?vention to any particu
lar material, and' as examples of some of thema
the pre-formed printed marking. said- solív'ent of
terials'whi'ch I can use in the ?lm-forming mass, IO the. ?lm-forming; mass„ which is uniformlyjintle?'
I' refer to cellulose, cellulose hydrate, cellulose
acetate, cellulose acetate butyrate, cellulose ni
trate, cellulose n-itrate acetate, ethyl cell'ulose and
mixed with the other íngredient or ingredíients
of the ?lm-formim;r mass, dissolves and transfers
saidpre-fbrmed printed marking into?the interier
other cellulose ethers,.rubber, rubber hydrochlo
of the'?lm-formin'giimass;without bleeding or
ride& proteins. such as gelatin and casein, poly 15 other distortion of said. .pre-formed marking.
mers` such as polyvinyl alcohol, polyv-inyl alcohol
For this? purpose, the?lm-formí'ng mass is made
of suitable consistency, With: a suitable concen
polystyrol, methyl_ methacrylate and other acrylic
tration of its_ dissolved or dispersed ingredient or
ingredients. The ?lmeforming mass is then al
One; of ' the_ Well-known methods of makin?g 20 lowed-to set or_ harden,v and it isthen stripped
such ?lms is to deposit: the ñlm-forming mass on.
from said' cl'ay casting› surface. I” can thus use
' a perfectly smooth casting'surf'ace, to harden or
any known type of casting device. or castingima
set. the?lms-f?ormingr mass. while it is in contact
chine? in which the paper carrier is af?xed to
with said: casting surface, and` then to› strip the
belt, wheel, orother casting devicev :The in_
set: mass' from said casting surface.` The casting 25 Vention appl'ies to making `bodies of any thíck~
surfaces: now used are metal? belts, metal wheels,
ness or bendability or permeability to light'. The
coated rubber' belts; glass sheets, etc. Heavy
bodies may be translucent or even opaque; and
acetate; polyvinyl ` chloride, polyvinyl butyral,
sheets are; made'by mol'ding blocks and'then slic
inlg the molded blocks.
The invention is. further illustrated by' the an
nexed diagrammatic drawing.
and thickness, and in this respect, I can use' the
well-known methods of making such bodies', save
that I transfer a pre-formed printed markin?ginto
the interior of the set body..
Fig.. 1! is; a top« plan V?éW` which shows a sheet
of paper l, which has a clay coating 2, on which
a: marking 3; has been'printed?. Part of the rep
rescntation of the.` clay'coating 2.' has been: emit
ted›„ in order. to show-the paper l.,
, By making the body in the form of a thin and
transparent ?lm, which is preferably very ?ex
ible, the incorporated* marking is equallygvisible,
rlí'igv. 2 is a horizonal' sectional. View on the line
2-2 of Fig. 1, which shows a mass -4 of '?lm-r
forming material applied tzo the marked casting ›
layer 2.
ofjany' degreeof' rigidity: The method of form
ing~ and: setting the ?nished'` body from its start
ing material', will depend upon its composition
at. both' surfac'es' of said ?lm. The 'invention is
According'to- my-invention, I print a pre-formed
marking on the casting' surface. 'This marking.
can` censist of pictures; Words, etc. This' mark.
iíng is printed' With any- suitable marking mate:
particularly usefulíin making'labels, maps, Charts,`
inserts* for books and' periodi'cals', advertisements,
etc. Since" the '?lme can be' made of twater-proof.
material such as Water-proof “Cellophane? wa;
ter-proof resins and other plastics, etc., the ?n
ished bodies can be resistant to Water. ~ .
rial or ink; The- casting' surface on 'which said 45
The ink, can be made of any ingredient which
pre-formedí printing is made, can be the free or
is, preferably „compatible with the material of
exposed surface of a_ clay coating of a highmgrade,
the markedbodyv Without limiting` the inven
well-sized, sheet of- paper, of the type which is
used. for printing books, and high-grade periodi
cals. sucht paper. can be very ?exible, or sufri
ciently thick to, have› any desired degree of ri?gid-V
ity.. Theexposed_ clay surface should- be smooth. i
Whensuch? printed markirrg is., dry& the ink, is 10-'
cated substantially' wholly on, the free surface. of
tion to' any particular type. of ink, it can be of
50 the type dísclosedin U. S. Patent No. 2,087,190,
in which'the markingv material consists of cellu
losic material and „a resinv or resins.
such ink
need, not containcolori'ng- matter, if a mono-color
marking is. required; because. the opacity' of. the
transf?r?íed?'marking will furnish; the necessary
said; clayr coating, or- close thereto; The ?lm-v 55
contrast with the transparent body of a ?lm.
the use of ethyl cellulose, said ethyl cellulose can
be thoroughly dried.
The “Nevinol'” is a solution of polymerized para
such ink can include a coloring pigment or a col
oring dye. The transferred marking is prefer
ably, but not necessarily, wholly located_ in the
coumarone-indene resin. This is a well-known
product. It has a light straw color.
The diphenyl amine is also designated as
interior of the set ?lm or other set body.
The preferred ?lm-forming materials which I
use in the ?lm-forming mass, are ethyl cellulose
phenylaniline, (C6H5)2NH.
and cellulose acetate.
Some of the other details of my invention are
stated in the following examples, which state
Example 3
Per cent
formulas for respective ?lm-forming masses or
materials. The invention is not limited to the
proportions or other details stated herein. In said
Cellulose acetate ________________________ __
examples, the proportions are by weight.
Example 1
Per cent_
T-type ethyl cellulose _________________ ___
12 ~
1.0 '
14:' `
Butyl acetate _________________________ __
Ethyl alcohol __________________________ __
Butyl alcohol ___________________________ __
Triacetin ______________________________ __
The butyl alcohol, CI-I3(CH2)2CH2OH, is nor
20 mal butanol.
Alcohol S. D. #1 ______________________ __
Acetone _______________________________ __
Triphenyl phosphate __________________ __
Dibutyl phthalate ______________________ __
Toluene _______________________________ __
The triacetin, C3H5(CO2CI-I3)3, is glyc?ryl tri
Example 4
The T-type ethyl cellulose has an ethoxy con
tent of about 48%-50%. This ethoxy content
may be varied, without departing from the in
The triphenyl phosate, PO'(OC6H5)3 is a color 30
less solid. It is used as a plasticizer for the ethyl
The .dibutyl phthalate, C6H4(COOC4H9)2 , is
also a plasticizer for the ethyl cellulose. It is
an oily liquid.
The butyl acetate is the normal butyl ester
Per cent
Cellulose acetate _______________________ __
Acetone _______________________________ __
Ethanol _______________________________ _..
Diethyl phthalate _______________________ __
Santicizer M-17 ________________________ __
whenever I refer to the use of ethanol, I can
use the aforesaid industrial ethanol.
The santicizer M_17, which is described on page
562 of the 1942 edition of "The Condensed Chemi
cal Dictionary," published by Reinhold Publish
ing Company, is methyl phthalyl ethyl glycollate.
of acetic acid. Its formula is CH3COOC4H9. It is
a solvent for the ethyl cellulose.
Triphenyl phosphate ___________________ __
It is a colorless liquid. The formula of diethyl
I The “alcohol S. D. #1" is industrial ethanol,
of 95% strength, this proportion being by Volume. 40 phthalate is CsH4(CO2C2I-I5) 2. It is a solvent and
plasticizer for cellulose acetate.
The. above ingredients, in a uniform.mixture,
The ?nished and set ?lm or body ?'s not in
constitute the ?lm-forming mass. This mass is
juriously affected_ by the transferred ink. That
applied to the free surface of the clay coating of
the paper, on which the pre-formed marking'has
is, the ink can consist of a material which is the
been printed. The method of casting the ?lm, 45 same as the material of the set'body, or the ma
terial of the ink is compatible with the material
including the temperature of casting, etc., fol
of the set body.
lows known practice. The ?lm-forming mass can
The ink can consist of a plu
rality of materials which are compatible with'the
be applied and set at ordinary room temperature
material of the set body. The set body can con
of 20° C.-25° C., and its solvent can be evaporated,
in order to set the ?lm-forming mass, at 20° C. 50 sist of a plurality of materials. The ink can
25° C.
Other formulas for the ?lm-forming mass are
consist of materials which act as plasticizers or
for the material or materials of the set
as follows:
As an example of a suitable printing ink in
Example 2
55 which the coloring matter is a basic dye, which
T-100 ethyl cellulose __________________ __
can be transferred to cellulose foils, after the sol
vent of said ink has evaporated, the following is
Per cent
____ __
Alcohol S. D. #1 _____________________ __
Butyl acetate _________________________ __
Diphenylamine _______________________ __
The "T-100„ ethyl cellulose designates ethyl
cellulose whose ethoxy content is about 48%-50%,
and which has a viscosity of 100 centipoises, when
a 5% solution by weight of said ethyl cellulose
is made in a solvent -which consists of 80% of
toluene and 20% of said industrial ethanol. The
proportions of toluene and industrial ethanol are
Example 5
Acetone _› ____ _'_ ______ __cubic centimeters--
Benzene ________________________ __do____ 500
Ethanol _________________________ __do____ 2000
Shellac ____________________ __kilograms__ 1500
Victoria blue ________________ --per cent__
Cellulose acetate ________________ __do____ 1-3
Another type of ink, which is free from dry
ing oils, is disclosed in British Patent No. 513247.
I do not exclude the use of inks which contain
oils, because numerous oils are compatible with
cellulose derivatives, for example, in producing_
by Volume. To make said test, the ethyl cellulose
is thoroughly dried, in the 'well-known manner.
lacquers which dry to produce coherent ?lms.
In making the compositions disclosed herein with
used for making the pre-formed markíng include'
such compatible oils include raw _castor oi1,› etc.
The resins which can be used in the ink which is
` %406,705
when. it '?s absorbed ,in the _.?im-forming,_mass,
rthus producing an' imperfect .representat?on 'of
pictures which _have ?ne lines. Howevenbyusing
'those which are used_ in ;the spirit varnish in
2~Of {course it .has been well known to make
pre-formed markings with fusible marking
water-insoluble ?lm-forming materials, :and .a
compositions, upon a sheet of paper, and then to
tion, which is preferably free from oil, an exact
thoroughly dry water-insolnble marking .composi
transfer said pre-formed markings by means of
and :accurate reproduction is producedin'therin
heat and pressure. According to my method, the
ink is not fused, during the transfer of the mark
It has also been well known to make decalco
terior of the set body.
The designation` "?lm-forming” material 'is
10 well-known as identifying material which is suit
mania markings, and to transfer the same. ' How
able for making thin ?lms, as distinguished'from
paint and 'lacquer ,?lms which must be perma
ever, such markings could not be ?transferred into
, nently supported `on the rigid surface on which
the interior of a body which is made of ?lm
said paint and lacquer ?lms are formed.
forming material, especially if said material was
Theink or marking composition can consist of
a, 'plastia 'I transfer the pre-formed marking into
?substances which are plasticiz'ers or modi?ers of
the `interier of the body, while said body 'is in
the rethyl'cellulose or'cellulose acetate or other
non-set condition, and I then set the body.
major ingredient of the set ?lm or body." Henes,
The solution of the mass maypenetrate the
when I refer to the intermixture ;of the ;marking
clay coating, although I prefer that there should
composition with the ?lm-forming mass; I .in
be littleor no penetration. The solvent of the
clude such íntermixture which is a physical or
solution of .the mass may penetrate the clay coat
Chemical combination of the êthyl cellulose or cel
ing su?äciently to dissolve all the ink of the mark
lulose acetate or the like, with the marking com
ing. I prefer that the entire vmarking on the cast
position, as though said marking composition
ing surface should be transferred in a single step,
were an original compatible ingredient of said
to a single ?lm-forming mass. However, the
marking composition. Such intermixture is local
marking on the casting surface may be suf?cient
ized, in order to secure the marking eifect. The
to mark a plurality of bodies.
original solvent of the marking composition is
I can also use a casting surface which is made
preferably wholly or substantially evaporated, be
of metal, glass, etc., which has the desired mark
fore the marking is transferred, but the invention
ing in intaglio, and apply the ?lm-forming mass 30
is not limited to this feature.
to said pre-formed intaglio marking, thus elimi
In order Conveniently to separate the ?nished
nating the use` of the paper casting member.
set sheet from the paper sheet carrier, said paper
The prefered embodiment of my invention is
sheet carrier can be thoroughly wetted with water.
to apply the ?lm-forming mass, while it is uni 35 The wetted paper sheet can then be easily peeled
formly intermixed with the ink-solvent, to a coat
off the ?nished set sheet.
ed paper on which the pre-formed marking has
Instead of using the usual casting machine, the
been printed. This permits the transfer of in
?lm-forming mass can be made with .a suitable
tricate three-color and four-color designs. Like
low percentage of liquid ingredienta'so'that it is
wise, since the solvent of the ?lm-forming mass 40 a spreadable paste. This paste can be spread
can be the same solvent which was used in the
unifcrmly under suitable applied pressure, as by
original marking ink, the use of a coated paper
means of a roller or other suitable device, upon
base enables the ef?cien-t transfer of the mark
the printed face of the coating of the paper or
ing. The solvent of the ?lm-forming base can
other carrier for the coating which has the print
consist partially of the solvent of the ink. Hence, 45 ed impression. If desired, _two or more layersof
the solvent of the ?lm-forming composition can
the ñlm-forming mass can thus be mechanically
have the same penetration into the paper or clay
casting surface, as the ink of the marking.
applied in order to produce a ?lm-forming mass
of any desired thickness. This ?lm-forming mass
The paper base is not necessarily coated with
absorbs the printed vimpression, because it has
clay, since other coating pigments and other coat 50 enough solvent for this purpose. It is thus possi
ing materials have been used. The particles of
ble to produce a ?nal set mass of substantial
such coating pigment are held in a solution of
thickness and rigidity, in which the marking does
glue or casein or other adhesive. This coating
composition is applied to the paper, excess so
lution is removed, the paper is dried, and the
coating is burnished to a smooth surface. This
type of coating is suitable for the reproduction
of Very ?ne lines, such as half-tone prints. The
adhesive is preferably inert to the solvent of the
not extend from one face of the set body to the
opposed face thereof.
If desired, the ?nished set sheet or 'other body
of plastic need not be separated from the paper
carrier, which remains adhering to the set body,
thus serving as a backing sheet. However, I pre
fer to soak the paper sheet in water for about
?lm-forming mass, so that neither the paper nor 60 5-1O minutes, at ordinary room temperature of
its coating are añected by the casting and set
ting of the ñlm-forming mass.
There is some intermixture of the marking
composition of the pre-formed printed marking
20° C.~25° C., so that the paper sheet carrier can
be easily stripped from the sheet of plastic.
A specimen of an article made according to my '
invention is annexed and made a part of this
with the solute of the ?lm-forming mass, when
said marking is transferred wholly or partially
I have disclcsed preferred embodiments of my
into the interior of the ?lm-forming mass, How_
invention, but numerous changes and additions
ever, this does not result in any substantial dis
and omissions can be made without departing
tortion of the pre-formed marking. The set body
from its scope.
is impervious to the marking composition, when 70 I claim:
1. A method of making a marked body of ?lm
said marking composition is in the undissolved
forming material, which consists in casting a mass
state. It would ordinarily be expected that since
of a solution of said ?lm-forming material against
the marking composition is dissolved in the sol
a casting layer, said casting layer being smooth
vent which is part of the ?lm-forming mass, that
the marking composition would spread laterally 75 and absorbent and consisting of solid particles,
`'which' are connected by an adhesive which is in
ert to the solvent of said solution, said particles
being also inert to said solvent, said casting layer
having a marking which is at least partially ab
sorbed in said casting layer, substantially all the
ingredients of said marking being soluble in said
of a› solution of said' ?lm-forming `material
against a casting layer, said casting layer being
smooth and absorbent and cbnsisting of solid
particles which are connected by an adhesive
which is inert to the solvent of said solution, said
particles being also inert to said solvent, said
casting layer having a dry and printed original
marking which is transferable by said. solvent
marking has been dissolved in said solvent to form
from said casting layer by said solvent into said
a duplicate thereof in said mass, and evaporat 10 mass, at least part of said printed marking being
ing said solvent while said mass is maintained in
absorbed in said casting layer, maintaining said
contact with said casting layer until said mass
mass of solution in contact with said casting layer
has set into ?nal form against said casting layer.
until said original marking has been transferred
2. A method according to claim 1 in which
by said solvent to form a transferred duplicate
' said ñlm-forming material is selected from a class 15 thereof in said mass, and evaporating said solvent
solvent, maintaining said mass of solution in con_
tact with said. casting layer until suf?cient of said
` which consists of › cellulose ethers and cellulose
while said mass is maintained in contact with said
esters, and said. marking includes a substance se_
casting layer until said mass has set into ?nal
lectecl from said class.
form against said casting layer.
3. A method of making a marked body of ?lm
- forming material, which consists in casting a mass 20
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