U.S. patent number 3,922,457 [Application Number 05/426,105] was granted by the patent office on 1975-11-25 for dry wipe writing system and ink therefor.
This patent grant is currently assigned to Stratabord Limited. Invention is credited to George Derrick Barnwell, Reginald Charles Peter.
United States Patent |
3,922,457 |
Barnwell , et al. |
November 25, 1975 |
Dry wipe writing system and ink therefor
Abstract
This invention provides a dry-wipe writing system, particularly
useful in the education field. The system comprises a writing
surface formed from a polyfluorocarbon polymer laminated to a
support, and a resin-bodied solvent ink on the writing surface in
any desired configuration, the resin-bodied solvent ink comprising
a volatile, organic solvent, a coloring material selected from the
group consisting of dyestuffs and pigments, and a resin.
Inventors: |
Barnwell; George Derrick
(Harrogate, EN), Peter; Reginald Charles (Uxbridge,
EN) |
Assignee: |
Stratabord Limited (Harrogate,
EN)
|
Family
ID: |
27447304 |
Appl.
No.: |
05/426,105 |
Filed: |
December 19, 1973 |
Current U.S.
Class: |
428/207; 427/256;
428/422; 428/500; 434/425; 106/32.5; 428/421; 428/475.5; 428/524;
503/221 |
Current CPC
Class: |
B05D
5/08 (20130101); C09D 11/16 (20130101); C09D
11/00 (20130101); B32B 27/322 (20130101); B43L
1/00 (20130101); B32B 27/08 (20130101); B32B
27/00 (20130101); B32B 7/12 (20130101); B32B
2307/4023 (20130101); Y10T 428/3154 (20150401); Y10T
428/31855 (20150401); Y10T 428/31942 (20150401); Y10T
428/24901 (20150115); Y10T 428/31544 (20150401); Y10T
428/31739 (20150401); B32B 2432/00 (20130101) |
Current International
Class: |
B43L
1/00 (20060101); C09D 11/16 (20060101); B32B
27/00 (20060101); B05D 5/08 (20060101); C09D
11/00 (20060101); B32B 003/10 () |
Field of
Search: |
;117/37R,38,138.8UF,161UG ;161/97,189,146,88,87 ;35/66 ;106/32.5
;260/92.1 ;427/256 ;428/195,207,421,422,474,500,524 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Herbert, Jr.; Thomas J.
Assistant Examiner: Hess; Bruce H.
Attorney, Agent or Firm: Liberman; William R.
Claims
What is claimed is:
1. A dry-wipe writing system comprising a writing surface which is
a sheet of a polyfluorocarbon polymer selected from the group
consisting of polytetrafluoroethylene, fluoroethylene propylene
copolymer and ethylenetetrafluoroethylene copolymer; a support to
which the said sheet is laminated; and a resin-bodied solvent ink
on the said writing surface in any desired configuration, the
resin-bodied solvent ink comprising a volatile, organic solvent, a
coloring material which is selected from the group consisting of
dyestuffs, in combination with an inorganic salt, and pigments, and
a resin selected from the group consisting of phenol-formaldehyde
novolacs, alkoxy-alkylated nylons and vinyl resins, which, together
with the coloring material, forms, when dry, an amorphous,
granular, brittle film wipably removably adherent to the writing
surface.
2. The system of claim 1 wherein the said writing surface is a
sheet of ethylenetetrafluoroethylene copolymer which is adhered to
a rigid support by high tack adhesive.
3. The system of claim 2 wherein the said support is white in
colour.
4. The system of claim 1 wherein the solvent is selected from the
group consisting of alcohols, ethers, esters and ketones.
5. The system of claim 4 wherein the coloring material is a
dyestuff of the metal complex type.
6. The dry-wipe writing system of claim 1 wherein the coloring
material is a pigment.
7. A method of writing on a surface to give a dry-wipe image
comprising applying to a writing surface which is a sheet of a
polyfluorocarbon polymer selected from the group consisting of
polytetrafluoroethylene, fluoroethylene propylene copolymer and
ethylenetetrafluoroethylene copolymer which is laminated to a
support, in any desired configuration a resin-bodied solvent ink
comprising a volatile organic solvent, a coloring material which is
selected from the group consisting of dyestuffs, in combination
with an inorganic salt, and pigments, and a resin selected from the
group consisting of phenol-formaldehyde novolacs, alkoxy-alkylated
nylons and vinyl resins, which, together with the coloring
material, forms, when dry, an amorphous, granular, brittle film
wipably removably adherent to the writing surface.
8. The method of claim 7 wherein the sheet of polyfluorocarbon
polymer is of ethylenetetrafluoroethylene copolymer.
9. The method of claim 7 wherein the said sheet has been adhered to
a rigid support by a high tack adhesive.
10. The method of claim 9 wherein the said support is white in
colour.
11. The method of claim 7 wherein the solvent is selected from the
group consisting of alcohols, ethers, esters and ketones.
12. The system of claim 7 wherein the coloring material is a
dyestuff of the metal complex type.
13. The method of claim 7 wherein the coloring material is a
pigment.
Description
This invention relates to a new dry-wipe writing system of
particular application in education and in other fields where it is
desired to write indicia, such as letters and figures, on a display
sheet and to be able to rub off the indicia simply by dry-wiping
e.g. with a dry duster or cloth. It also relates to an ink of
particular utility in the new dry-wipe system.
It is an object of the invention to provide a new dry-wipe system
on which indicia can readily be written and removed at will by
dry-wiping.
According to the invention there is provided a dry-wipe system
comprising a sheet of polymeric material which is a homopolymer or
copolymer of at least one perfluorinated olefine and a support for
the sheet, the sheet being capable of receiving a resin bodied
solvent ink to form a dry-wipe image.
The invention is based on the observation that contrary to
expectation it is possible to write on these fluorocarbon polymers
using a resin bodied solvent ink without break up of the ink and
furthermore that after the ink has dried it may readily be rubbed
off.
The fluorocarbon polymer used for the sheet is preferably
polytetrafluoroethylene (PTFE), fluoroethylene propylene (FEP) or,
most preferably ethylene tetrafluoroethylene copolymer (EFTE).
The FEP is a thermoplastic copolymer of tetrafluoroethylene and
hexafluoropropylene and is available from du Pont.
The EFTE is also a thermoplastic copolymer but of ethylene and
tetrafluoroethylene, and again is available from du Pont.
The PTFE is preferably a type of smoothed PTFE supplied by
Fluorplast Ltd., of Stoke-on-Trent, Staffordshire, England. PTFE,
FEP AND EFTE are all generally translucent in appearance and will
therefore show the colour of, or any designs or guide lines or
indicia generally, with which the support may be provided. The
writing surface of the material may be evenly embossed to cut down
reflectance; this embossing also has the effect of masking skive
marks and increasing scratch resistance. The support may be of any
desired material which will allow one to write on the sheet and
then to rub the writing off. Although a rigid support is preferred,
supports with some flexibility may also be used. Preferred rigid
supports include metal sheets, such as steel, which are preferably
provided with a coloured coating by dipping, spraying or like
process, the coating preferably being white in colour.
The sheet of polymeric material may be attached to the support in a
semipermanent manner for example by use of springs or clips or a
like mechanism or may be permanently bonded using an adhesive. A
suitable adhesive is a high-tack adhesive. For ease of assembly the
polymeric material can be provided with a layer of a high-tack
adhesive which is covered with a release paper such as silicone
coated paper, which may be removed before bonding.
The polymeric sheet can then be adhered to any desired support.
However the polymeric sheet may be first applied to a flexible
backing sheet, e.g. a polyvinyl chloride foil and the other side of
the backing sheet can be coated with adhesive and, if desired,
provided with a release paper. This assembly of the polymeric
material and backing sheet can then be adhered to any desired
support. The backing sheet may be translucent or opaque and can, if
desired, be printed in any desired way.
The sheet of polymeric material can be formed on the backing sheet
or support by spraying or otherwise applying the polymer to the
backing sheet or support.
For permanent use the polymeric sheet and support is preferably
applied to a sheet of blockboard, chipboard or like material, with
the use of impact adhesive, and edged with a suitable trim. In this
manner articles such as blackboards and display boards generally
may be made.
The ink to be used should be a resin bodied solvent ink. This means
that the ink comprises a solvent and dispersed or dissolved therein
a colouring material which may either be a dyestuff or a
pigment.
Clearly if such a simple ink were used the colouring material would
simply tend to fall off the surface to which it had been applied.
Thus the ink also must contain resin which causes the colouring
material to adhere to the surface to which it has been applied when
the solvent has evaporated. The term "resin bodied solvent ink" as
used herein means an ink containing dyestuff and/or pigment
dissolved or dispersed in a solvent and resin which causes the
dyestuff or pigment to adhere to substrates to which it is
applied.
Preferred inks which may be used according to the invention are
resin bodied solvent inks, in which the solvent is a water miscible
organic solvent, and the constitution of the ink is such that on
application to a smooth, non-absorbent surface, such as PTFE, FEP
or EFTE it dries to deposit an amorphous, non adherent, granular
and brittle film which may be readily dusted off the surface.
According to an aspect of the invention there is provided a method
of writing on a surface to give a dry-wipe image which comprises
applying in any desired configuration a resin bodied solvent ink to
a supported sheet of polymeric material which is a homopolymer or
copolymer of at least one perfluorinated olefine.
The invention also provides a dry-wipe writing system which
comprises a sheet of polymeric material which is a homopolymer or
copolymer of at least one perfluorinated olefine, the sheet being
provided with a support and a resin bodied solvent ink which will,
on application to the sheet, form a dry-wipe image.
The suitability of any particular ink for forming a dry-wipe image
on EFTE, PTFE or FEP can be determined by a simple test, that is by
application to a sheet of the polymer.
These resin bodied solvent inks may also be used for writing on
smooth surfaces other than fluorocarbon polymers as specified such
surfaces including for example, glass, porcelain, enamel and
similar surfaces.
The water miscible organic solvent is preferably an alcohol or an
alcohol-ether. Examples of water soluble alcohols include ethyl
alcohol and industrial methylated spirits as well as glycols, such
as ethylene glycol and glycol derivatives in particular ethers
thereof such as the monoethyl ether of ethylene glycol (Cellosolve)
and the monomethyl ether of ethylene glycol.
There are two major preferred classes of inks, one containing
dyestuffs and the other containing pigments as the colouring
materials.
The resin in the dyestuff-containing ink is preferably a
phenol-formaldehyde Novolac resin. Suitable Novolac resins include,
for example, Alvonol PN430 sold by the Albert Resin Co.
(Reinhold-Albert GmbH) of Wiesbaden-Biebrich, Germany. Other resin
materials which may be used include alkoxy-alkylated nylon such as
Tresin 30.
The dye used in the ink is preferably of the metal complex type;
particularly suitable are those of the copper of chromium complex
type.
The dyestuff-containing ink preferably contains an inorganic salt
which is soluble in the solvent used. Calcium chloride which is
alcohol soluble is suitable. It is preferred that the salt, like
CaCl.sub.2, be hygroscopic but this is not essential.
The ink according to the invention may contain water but only in a
minor proportion (2 to 10%).
Preferred ratios of the components of the dyestuff-containing ink
are as follows:
Percent (a) Water miscible organic solvent 85-97 (b) Novolac resin
2-6 (c) Dyestuff 1-4 (d) Inorganic salt 1-3 (e) Water 2-10 (f)
Other ingredients 2-4 ______________________________________
A preferred type of pigment for use in the inks is one in which the
pigment particles are already resin coated -- this means that
addition of further resin to promote adherence is not always
necessary. Such pigments are available under the "Hoesta" tradename
from Farbwerke Hoescht. These pigments are already coated with a
vinyl resin. The solvent used preferably has at least some solvent
action on the vinyl resin. A particularly preferred mixture of
solvents is of butyl acetate, ethyl acetate and methyl isobutyl
ketone. In the inks containing pigments a barrier system is
preferably used to prevent too strong an adherence of the pigment
to the fluorocarbon polymers; such systems include mixtures of
fatty acid alcohols and esters. Plasticisers are also preferably
used.
The dry-wipe surface of the PTFE, FEP or EFTE and the ink combine
to form a dry-wipe system of outstanding properties.
The invention is illustrated by the following Examples:
EXAMPLE 1
A dry-wipe system was made up as follows.
To a sheet of smoothed PTFE obtained from Fluorplast Ltd., there is
applied a layer of high-tack adhesive.
If this material with an adhesive coating is to be stored before
further processing there is applied to the adhesive a conventional
silicone coated release paper. Otherwise the PTFE sheet is applied
to a sheet of steel coated with a Colorcoat coating (Colorcoat is
supplied by The British Steel Corporation) with the adhesive in
contact to form the laminate which for final use is preferably
adhered to a sheet of blockboard, chipboard, hardboard or like
material with the use of impact adhesive and edged with a suitable
trim. Any desired permanent markings may be printed on the coated
steel before the PTFE is bonded to it.
The PTFE surface of the above material can readily be written upon
using the inks referred to herein, representative inks being as
follows:
EXAMPLE 2 (Dyestuff based)
"Alvonol PN 430" Resin (Albert Resin Co.) 4 gms. Calcium Chloride
(CaCl.sub.2) 2 gms. Zapon Fiery Red B* 2 gms. 95% Industrial
Methylated Spirits 100 mls. * Chromium complex dyestuff sold by
B.A.S.F. (Badische Anilin & Sodafabrik), Ludwigshafen,
Germany.
EXAMPLE 3 (Dyestuff based)
"Alvonol PN 430" Resin 4 gms. Crystalline Sodium Acetate
(non-hygroscopic) 1 gm. Zapon Fast Blue FLE** 4 gms. 98% Industrial
Methylated Spirits 100 mls. **Copper complex dyestuff sold by
B.A.S.F. (Badische Anilin & Sodafabrik) Ludwigshafen,
Germany.
EXAMPLE 4 (Pigment based)
Hoesta print Black L 5.5 gms. Paraplex G 53 1.0 gms. Barrier
system* 5.5 gms. Ethyl acetate 6.7 mls. Butyl acetate 26.8 mls.
Methyl isobutyl ketone 6.7 mls. *50:50 mixture of Alfoil 1216 and
Estol 653.
EXAMPLE 5 (Pigment based)
Hoesta print Green GG 5.0 gms. Paraplex G 53 1.0 gms. Ethyl acetate
6.7 mls. Butyl acetate 26.8 mls. Methyl isobutyl ketone 6.7
mls.
EXAMPLE 6
A dry-wipe system was made up as follows.
To a sheet of FEP (du Pont) there is applied a layer of a high-tack
adhesive.
If this material with an adhesive coating is to be stored before
further processing there is applied to the adhesive a conventional
silicone coated release paper. Otherwise the FEP sheet is applied
to a sheet of steel coated with a Colorcoat coating with the
adhesive in contact to form the laminate which for final use is
preferably adhered to a sheet of blockboard, chipboard, hardboard
or like material with the use of impact adhesive and edged with a
suitable trim. Any desired permanent markings may be printed on the
coated steel before the FEP is bonded to it.
The FEP surface of the above material can readily be written upon
using the inks referred to in Examples 2 to 5.
EXAMPLE 7
A dry-wipe system was made up as follows.
To a sheet of EFTE (sold bu du Pont as "TEFZEL") there is applied a
layer of a high-tack adhesive.
If this material with an adhesive coating is to be stored before
further processing there is applied to the adhesive a conventional
silicone coated release paper. Otherwise the TEFZEL sheet is
applied to a sheet of steel coated with a Colorcoat coating with
the adhesive in contact to form the laminate which for final use is
preferably adhered to a sheet of blockboard, chipboard, hardboard
or like material with the use of impact adhesive and edged with a
suitable trim. Any desired permanent markings may be printed on the
coated steel before the TEFZEL is bonded to it.
The TEFZEL surface of the above material can readily be written
upon using the inks referred to in Examples 2 to 5.
In Examples 4 and 5 Paraplex G53 is a polyester plasticiser
available from Messrs. Rohm and Haas; Estol 653 is glycerol
monooleate and Alfoil 1216 is a mixture of higher fatty alcohols
available from Messrs. Conoco.
* * * * *