ELECTROPHOTOGRAPHIC TONER RECEPTIVE RELEASE COATINGS

COUCHES DE RECEPTION DE TONER ELECTROPHOTOGRAPHIQUE

English Abstract

ABSTRACT
A release coating receptive to toner particles
emitted by electrophotoconductive devices comprises a
polymer having at least one vinyl polymeric segment
having a Tg° between -10°C and 65°C and at least one
siloxane polymeric segment.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A release coating receptive to particles emitted
by electrophotoconductive devices comprising a polymer
having at least one vinyl polymeric segment having a Tg
between -10°C and 65°C and at least one siloxane polymeric
segment wherein release coat is capable of substantially
anchoring said particles thereto.
2. The release coating of Claim 1 wherein said
polymer is a copolymer comprising the formula:
<IMG>
wherein
R1 are monovalent moieties which can independently
be the same or different and are selected from
the group consisting of alkyl, aryl, alkaryl,
alkoxy, alkylamino, hydroxyl, hydrogen, and
fluoroalkyl;
R2 can independently be the same or different and
are divalent linking groups;
R3 are monovalent moieties which can independently
be the same or different and are selected from
the group consisting of alkyl, aryl, alkaryl,
alkoxy, alkylamino, hydroxyl, hydrogen, and
fluoroalkyl;
R4 can independently be the same or different and
are divalent linking groups;
x is an integer of 0-3;
y is an integer of 10 or greater;
q is an integer of 0-3;; and
G5 are monovalent moieties which can independently be
the same or different selected from the group
-27-

- 28 -
consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino,
fluoralkyl, hydrogen, and -WSA;
A is a vinyl polymeric segment or block consisting
essentially of polymerized free radically polymerized
monomer;
G6 are monovalent moieties which can independently
be the same or different selected from the group
consisting of alkyl, aryl, alkoxy, alkylamino,
fluoroalkyl, hydrogen and -WSA; and
G2 and G4 are A.
3. The release coating of Claim 1 wherein said
polymer is a copolymer of D and E monomers
copolymerized to form a polymeric backbone with F
monomer grafted thereto wherein:
D is at least one free radically polymerizable
vinyl monomer;
E is at least one polar monomer copolymerizable
with D, the amount of E being up to 30% of
the total weight of all monomers, and
F is a monomer having the general formula
X-(Y)nSiR(3-m)Zm wherein
X is a vinyl group copolymerizable with
the D and E monomers,
Y is a divalent linking group where n is
zero or 1;
m is an integer of from 1 to 3;
R is hydrogen, lower alkyl (e.g.,
methyl, ethyl, or propyl), aryl (e.g.,
phenyl or substituted phenyl), or
alkoxy; and
Z is a monovalent siloxane polymeric
moiety having a number average molecular
weight above about 1,000 and is
essentially unreactive under
copolymerization conditions.

- 29 -
4. The release coating of Claim 3 wherein said D
monomer is selected from the group consisting of
styrene, vinyl acetate, vinyl chloride, vinylidene
chloride, acrylonitrile, acrylic or methacrylic acid
esters of non-tertiary alcohols and tertiary alcohols
having from 1 to about 18 carbon atoms and mixtures
thereof.
5. The release coating of Claim 3 wherein said E
monomer is selected from the group consisting of
acrylic acid, methacrylic acid, itaconic acid,
acrylamide, methacrylamide, N,N-dimethylacrylamide,
methacrylonitrile and maleic anhydride.
6. An image receiving article comprising:
a. a release coating coated over a portion
of a front face of a liner comprising a polymer having
at least one vinyl polymeric segment having a Tg between
-10°C and 65°C and at least one siloxane polymeric
segment wherein said coating is capable of
substantially anchoring toner particles emitted by an
electrophotoconductive device; and
b. at least one substrate having a front
and a back face, at least a portion of said back face
coated with an adhesive wherein said back face of said
substrate is secured to said liner.
7. The release coating of Claim 6 wherein said
polymer is a copolymer comprising having the formula:
<IMG>
wherein
R1 are monovalent moieties which can independently
be the same or different and are selected
from the group consisting of alkyl, aryl,

- 30 -
alkylaryl, alkoxy, alkylamino, hydroxyl,
hydrogen, and fluoroalkyl;
R2 can independently be the same or different and
are divalent linking groups;
R3 are monovalent moieties which can independently
be the same or different and are selected
from the group consisting of alkyl, aryl,
alkylaryl, alkoxy, alkylamino, hydroxyl,
hydrogen, and fluoroalkyl;
R4 can independently be the same or different and
are divalent linking groups;
x is an integer of 0-3;
y is an integer of 10 or greater;
q is an integer of 0-3;; and
G5 are monovalent moieties which can independently
be the same or different selected from the group
consisting of alkyl, aryl, alkylaryl, alkoxy,
alkylamino, fluoralkyl, hydrogen, and -WSA;
A is a vinyl polymeric segment or block consisting
essentially of polymerized free radically polymerized
monomer;
G6 are monovalent moieties which can independently
be the same or different selected from the group
consisting of alkyl, aryl, alkoxy, alkylamino,
fluoroalkyl, hydrogen and -WSA; and
G2 and G4 are A.
8. The release coating of Claim 6 wherein said
polymer is a copolymer of D and E monomers
copolymerized to form a polymeric backbone with F
monomer grafted thereto
wherein
D is at least one free radically polymerizable
vinyl monomer;
E is at least one polar monomer copolymerizable
with D, the amount of E being up to 30% of
the total weight of all monomers, and
F is a monomer having the general formula

- 31 -
X-(Y)nSiR(3-m)Zm wherein
X is a vinyl group copolymerizable with
the D and E monomers,
Y is a divalent linking group where n is
zero or 1;
m is an integer of from 1 to 3;
R is hydrogen, lower alkyl (e.g.,
methyl, ethyl, or propyl), aryl (e.g.,
phenyl or substituted phenyl), or
alkoxy; and
Z is a monovalent siloxane polymeric
moiety having a number average molecular
weight above about 1,000 and is
essentially unreactive under
copolymerization conditions.
9. The release coating of Claim 8 wherein said D
monomer is selected from the group consisting of
styrene, vinyl acetate, vinyl chloride, vinylidene
chloride, acrylonitrile, acrylic or methacrylic acid
esters of non-tertiary alcohols having from 1 to about
18 carbon atoms and mixtures thereof.
10. The release coating of Claim 8 wherein said E
monomer is selected from the group consisting of
acrylic acid, methacrylic acid, itaconic acid,
acrylamide, methacrylamide, N,N-dimethylacrylamide,
methacrylonitrile and maleic anhydride.
11. The article of Claim 6 wherein said substrate
is a label.

Description

ELECTROP~OTOGRAPHIC TONER R~CEPTIVE 211~ 3 2 9
RELEA8E COATI~G~
Field of the Invention
The present invention relates to release coatings.
In particular, the present invention relates to release
coatings which anchor toner.
10 Backround of the Invention
A number of conventional electrophotoconductive
devices such as printers and copiers employ dry toner.
These printers and/or copiers employ toner to form a
latent image transferable from an imaging device to a
'~ 15 substrate such as paper, tag or label stock. The toned
u latent image is then subjected to heat fusing in order
to obtain the best print quality and toned image
density.
Although the resulting images are often of good
20 quality, there are problems associated with the imaging
- processes employed by printers and/or copiers. For
example, there is the problem of backgrounding which is
!' the accumulation of various unwanted materials such as
toner particles on the substrate. Backgrounding can
25 occur when the imaging device evenly disperses toner
particles over a non-imaged area of the substrate.
Additional backgrounding problems can be
experienced when label stock is utilized. Label stock
comprises one or more non-continuous substrates
30 referred to as labels which are adhered by an adhesive
to a protective backing or liner. To permit the label
to be removed from the protective liner, it is
customary to coat a release coating over the liner in
order to permit ready separation of the two members.
Although the release coating permits ready
separation, detrimental backgrounding problems can be
experienced when a partially used sheet of label stock
is repassed through an electrophotoconductive printing
device. Usually after the first printing, one or more
:
: ~

211~329
-- 2 --
labels are removed thereby exposing the release
coating. Thus, backgrounding occurs not only on the
label, but also upon exposed release coating. The
toner will not anchor to conventional silicone release
5 coatings due to the fact that these coatings have a
different polarity than do the toner particles and
because the silicone coatings have much lower glass
transition temperatures than the toner particles.
Therefore, the unwanted particles which are dispersed
10 on the release coating tend to flake off the coating,
then transfer to rollers found in printers and then
possibly, relocate themselves to the succeeding labels
or sheets.
- World Patent Application No. US/90/03286 (Josephy
15 et al.) describes a toner receptive coating which can
be applied to compressible substrates such as paper.
Similarly, U.S. Patent No. 4,492,410 (Fitch et al.)
describes a toner receptive coating applied to
substrates such as paper. However, neither of these
~0 two references teach the use of a release coating which
can also anchor toner particles.
Thus, there currently exists a need for a release
coating which will anchor toner particles and yet,
maintains good release properties for substrates such
25 as labels.
Summary of the Invention
The present invention comprises a release coating
which is capable of anchoring toner particles emitted
by electrophotoconductive devices and yet, ~aintains
30 good release properties. The release coating of the
present invention is coated onto a liner over which one
or more substrates such as labels can be applied. The
coating comprises a polymer having at least one vinyl
polymeric segment having a T~ between -10C and 65C and
35 at least one siloxane polymeric segment. Preferably,

. .
2115329
- 3 -
the T8 should be between 20C and 45OC of the vinyl
polymer segment.
In one embodiment of the present invention, the
coating is a copolymer which comprises the formula:
~ I~X\Si--(OSi~-- OSi/ 3~q
,, (G2SR2)X/ G6 (R4sG4)q
wherein
R~ are monovalent moieties which can independently
be the same or different and are selected
from the group consisting of alkyl, aryl,
alkaryl, alkoxy, alkylamino, hydroxyl,
hydrogen, and fluoroalkyl;
R2 can independently be the same or different and
are divalent linking groups;
R3 are monovalent moieties which can independently
be the same or different and are selected
from the group consisting of alkyl, aryl,
alkylaryl, alkoxy, alkylamino, hydroxyl,
hydrogen, and fluoroalkyl;
R4 can independently be the same or different and
are divalent linking groups;
x is an integer of 0 to 3;
y is an integer of 10 or greater;
q is an integer of 0 to 3;
G5 and G6 are monovalent moieties which can
independently be the same or different selected from
the group consisting of alkyl, aryl, alkaryl, alkoxy,
alkylamino, fluoralkyl, hydrogen, and -WSA wherein W is
a divalent linking group and A is defined below; and

-
- 2115329
G2 and G4 are A wherein A is a vinyl polymeric
segment or block consisting essentially of a
polymerized free radically polymerized monomer.
~` In another embodiment of the present invention,
5 the coating comprises a copolymer of D and E monomers
copolymerized to form a polymeric backbone with F
monomer grafted thereto wherein:
D is at least one free radically polymerizable
vinyl monomer;
E is at least one polar monomer copolymerizable
with D, the amount of E being up to 30~ of
the total weight of all monomers, and
F is a monomer having the general formula
X-(Y)~SiR~m,Zm wherein
X is a vinyl group copolymerizable with
; the D and E monomers,
Y is a divalent linking group where n is
zero or 1;
m is an integer of 1 to 3;
R is hydrogen, lower alkyl (e.g.,
methyl, ethyl, or propyl), aryl (e.g.,
phenyl or substituted phenyl), or alkoxy
groups; and
Z is a monovalent siloxane polymeric
moiety having a number average molecular
weight above about 1,000 and is
essentially unreactive under
copolymerization conditions.
~he present invention also includes a toner
30 receptive article comprising a liner, a release coating
and a substrate such as a label mounted over the liner.
Drawinas
Fig. 1 is a representation of an embodiment of
Applicants' invention tested in accordance with the
35 procedures described below.
. ~:

2115329
- 5 -
Fig. 2 is a representation of Avery 30-up stock
#5160 which has been tested in accordance with the
procedures described below.
Detailed Descri~tion
The present invention includes a release coating
which is capable of anchoring toner. The release
; coating has at least one siloxane polymeric segment and
at least one vinyl polymeric segment having a T~ between
-10C and 65C. By virtue of its chemical composition
10 and structure and the resultant properties, the relea~e
coating is well-suited to control toner anchorage
applications. In particular, it is thought that the
silicone segment presents a low energy, "siliconized"
release surface and the higher energy vinyl polymeric
15 segment provides the adhesion for the toner particles.
In one embodiment of the present invention, the
coating is a copolymer which comprises the formula:
( I)~x~si_(oS5~-- osi/(R3)~q
(G2SR2)/ G6 (R4sG4)q
R1 are monovalent moieties which can independently
25 be the same or different which are selected from the
group consisting of alkyl, aryl, alkylaryl, alkoxy,
alkylamino, hydroxyl, fluoroalkyl, and hydrogen.
Preferably, Rl are monovalent moieties which can
independently be the same or different selected from
30 the group consisting of Cl4 alkyl and hydroxyl. Most
preferably, R~ is selected from the group consisting of
methyl and butyl.
R2 are divalent linking groups which can
independently be the same or different. Suitable
35 divalent linking groups include but are not limited to
the following: Cl to ClO alkylene, arylene, alkylarylene

211~329
- 6 -
and alkoxyalkylene. Preferably, R2 is selected from the
group consisting of Cl3 alkylene and C7-C~o alkylarylene
due to ease of synthesis of the compound. Most
preferably, R2 is selected from the group consisting of -CH2-
; 1,3-propylene; and
.,
2 ~ CH2cH2-
' 10
R3 are monovalent moieties which can independently
be the same or different which are selected from the
group consisting of alkyl, aryl, alkaryl, alkoxy,
15 alkylamino, hydroxyl and fluoroalkyl, and hydrogen.
Preferably, R3 are monovalent moieties which can
independently be the same or different selected from
the group consisting of C14 alkyl and hydroxyl. Most
preferably, R3 is selected from the group consisting of
20 methyl and butyl.
are divalent linking groups which can
independently be the same or different. Suitable
divalent linking groups include but are not limited to
the following: C~ to C~0 alkylene, arylene, alkylarylene
25 and alkoxyalkylene. Preferably, ~ is selected from the
group consisting of Cl,3 alkylene and C7-CIo alkylarylene
for reasons of ease of synthesis. Most preferably,
is selected from the group consisting of -CH2-; 1,3-
propylene; and
CH2 ~ CH2CH2
G5 and G6 are monovalent moieties which can
independently be the same or different selected from -

.
_ 7 _ 2 1 ~ ~ 3 2 ~
the group consisting of alkyl, aryl, alkylaryl, alkoxy,
alkylamino, fluoralkyl, hydrogen, and -WSA wherein W is
a divalent linking group and A is defined below.
W are divalent linking groups. Suitable divalent
5 linking groups include, but are not limited to, Cl to ClO
alkylene, alkarylene, arylene, and alkoxyalkylene.
Preferably, W is selected from the group consisting of
methylene and propylene.
G2 and G4 are the same or different and comprise A.
lO A is a vinyl polymeric segment consisting essentially
of polymerized free radically polymerizable monomer. A
can comprise either a homopolymer segment or block or a
copolymer segment or block. The toner anchorage
properties of the coating are determined by the vinyl
15 polymeric segment content. The chemical nature or
composition of the vinyl polymeric segments can be
modified independent of the release aspect to improve
toner anchorage and adhesion to the substrate. Thus,
the release coating can be chemically tailored to
20 provide a specific level of toner anchorage. The
selection of the composition of A is typically based
upon the intended use of the release coating and the
properties the release coating must possess in order to
accomplish its intended purpose.
A can include, but is not limited to, those
monomers wherein the free radically polymerizable
monomer or monomers are chosen such that a vinyl
segment has a T~ or Tm above about -20C. The preferred
free radically polymerizable monomers are selected from
30 the group consisting of styrene, methyl methacrylate,
methyl acrylate, acrylic acid, methacrylic acid,
acrylonitrile, isobornyl acrylate, isobornyl
methacrylate, N-vinyl pyrrolidone, butyl methacrylate,
isopropyl methacrylate, vinyl acetate, hydroxy
35 propylacrylate, hydroxy ethyl acrylate and mixtures
thereof.

~ 2115329
- 8 -
The amount and composition of the vinylic segment
to silicone should range from about 98 to about 2 parts
preferably, from about 40 to about 60 parts by weight.
It is preferred that the vinyl polymeric segments
5 should have a molecular weight in the range of 2,000 to
80,000, more preferably 5,000 to 50,000.
The release properties of the coating are
determined by both the silicone content (weight
percentage) present in the copolymer and the molecular
10 weight of the silicone segment, with higher silicone
content and/or molecular weight providing easier
release. A copolymer or copolymer blend can,
therefore, be chemically tailored to provide a specific
level of release which can be reproduced with
15 consistency, thus making possible the variation of the
release properties of a liner over a range of values in ;~
a controlled fashion.
The silicone polymeric segment must have an
average molecular weight above about 1000 in order for
20 the release coating to function properly. Preferably,
the silicone polymeric segment has a number average
molecular weight of about 1000 to about 20,000. Most
preferably, the silicone polymeric segment has a number
average molecular weight ranging from about 2,000 to
25 about 15,000. The silicone polymeric segment can
comprise about 2 to 60 wt% of the release coating in
order to allow for a wide range of release performance. ~;
In another embodiment of the present invention,
the release coating comprises a copolymer of D and E
30 monomers copolymerized to form a polymeric backbone. ;
Grafted to the backbone is an F monomer. The D and E
monomers provide the toner anchorage properties of the
coating and the F monomer provides the release
properties.
The D monomer or monomers (there may be more than
one) are chosen such that the backbone T~ or T~ is above
about -20C. Representative examples of D monomers
, ~ ~' : ' ' ': ' ' " '

21~ 5329
include styrene, vinyl acetate, vinyl chloride,
vinylidene chloride, acrylonitrile and acrylic or
methacrylic acid esters of nontertiary alcohols or
tertiary alcohols such as methanol, ethanol, propanol,
5 isopropanol, butanol, isobutanol, cyclohexanol, benzyl
alcohol, dodecanol, hexadecanol, and octadecanol, the
alcohols having from 1 to 18 carbon atoms.
Especially preferred D monomers include methyl
methacrylate, butyl methacrylate, vinyl acetate,
10 partially hydrolyzed vinyl acetate, methyl acrylate and
octadecyl acrylate.
Representative E monomers useful in practicing the
invention, and which may be used either individually or
in combination, include carboxylic acids such as
15 acrylic acid, methacrylic acid, itaconic acid, maleic
acid, fumaric acid, and 2-carboxyethyl acrylate and
their ammonium or metal salts; sulfonic or phosphonic
acids such as 2-sulfoethyl methacrylate, 3-sulfopropyl
acrylate, 3-sulfopropyl methacrylate, styrene sulfonic
20 acid, and vinyl benzyl phosphonic acid and their
ammonium or metal salts; amides such as acrylamide,
methacrylamide, N,N-dimethyl acrylamide, and N-vinyl
pyrrolidone; and monomers having hydroxyl functionality
(e.g., 2-hydroxyethyl acrylate, 2-hydroxyethyl
25 methacrylate, hydroxypropyl acrylate, and
dihydroxypropyl acrylate), ammonium functionality
derived from reaction of amine-containing monomers
, (e.g., N,N,-dimethylaminoethyl methacrylate and vinyl
pyridine) with alkylating agents or protic acids, or
30 zwitterionic functionality such as that derived by
reaction of amine monomers with hydrogen peroxide or
propane sulfone.
The F monomer has the general formula:
X~ ( Y ) nS iR~m) Zm
X is a vinyl group copolymerizable with the D and
E monomers.
Y is a divalent linking group.

211~3~9
-- 10 --
R comprises hydrogen, lower alkyl groups such as
methyl, ethyl, or propyl, aryl groups such as phenyl or
substituted phenyl and alkoxy groups such as methoxy
and ethoxy groups.
Z is a monovalent siloxane polymeric moiety having
a number average molecular weight above about 1,000 and
is essentially unreactive under copolymerization
conditions.
The preferred F monomer may be further defined as
10 having an X group which has the general formula
Rl R2
CH = C -
wherein Rl is a hydrogen atom or a COOH group and R2 is
a hydrogen atom, a methyl group, or a CH2COOH group.
The Z group of the F monomer has the general
formula
R4 ~ Si- O -)
R5
:
wherein R3 and R5 are independently lower alkyl, aryl,
or fluoroalkyl, where lower alkyl and fluoroalkyl both
refer to alkyl groups having from one to three carbon
30 atoms and where aryl refers to phenyl or substituted
phenyl. R4 may be alkyl, alkoxy, alkylamino, aryl,
hydroxyl, or fluoroalkyl, and r is an integer from
about 5 to about 700. Preferably, the F monomer has a
general formula selected from the group consisting of
35 the following, where m is 1, 2 or 3, p is zero or 1,
.

2115329
- 11 -
R" may be alkyl or hydrogen, and X, R, and Z are as
defined above:
O
X--C--O--(CIOq (O)~Si(R)3~mZm
' ~
. wherein q is an integer from 2 to 6;
X ~ --o--si~R~-mzm~
~;
~ '
~o~o~si~R~ mZm
'' ~; '
wherein q is an integer from zero to 2;
O H O R~
X-C-O~ N-C-N -(C~Oq Si~R)~ mzm
wherein q is an integer from 2 to 6;
::
- ":, ~.

211~32 g
- 12 -
.. . . :
0 H 0 R"
X--C--O--CE~-C~-N--C--N ~ Si~R~Lm~m
5 and
X-~-0~ CH-Cl5-~ -(CH~q ~R~ ~ m
wherein q is an integer from 2 to 6.
The release coating of the present invention may
comprise the copolymers of the two embodiments alone,
15 or may comprise copolymers blended with other
3 compatible homopolymers and/or copolymers. The low -
percentage of silicone contained in the copolymers
makes the copolymers readily compatible with polymers
of similar composition to the vinyl Polymeric blocks or
20 segments. In addition, there are several pairs of
dissimilar polymers that yield compatible blends due to
- specific interaction as described by S. Krause in
Polymer Blends, Academic Press, New York, 1978. -
Introduction of a low level of silicone block onto one
25 of these polymers will not influence compatibility.
In addition, additives, fillers or pigments such
as alumina, ~ilica, titanate, or calcium carbonate may,
of course, be added to the copolymer compositions.
The release coating of the present invention
30 should provide sufficient anchorage to anchor at least
50% of the toner. It is understood that ~ ~`
"substantially" means at levels of at least 50%. More
preferably, it should anchor at least 70% of the toner.
; In addition, the release coating should have a
35 surface release value not greater than about 10 oz./in
(ll N/dm). It should be understood that this upper
l1=it appliee to use w1th highly aggr-s-lve pr-ssure-

211.~329
- 13 -
sensitive adhesives (PSAs) which have peel adhesion
values of 4S N/dm or higher. PSAs as a group fall into
three broad categories (1) low (5-15 N/dm), (2)
intermediate (25-50 N/dm), and (3) high (60-100 plus
5 N/dm) peel adhesion ranges. It is apparent that the
degree of release can be selected to match the
aggressiveness of the PSA with which it will be in
contact and it is only for the most aggressive PSAs
that a release value as high as 10 oz/in. (11 N/dm)
10 would be selected. Release coatings for less
aggressive PSAs would be selected to be correspondingly
lower.
The release compositions do not require curing or
crosslinking; however, if solvent resistance is desired
15 for a particular application, crosslinking can be
effected by standard methods well-known in the art, -
such as radiation curing (electron beam or ultraviolet
light) or chemical crosslinking.
The release coating compositions may be applied to
20 any suitable backing or liner by means of conventional
coating techniques such as wire-wound rod, direct
gravure, offset gravure, reverse roll, air-knife and
trailing blade coating. Suitable liners include paper,
non-woven fabrics and films of thermoplastic resins
25 such as polyesters, polyamides, polyolefins,
polycarbonates and polyvinyl chloride.
In addition, any substrate which can be applied to
a liner by a pressure sensitive adhesive can be
utilized. For example, paper is a suitable substrate.
In a preferred embodiment, the release coating of
the present invention is utilized as a component of
label stock. In this preferred embodiment, one or more
non-continuous substrates such as labels are adhered to
protective liner by a suitable adhesive. To permit the
35 substrate to be removed from the liner, the release
coating of the present invention is coated the liner.

` `- 14 - 211~3~9
The following examples are illustrative in nature
and are not intended to limit the invention in any way.
TEST SAMPLES
The polymer solutions of Examples 1 to 19
5 discussed below were diluted to 15% solids in distilled
water. The solutions were then coated onto
commercially available roll base paper with a gravure
; roll having a pyramidal pattern of 200 cells per inch.
A two roll direct gravure coating was applied to each
10 sample. Two different roll base papers were utilized.
Supercalendered ClS paper supplied by the Simpson Paper
Company was coated with the diluted polymer solutions
of Examples 1 to 4 and machine glazed base paper sold
by Akrosil were coated with the diluted polymer
15 solutions of Examples 4 to 19. After coating, the base ~ -
papers were dried at 77 C.
Test Methods
Release Properties
The release property of an adhesive refers to ease
20 that an adhesive separates from another surface. It is
the force required to remove a flexible adhesive tape
¦ from a test sample at a specific angle and rate of
removal. It is measured in Newtons per decimeter
(N/dm) Two test methods are used to evaluate the
` 25 release properties of coated flexible sheet materials.
Both tests are modified versions of the industry
standard peel adhesion test ASTM D3330-78 PSTC 1 and 3 -
used to evaluate PSA coated materials. The two modified
release property tests are described below.
30 1. Immediate Release Value
Each test sample was conditioned overnight at
constant temperature (22 C) and humidity (50% RH).
Thereafter, a 5.08 cm by 25.4 cm strip of the test
sample is laminated to a constant 90- angle jig
35 commercially available as the Deltron Ball Slide from
the J.R. Brass Co. of Eden Praire, MN with double
coated tape. Then a 2.54 cm strip of a PSA coated test

- 15 - 2115329
tape was rolled down onto the laminate with a 1.82 kg
rubber roller. The force required to remove this tape
at 90 and 30.5 cm/minute was then measured was
measured by a Sintech/Instron Tensile Tester System
5 commercially available from Sintech Corporation, a
division of MTS Systems Corporation, Research Triangle
Park, North Carolina.
2. Aged Release Test
The aged release test was conducted in the same
10 manner as the immediate release test with the exception
that the test tape was allowed to dwell in contact with
the coated paper for 3 days at 65 C and 50% RH, 11 days
at 21-C and 80% RH, 11 days at 49 C dry, and 11 days
49 C at 6~% RH, prior to removal.
15 Toner Receptivity Testina
The toner receptivity of the test samples was
assessed by printing on a 21.6 cm x 27.9 cm test sample
an asterisk pattern, i.e., (****), in an Hewlett
Packard LaserJet II printer. The imaged coated sheets
~0 then sat overnight in a controlled environment of 21-C
and 50% RH. Thereafter, a 2.54 cm x 25.4 cm strip of
Scotch~ Brand 810~ tape manufactured by the Minnesota
Mining and Manufacturing Company was rolled down over
the imaged test samples using two passes of a 1.82 kg
25 rubber roller. After the two passes, the test samples
were allowed to sit in a controlled environment of 21-C
and 50% RH for 24 hours. Then the Scotch~ Brand 810
tape was laminated image side up to the stage of in
TIMI Release and Adhesion Tester sold by Testing
30 Machines Inc. of Mityville, New York with double coated
tape. The 810~ tape was then removed at a peel angle
of 180-C at 3048 cm/minute. Image analysis was used to
determine the amount of toner which remained anchored
to the coated sheet.
35 Abbreviations
AA - acrylic acid
AIBN - 2-2'-azobisbutyronitrile

16 211~329
.
BMA - butyl methacrylate
EMA - ethyl methacrylate
IPA - isopropyl alcohol
KF2001 - a mercaptofunctional dimethyl siloxane with 4-
5 5 mole % mercapto functionality commerciallyavailable from Shin-Etsu.
MA - methacrylic acid
NAA - methyl acrylate
MEK - methyl ethyl ketone
10 MMA - methyl methacrylate
ODA - octadecyl acrylate
Example l
The composition of Example 1 was prepared in the
following manner:
First, a solvent borne sample was prepared by
charging a 32 oz. reaction bottle with 45 grams of
mercaptofunctional dimethyl siloxane with 4-5 mole %
mercapto functionality commercially available as KF-
2001 from Shin-Etsu, 169 grams of methyl acrylate, 11
20 grams acrylic acid, 335 grams of methyl ethyl ketone
(MEK) and O.56 grams 2-2'-azobisisobutyronitrile
(AIBN). The solution mixture was then purged with
nitrogen for 2 minutes at a rate of 1 L/min, after
which the bottle was sealed. The sealed bottle
25 containing the clear solution was tumbled in a constant
temperature bath for 20 hours at 55 C resulting in a
viscous cloudy white solution.
Thereafter, a waterborne solution was prepared by
filling a gallon jar with 860 grams deionized (DI)
30 water and 9 grams NH40H. Next, 537 grams of the
solvent borne solution (40.0 % solids) was added to the
solution in the gallon jar. The resulting solution was
placed on a shaker and shaken for one-half hour in
order to complete the neutralization. The MEK was then
35 stripped from the resulting viscous solution on a
rotary evaporator at 40 C using an aspirator vacuum to

211~32~
- 17 -
yield 19.0 ~ solids aqueous solution. An additional
amount of DI water was added to obtain
15.0 % solids solution. The ingredients utilized in
forming a solvent borne solution and water borne
5 solution and the amount of the ingredients utilized are
reported in Tables 1 and 2 respectively. The
ingredients of the release coating, the weight
percentage of the ingredients and the test results are
~3~ reported in Table 3.
Examples 2-20
s' The copolymers of Examples 2-20 were prepared in
~,
accordance with the procedure outlined in Example 1.
The ingredients utilized in forming a solvent borne
solution and water borne solution and the amount of the
15 ingredients utilized are reported in Tables l and 2
respectively. The ingredients of the release coating,
the weight percentage of the ingredients and the test
results are reported in Table 3.
.,
2 20
"
" .

211~329
- 18 -
TABLE 1
. . .
¦ Example Ingredients Utilized Amount of Ingredient~
l in Polymerization Utilized ~gms.)
¦ 1 ~MER/AIBN 45/169/11/335/0.56
', l ~
¦ 2 KF2001/MA/AA/NER/AIBN 25/70/10/157.5/0.52 l ~ :
¦ 3 KF2001/MA/AA/MER/AIBN 5~l4D/~ 5~ ¦
¦ 4 KF2001/MA/MAA/MER/AIB 50/140/10/300/0-5
¦ 5 KF2001/MA/NAA/MEK/AIB 52/182/26/390/0.65
¦ 6 KF2001/MA/MAA/MEK/AIB 62/173/25/390/O.fi5
¦ 7 KF2001/MA/NAA/MEK/AIB 60/140/20/330/0.55
l N
¦ 8 KF2001/MA/MAA/MEK/AIB 60/140/10/315/0.53
KF2001/MA/MAA/MEK/AIB 5C/120/10/300/0.5
KF2001/MA/MAA/MNA/NEK 65/130/13/52/390/0.65
¦ 11 KF2001/MA/NAA/NNA/MEK 30/75/7.5/37.5/225/ l
l /AIBN 0.38 ¦¦ - --
¦ 12 KF2001/MA/NAA/MMA/MER 37.5/60/7.5/45/225/
l /AIBN 0.38
¦ 13 KF2001/MA/NAA/NNA/MEK 37.5/45/7.5/60/225/
l /AIBN 0.38 ¦¦
¦ 14 KF2001/MA/MAa/MMA/MEK 37 5/30/7.5/75/225/
/AIBN 0.38
¦ 15 KF2001/MA/MAA/MMA/MEK 39.5/71/7.9/31.6/225/~
¦ 16 KF2001/MA/NAA/NMA/MEK 35.7/78.6/7.1/28.6/
l /AIBN 225/0.38
¦ 1~ KF2001/MA/NAA/MMA/MEK 34.1/81.8/6.8/27.3/225/0.
2 0 ¦ 18 KF2001/NA/MAA/MMA/MEK 32.6/84.8/6.5/26.1/225/0.
¦ 19 KF2001/MA/MAA/MNA/MEK 31.2/87.5/6.2/25/225/0.38
¦ 20 ~A2IBNl/MA/NAA/NMA/M lC 50/100/10/40/300/1.0

2115329
1 9
~ TA~LE 2
~' . _ .
; Example Ingredients Utilized In Amount of Ingredients
Preparatio~ of Water- Utilized ~gms.
.~ borne Solution
1 Polymerl/NH4oH/H2o 537/9/860
5 2 Polymer/NH40H/H2o 537/9.0/645
3 Polymer/NH4oH/~2o 520/8.8/650
4 Polymer/NH4oH/H2o 326/5/540
Polymer/NH40H/HzO 320/9/500
6 Polymer/NH4oH/H2o 320/8/500
10 7 _ Polymer/NH4oH/H2o 321/540/9
8 Polymer/NH4oH/H2o 325/5/540
9 Polymer/NH4oH/H2o 317/5/540 _
Polymer/NH4oa/H2o 320/4.3/500 ll
11 Polymer/NH4oH/H2o 360/7-5/576 ¦¦
15 12 Polymer/NH4oH/H2o 345/4.6/530 ll
13 Polymer/NH4oH/H2o _ 345/4.7/530 ¦¦
14 Polymer/NH4oH/H2o 345/4.6/520
Polymer/NH4oH/H2o 340/5/530 ¦¦
16 Polymer/NH4oH/H2o 340/4-4-/530 ¦¦
20 17 Polymer/NH4oH/H2o 340/4.2/530 ll
18 Polymer/NH4oH/H2o 340/4/530 ¦¦
19 Polymer/NH4oH/H2o 340/4/530
Polymer/NH~oH/H2o 480/5/760
25 .. _ . .. __
I The polymer is the reaction product of KF2001, MA and AA -~
and/or MAA or MMA.
- ;

211~32.9
~= 1 G~ I ~1 ¦ Nl I N
L~ E~ S l X _ _ 0 _ _ N N 0~ t`
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. ..
- 211~329
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- 22 - 2 1 1 ~ 3 2 9
;;~
;, Example 21
The composition of Example 21 was prepared in the
,'~ following manner:
First, a solvent borne sample was prepared by
s charging a 4 ounce glass bottle with 4 grams of 15K
; silicone macromer (SiMac), the preparation of which is
' described in U.S. Patent No. 7,728,571, 16 grams ethyl
methacrylate (EMA), 30 grams methyl ethyl ketone (MEX)
and 0.06 g 2-2'-azobisbutyronitrile (AIBN).
10 Thereafter, the contents of the bottle was purged with
nitrogen gas for two minutes. Then the bottle was
sealed and tumbled in a 55C water bath for 48 hours.
The sample was then diluted to 10% solids for
coating. 40 grams of 40% solids polymer solution, 96
15 grams of toluene and 24 grams of isopropanol (IPA)
~, were added to a 16 ounce wide mouth jar. The mixture
was then shaken to form a homogenous mixture. The
ingredients utilized in forming a solvent borne
solution and the amount of the ingredients utilized are
20 reported in Tables 4 and 5 respectively. The
ingredients of the release coating, the weight
percentage of the ingredients and the test results are
reported in Table 6.
~, Examples 22-27
The copolymers of Examples 22-27 were prepared in
accordance with the procedure outlined in Example 21.
The ingredients utilized in forming a solvent borne
solution and the amount of the ingredients utilized are
reported in Tables 4 and 5 respectively.

211~329
-- 23 --
TABLE 4
. _
Example Ingredients Amount of Ingredients
Utilized in Utilized (gms.)
Polymerization _
21 15K SIMAC/ 4/16/30/0.06
EMA/NEK/AIBN
22 15K SIMAC/ 5/7.5/7.5/30/0.06
EMA/MMA/MEK/AIBN
23 15K SIMAC/ 5/7.5/7.5/30/0.06
EMA/BMA/MEK/AIBN
24 15K SIMAC/ 5/7.5/7.5/30/0.06
EMA/MA/NEK/AIBN
15K SIMAC/ 5/7.5/7.5/30/0.06
MMA/BMA/MEK/AIBN
26 15K SIMAC/EMA 5/11/4/30/0.06
/ODA/MEK/AIBN
27 15 K SIMAC/EMA/ 5/7.5/7.5/30/0.06
AA/MEK/AIBN
TABLE 5
¦Example Ingredients Utilized Amount of Ingredients
In Preparation of Utilized (gms.)
Solvent-borne
l dilution
15 ¦21 polymer2/toluene/IPA 40/96/24
¦22 polymer/toluene/IPA 40/96/24
¦23 polymer/toluene/IPA 40/96/24
24 _ polymer/toluene/IPA 40/96/24
polymer/toluene/IPA 40/96/24
26 polymer!toluene/IPA 40/96/24
27 polymer!toluene/IPA 40/96/24
: ~:
2 The polymer is the reaction product of the
components listed in Table 5 for each example.

--` 2115329
- 24 -
Table 6
E~.Ingredients Wt% Tg T p~ Release g/inch % Toner
~Icdi~ts ' C _ Inibal 3 d ys R ~ceptivib
21EMA/lSKSiMac 80/20 47 A 34 88
22EMA/MMA/lSKSiMac 37.5137.5/25 84 A 70 905 88
23EMA/BMA/lSKSiMac 37.5l37.5l25 41 A 61 123S 90
_ _
24EMA/MA/lSKSiMac37.5137.5125 35 A 23 498 87
25MMA/BMA/lSKSiMac 37.5l37.5l25 57 A 32 954 88
26EMA/ODA/lSKSiMac SS/20/25 A 91 1191_ 96
1 0 27EMA/AA/lSKSiMac37.5/37.5/25 8S A 34 419 99
A=acrylic
COMPARATIVE EXAMPLES 1--5
The samples of Comparative Examples 1-5 comprised
commercially available label stock coated with toner
receptive materials. The samples were tested in
accordance with the procedures outlined above utilizing
acrylic tape. The label stock utilized and the test : .
20 results is reported in Table 7. ~.~

J 3 2 9
- 25 -
Table 7
:
Percentage TonerRelease (g/in)
Receptivity ¦
Ex.180- Peel/90"70-F/50%RH l
per min. Immediate (initial) ¦¦ '
C1l1.88 109
5 c220.47 _ 65
'~ C330.28 80
.~ C440 43 - 160
C551.65 216
I Lazer Printer Labels 30-up stock #5160
manufactured by the Avery Commercial Product
^ Division of Avery International Corporation of
; Azusa, CA.
2 Lazer Label Z-Label 30-up stock ~ LP30101
manufactured by Z-Label of Kansas City, M0.
3 Presaply Laser Printer Labels Dennison 30-up
stock # 37-505 manufactured by Dennison Mfg.
Company of Framington, MA.
4 Hewlett Packard 30-up stock # 92157K manufactured
by the Hewlett-Packard Company. ~ ~`
5 Laser/PPC Labels Rayven 30-up stock # BJ05-G
manufactured by Rayven, Inc. of St. Paul, MN.
The test results indicate that the release coating
25 of the present invention anchors toner much more ~-~
effectively than the release coatings utilized in the
- Comparative Examples. Visually this is seen in a
comparison of Figs. 1 and 2 wherein the samples were
tested in accordance with the Toner Receptivity Test ` ;
30 described above. The asterisk pattern in Fig. 2 was
not substantially anchored compared to Applicants'
release coating shown in Fig. 1. Applicant's
composition utilized in Fig. 1 comprises ~ ;~
MA/MAA/MMA/XF2001 in the following amounts 50/5/20/25.
Thus, the coating of the present invention
significantly decreases the attendant problems
~ associated with toner particles which are dislocated
I from release coatings.
:

--
- 211~329
- 26 -
In summary, a novel toner receptive release
coating is described. Although specific embodiments
and examples of the present invention have been
described herein, it should be borne in mind that these
5 are by way of explanation and illustration and the
present invention is not limited thereby. Certainly,
modifications which are within the ordinary skill in
the art are considered to lie within the scope of this
invention as defined in the following claims including
10 all equivalents.