CA2229165A1 - Articles coated with electrophotographic toner receptive release coatings - Google Patents
Articles coated with electrophotographic toner receptive release coatings Download PDFInfo
- Publication number
- CA2229165A1 CA2229165A1 CA002229165A CA2229165A CA2229165A1 CA 2229165 A1 CA2229165 A1 CA 2229165A1 CA 002229165 A CA002229165 A CA 002229165A CA 2229165 A CA2229165 A CA 2229165A CA 2229165 A1 CA2229165 A1 CA 2229165A1
- Authority
- CA
- Canada
- Prior art keywords
- group
- independently
- same
- aryl
- different
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
- G03G7/006—Substrates for image-receiving members; Image-receiving members comprising only one layer
- G03G7/0073—Organic components thereof
- G03G7/008—Organic components thereof being macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
An article that is capable of accepting and anchoring printed indicia and yet, maintains good release properties. The article of the present invention is coated with a release agent on a substrate such as paper. Release coatings receptive to toner particles emitted by electrophotoconductive devices comprise 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.
Description
CA 0222916~ 1998-02-10 W O 97/09388 PCT~US96/lZ286 ARTICLES COATED WIT~ ELECTROP~IOTOGRAPEIIC
TONER RE(~ E RELEASE COATINGS
Field of the Invention The present invention relates to release coatings and articles coated with such release co~tings In particular, the present invention relates to release coatings which anchor printed indicia, even when cont~cting a repositionable pressure-sensitive adhesive.
Background of the Invention A well known note pad comprises a stack of paper sheets, each having a narrow strip of low-tack pressure-sensitive adhesive ~ cent one edge on its rearside by which the sheets can be temporarily adhered to substrates such as doc~-m~ntc or other articles (often for message-bearing purposes), by which strip of adhesive the sheets are adhered together in the pad. In one pad configuration, all of the strips of adhesive are along one side of the note pad, whereas in another pad configuration the adhesive strip on each s-lcceccive sheet in the pad is along the opposite side ofthe pad as is illustrated in U.S. Patent No. 4,416,392. Note pads in both of these configurations are currently being marketed under the trademark "Post-it" by Minnesota Mining and M~nllf~ctllring Company, St. Paul, Minnesota.
A number of conventional electrophotoconductive devices such as p~ el ~
and copiers employ dry toner. These printers and/or copiers employ toner to form a latent image ~ n~rel~ble from an im~in~ device to a substrate such as paper, tag or label stock. The toned latent image is then subjected to heat fusing in order toobtain the best print quality and toned image density.
Although the reslllting images are often of good quality, there are problems associated with the im~ging processes employed by printers and/or copiers. For example, there is the problem of backgrounding which is the ~ccumlll~tiQn of various unwanted materials such as toner particles on the substrate.
Other conventional devices for office and commercial printing employ inks co.l~;..;..g pigm~ntc or inks along with a carrier vehicle. Examples of such printing CA 0222916~ 1998-02-lO
devices are ink jet, offset, flexographic, duplicators, and electrophotographic printers. The images are applied to the substrate, and the vehicle is absorbed into the substrate and evaporates. Occasionally, the substrate may be subjected to heat to ~onh~nce evaporation of the ink vehicle.
Problems with such printers include "ghosting", in which ink transfer to the substrate is inc~mplete. Typically, the residual ink is transferred to another roller in the printer and subsequently transferred to the substrate out of register. This results in a lightly colored image. Additional problems with ink jet printing is the tendancy of ink to dewet from the substrate, and failure to absorb into the substrate or dry.
In either case, the ink is smeared when a subsequent sheet contacts the image.
When printed sheets are formed into note pads, a release coating is typically used to provide facile removal of the sheets from pads. Such a release coating must be receptive to common writing instruments and printing inks (see U.W. Patent No.
5,154,962 columns 1 and 2 related background). The release coating is s~lected to permit high quality images with specific printing technologies and ready separation from the adhesive.
It has long been industry practice for commercial printing to employ offset printing devices located in centralized production facilities. However, desktop publishing and electronic commerce is rapidly çh~nging the printing industry away from centralized production with a single printing technology to decentralized production using various and multiple printing technologies. For in~t~nce~ a printing requirement may require both offset printing (e.g., a co~ )a,ly logo) followed by xerographic ~;u~,lo~ alion (e.g., a person's name).
In any event, the release-coated substrate must accept and firmly anchor 2~ indicia. The coated substrate must first accept the inidicia without "backg,.,unding"
in electrophotographic devices, "ghosting" in some printers, or smearing in liquid ink printers. Additionally, when formed into pads, the printed indicia must firmly anchor to the substrate without transferring to the adhesive of the preceding note in the pad.
Coatings have been prepared to ~nh~nce ink or toner particle receptivity.
World Patent Application No. US/90/03286 (Josephy et al.) describes a toner , CA 0222916~ 1998-02-10 W O 97/09388 PCTrUS96/12286 receptive coating which can be applied to paper. U.S. Patent No. 5,154,962 describes indicia receptive release co~tingC which are particularly useful for writing with pens co~ g waterbased inks. However no known refernces teach the use of a release coating which accepts and firmly anchors indicia from a wide array of S devices in~ rling offset, ink jet, and xerographic printers. Frequently, customization is performed using sheetfed devices such as laser printers, ink jet printers, and xerographic copiers. This printing is useful when pl epaling printed note pads. Such pads may be prepared using the structures and methods described in U.S. Patent No. 5,382,055. Thus, there currently exists a need for a release 10 coating which will accept and anchor toner particles, offset inks, and other liquid inks and toners.
Summary of the Invention The present invention comprises articles coated release coatings that are 15 capable of accepting and anchoring printed indicia and yet, .n~ c good release plOpelLies. The release coating ofthe present invention is coated onto a substrate such as paper. The articles are of the form described in U.S. Patent No. 5,382,055 and are useful to prepare a small amount of notes or note pads. The release coating COll~ lises a polymer having at least one vinyl polymeric segm~nt having a T~
20 bt;lwt;en -10~C and 65~C and at least one siloxane polymeric segm~nt Plerel~bly, the Tg should be between 200C and 450C of the vinyl polymer se~n~nt In one embodiment of the present invention, the coating is a copolymer which comprises the formula:
(Rl)3 x IGs ~(R3)3 q (G SR2~,~Si (~~Y OSi\(R4SG4)q wherein Rl are monovalent moieties which can independently be the same or di~el ell~ and are selected from the group con.cicting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen, and fluoroalkyl;
CA 0222916~ 1998-02-10 R2 can independently be the same or dirrelen~ and are divalent linking groups;
R3 are monovalent moieties which can independently be the same or di~el elll and are s.olected from the group con~;sL~.Ig of alkyl, aryl, alkylaryl, alkoxy, alkylamino, hydroxyl, hydrogen, and fiuoroalkyl;
R~ 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 di~rt;l GIlL selected from the group coll~;sL"Ig of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoralkyl, hydrogen, and -WSA wherein W is a divalent linking groupand A is defined below; and G2 and G4 are A whe~ein A is a vinyl polymeric se~m~nt or block concictin~
csf-nti~lly of a polymerized free radically polymerized monomer.
In another embodiment of the present invention, the coating comprises a copolymer of D and E monomers copolymerized to form a polymeric backbone with F monomer graf'~ed 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 tbe general formula X-(Y)nSiR~, n)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 l;
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 CA 0222916~ 1998-02-lO
W O 97/09388 PCT~US96/12286 z is a monovalent siloxane polymeric moiety having a number average molecular weight above about 1,000 and is ess~nti~lly unreactive under copolymerization conditions.
The present invention also in~ des a toner receptive article comprising a 5 liner, a release coating and a substrate such as a label mounted over the liner.
Brief Description of the Drawin~s Figure 1 is a rep. ~:se ~~aLion of an embodiment of Applicants' invention tested in accordance with the procedures described below.
Figure 2 is a representation of Avery 30-up stock #5160 that has been tested in accordance with the procedures described below.
Figure 3 is an edge view of a sheet assembly according to the present invention.
Figure 4 is a reduced sectional view taken approximately along line 4-4 of 15 Figure 3.
Description of the Preferred Embodiment(s) The present invention incl~ldes an article coated with a release coating that iscapable of anchoring toner. The release coating has at least one siloxane polymeric 20 segmPnt and at least one vinyl polymeric se mlont having a Tg between -10~C and 65~C. By virtue of its çhpnnic~l composition and structure and the res llt~nt p~.,pe.~ies, the release coating is well-suited to control toner anchorage applications. In particular, it is thought that the silicone segm~nt pl esenL~ a low energy, "siliconized" release surface and the higher energy vinyl polymeric Se m~nt 25 provides the adhesion for the toner particles.
In one embodiment of the present invention, the coating is a copolymer which comprises the formula:
(G S /Si--(O~y--OSi \(R 3 q CA 0222916~ 1998-02-10 W O 97/09388 PCT~US96/12286 Rl are monovalent moieties which can independently be the same or di~rt;. t;lll 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 dirrele;ll~ sPIected S from the group consisting of Cl~ alkyl and llydlo~yl. Most preferably, R, is sPlected from the group con~ietins~ of methyl and butyl.
R2 are divalent linking groups which can independently be the same or dirr~r~llL~ Suitable divalent linking groups include but are not limited to the following: Cl to C10 alkylene, arylene, alkylarylene and alkoxyalkylene. Preferably, 10 R2 is sPIected from the group consisting of Cl 3 alkylene and C,-C10 alkylarylene due to ease of ~yllLlle~is of the compound. Most preferably, R2 is selected from thegroup consisting of-CH2-; 1,3-propylene; and CH2~CH2CH2--R3 are monovalent moieties which can indepPn~lPntly be the same or 1~ dirrt;rell~ which are selected from the group consisting of allcyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl and fluoroalkyl, and hydrogen. Preferably, R3 are monovalent moieties which can in~lepenrlPntly be the same or di~e:~ellL sPlected from the group cc n.~ ~l;..g of C~ alkyl and hydroxyl. Most plere ably, R3 is s~lectecl from the group consisting of methyl and butyl.
R4 are divalent linking groups which can independently be the same or dirrt;re,~. Suitable divalent linking groups include but are not limited to the following: C~ to C~0 alkylene, arylene, alkylarylene and alkoxyalkylene. Preferably, R4 is sPIected from the group consisting of Cl3 alkylene and C7-C10 alkylarylene for reasons of ease of synthesis. Most preferably, R4 is selected from the group 25 co~ ;g of-CH2-; 1,3-propylene; and CH2~H2CH2 G5 and G6 are monovalent moieties which can independently be the same or diLrele.l~ selçcted from the group consisting of alkyl, aryl, alkylaryl, alkoxy, CA 0222916~ 1998-02-10 alkylamino, fluoralkyl, hydrogen, and -WSA wherein W is a divalent linking groupand A is defined below.
W are divalent linking groups. Suitable divalent linking groups inr.l~lde, but are not limited to, Cl to ClO alkylene, alkarylene, arylene, and alkoxyalkylene.5 Preferably, W is selected from the group consi~Li,lg of methylene and propylene.
G2 and G4 are the same or dirrelt;"L and colllplise A. A is a vinyl polymeric seg...~ consisting ess~nti~lly of polymerized free radically polymerizable monom~r. A can comprise either a homopolymer segment or block or a copolymer segm~nt or block. The toner anchorage properties of the coating are determined by the vinyl polymeric segment content. The chemical nature or composition of the vinyl polymeric seg- I~ri " ~ can be modified independent of the release aspect to improve toner anchorage and adhesion to the substrate. Thus, the release coatingcan be chemically tailored to provide a specific level of toner anchorage. The selection of the composition of A is typically based upon the int~.ncled use of the release coating and the properties the release coating must possess in order to accomplish its int~nrled purpose.
A can in~ d~, but is not limited to, those monomers wherein the free radically polymerizable monomer or monomers are chosen such that a vinyl segm~nthas a T,~ or Tl" above about -20~C. The plere-led free radically polymerizable monolllc;l ~ are selected from the group consisting of styrene, methyl meth~r.rylate, methyl acrylate, acrylic acid, meth~t~.rylic acid, acrylonitrile, isobornyl acrylate, isobornyl meth~rylate, N-vinyl pyrrolidone, butyl meth~.rylate, isopropyl m~th~- rylate, vinyl acetate, hydroxy propylacrylate, hydroxy ethyl acrylate andmixtures thereo~
The amount and composition of the vinylic segm~nt to silicone should range from about 98 to about 2 parts preferably, from about 40 to about 60 parts by weight. It is p~c;rel~t;d that the vinyl polymeric segm~nte should have a molecular weight in the range of 2,000 to 80,000, more preferably 5,000 to 50,000.
The release p. o~el Lies of the coating are determined by both the silicone ~ 30 content (weight pelcellLage) present in the copolymer and the molecular weight of the silicone segm~nt, with higher silicone content and/or molecular weight CA 0222916~ 1998-02-10 providing easier release. A copolymer or copolymer blend can, therefore, be I-.hPmic~lly tailored to provide a specific level of release which can be reproduced with con~ictency, 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 the release coating to function properly. Preferably, the silicone polymeric se~mPnt has a number average molecular weight of about 1000 to about 20,000. Most p~trel~ly, the silicone polymeric se~mçnt has a number average molecular weight ranging from about 2,000 to about 15,000. The silicone polymeric segmPnt can comprise about 2 to 60 wt% of the release coatingin order to allow for a wide range of release pe,rc,lnlallce.
In another embodiment of the present invention, the release coating comprises a copolymer of D and E monomers copolymerized to form a polymeric backbone. Gra~ed to the backbone is an F monnm~r. The D and E monomers provide the toner anchorage properties of the coating and the F monomer providesthe release properties.
The D monomer or monomers (there may be more than one) are chosen such that the backbone Tg or Tm is above about -20~C. Representative examples ofD monomers include styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile and acrylic or meth~rylic acid esters of nontertiary alcohols or tertiary alcohols such as mPth~nnl, ethanol, propanol, iso,olopallol, butanol, isobutanol, cyslohPY~nol, benzyl alcohol, dodecanol, heY~-iec~nol, and oct~dec~nol, the alcohols having from 1 to 18 carbon atoms.
Especially ~ rt;l-~d D monomers include methyl meth~çrylate~ butyl meth~rylate~ vinyl acetate, partially hydrolyzed vinyl acetate, methyl acrylate and octadecyl acrylate.
Repl t;~e.lLa~ e E monomers useful in practicing the invention, and which may be used either individually or in co---binalion, include carboxylic acids such as acrylic acid, mPth~rylic acid, itaconic acid, maleic acid, fumaric acid, and 2-carbo~yelllyl acrylate and their ammonium or metal salts; sulfonic or phosphonicacids such as 2-sulfoethyl mpth~rylate~ 3-sulr~,prol yl acrylate, 3-sulropropyl CA 0222916~ 1998-02-10 meth~rylate, styrene sulfonic acid, and vinyl benzyl phosphonic acid and their ~mmnnil-m or metal salts; amides such as acrylamide, meth~rylamide, N,N-dimethyl acrylamide, and N-vinyl pyrrolidone; and monomers having hyd~ yl functionality (e.g., 2-hydloxycl}lyl acrylate, 2-hydroxyethyl meth~-~rylate, S llydl~xy~JIopyl acrylate, and dihydroxypropyl acrylate), ammonium functionality derived from reaction of amine-cG..~ monomers (e.g., N,N,-dimethylaminoethyl methacrylate and vinyl pyridine) with alkylating agents or protic acids, or 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)nSiR(3 m)Zm X is a vinyl group copolymerizable with the D and E monomers.
Y is a divalent linking group.
R comprises hydrogen, lower alkyl groups such as methyl, ethyl, or propyl, lS 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 ees~-nti~lly unreactive under copolymerization conditions.
The plcrcl-cd F monomer may be further defined as having an X group which has the general formula IRl 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~ r CA 0222916~ 1998-02-10 W O 97/09388 PCT~US96/12286 where R3 and R5 are independently lower alkyl, aryl, or fluoroalkyl, where loweralkyl and fluoroalkyl both refer to alkyl groups having from one to three carbonatoms 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 5 to about 700. Preferably, the F monomer has a general formula sPIected from the group consisting ofthe following, where m is 1, 2 or 3, p is zero or 1, R" may be alkyl or hydrogen, and X R, and Z are as defined above:
1~l X--C--O--(cH2)q--(O)p--Si(R)3--mZm wherein q is an integer from 2 to 6;
1~l X--C--O--Si(R)3--mZm 1~l ~}~(CH2)q~(0)p--Si(R)3-mZm wherein q is an integer from zero to 2;
Ol H O R"
X--C--O--CH2--CH2--N--C--N--(cH2)q Si(R)3--mZm wl-c-cin q is an integer from 2 to 6;
X--C--O--CH2--CH2--N--C--~Si(R)3-mZm and Ol OH R"
X--C--O--CH2--CH--CH2--N--(cH2)q--Si(R)3--mZm 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, or may comprise copolymers blended with other CA 0222916~ 1998-02-lO
co"l~ible homopolymers and/or copolymers. The low percentage of silicone cont~ined in the copolymers makes the copolymers readily conlpa~ible with polymers of similar composition to the vinyl Polymeric blocks or segm~nt~ In addition, there are several pairs of rli~imil~r polymers that yield compatible blends S due to specific interaction as described by S. Krause in Polymer Blends, ~c~dçmic Press, New York~ 1978. Introduction of a low level of silicone block onto one ofthese polymers will not infl~lçn~ e compatibility.
In addition, additives, fillers or pigment~ such as ~lllmin~, silica, tit~n~te~ or calcium carbonate may, of course, be added to the copolymer compositions.
The release coating ofthe present invention should provide sl-ffi~i~nt anchorage to anchor at least 50% ofthe toner. It is understood that "subst~ntis-lly"
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 surface release value not greater than about 10 oz./in (11 N/dm). It should be understood that this upper limit applies to use with highly aggressive pressure-sensitive adhesives (PSAs) which have peel adhesion values of 45 N/dm or higher. PSAs as a group fall into three broad categories (1) low (5-15 N/dm), (2) intern ~ te (25-50 N/dm), and (3) high (60-100 plus N/dm) peel adhesion ranges. It is appale-,~ that the degree ofrelease can be s~lected 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/m. (11 N/dm) would be sÇlecte~l Release co~ting.c for less aggressive PSAswould be selected to be correspondingly lower.
The release compositions do not require curing or cros~linking; however, if solvent ,e~ nce is desired for a particular application, cros~linking can be effected by standard methods well-known in the art, such as radiation curing (electron beam or ultraviolet light) or ~h~mic~l cros~linking The release coating compositions may be applied to any suitable backing or liner by means of conventional coating te~hniquçs such as wire-wound rod, direct- 30 gravure, offset gravure, reverse roll, air-k~ife and trailing blade co~tinp Suitable CA 02229l6~ l998-02-lO
W O 97/09388 12 PCT~US96/12286 liners include paper, non-woven fabrics and films of thermoplastic resins such as polyesters, polyamides, polyolefins, polycarbonates and polyvinyl chloride.
In addition, any substrate which can be applied to a liner by a p.es~u~e .sensitive adhesive can be ut~ ecl For example, paper is a suitable substrate.
In a prefe.. ed embodiment, the release coating ofthe present invention is utilized as a co...ponent of label stock. In this p~ t;re. I ~d embodiment, one or more non-contimlQus substrates such as labels are adhered to protective liner by a suitable adhesive. To permit the substrate to be removed from the liner, the release coating of the present invention is coated the liner.
A particularly useful configuration is a sheet assembly wherein the assembly can be described as follows and in reference to Figures 3 and 4. The sheet assembly 10 is illustrated with release coatings 40 on at least one nonadhesive bearing area of the rear surfaces 15 ofthe sheets 12 and 13. The release coatings 40 can be applied strips and are slightly wider than strips 16 of adhesive, and extend transversely of the sheets 12 and 13 parallel to the edges 30, 36 and 37 with each strip releasecoating 40 being a~ cçnt and eYten~ing along an edge of a portion 34 of the sheet 12 and 13 that will be formed by sep~Li~g the sheets 12 and 13 along the paths of weakness 31 and 33, and in a position such that when the rear surfaces 15 of thesheets are placed face to face as illustrated in Figure 3, the strip layers 16 of the 20 adhesive will contact and will be generally centered on the strip release co5~ting~ 40.
Also, as illustrated, the entire front surface 14 of each of the sheets 12 and 13 is coated with a release coating 41, althought such a coating is not necessarily required. For example, the illustrated release coatings 40 on the rear surfaces 15 and the release co~ting~ 41 on the front surface 14 ofthe sheets 12 and 13 are not 25 needed when the layers 16 of the adhesive are of low-tack or repositionable adhesive (e.g., the low-tack adhesives based on tacky, ~l~ctQm~ric copolymer microspheres t~iccl~sed in U.S. Patent Nos. 3,961,140 and 3,857,731). The use ofthe release co~tin~s 40 and 41 allows the use of layers 16 of pressure-sensitiveadhesive that are more aggressive or permanent than repositionable adhesive.
30 Suitable release co~ting~ 40 and 41 are materials and tre~tm~nts those ofthe present invention. Even with layers 16 of aggressive p. ~;s~u. ~;-sensitive adhesive the release CA 0222916~ 1998-02-10 co~ting.C 40 and 41 might not be required if the sheets 12 and 13 are of a material, or are illlpl ~A ~ ed with the release material, from which the layer 16 of adhesive readily releases.
While Figures 3 and 4 I c;preselll a particular configuration of a sheet 5 assembly, such illustrations and descriptions are merely illustrative of the present invention and other embodiments could be contemplated to be within the scope of this invention.
The following examples are illustrative in nature and are not int~nded to limit the invention in any way.
TEST SAMPLES
The polymer solutions of Examples 1 to 19 ~1iccllcced 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 15 per inch. A two roll direct gravure coating was applied to each sample. Two di~elenL roll base papers were ~ltili7ed Supercalendered CIS paper supp1ied by the Simpson Paper Colll,~)a,ly was coated with the diluted polymer solutions of Examples 1 to 4 and m~çhine glazed base paper sold by Akrosil were coated with the diluted polymer solutions of Examples 4 to 19. After co~ting, the base papers 20 were dried at 77~C.
CA 0222916~ 1998-02-10 W O 97/09388 14 PCT~US96/12286 Test Methods Release Properties The release property of an adhesive refers to ease that an adhesive separates from another surface. It is the force required to remove a ~exible adhesive tapefrom a test sample at a specific angle and rate of removal. It is measured in Newtons per clecimeter (N/dm). Two test methods are used to evaluate the releaseand indicia anchorage 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.
1. Release Value Each test sample was conditioned overnight at conct~nt temperature (22~C) and humidity (50% RH). Thereafter, a 5 .08 cm by 25 .4 cm strip of the test sample is l~min~ted to a consLa-~l 90~ angle jig commercially available as the Deltron Ball Slide from the J.R. Brass Co. of Eden Prairie, MN with double coated tape. Then a 2.54 cm strip of a PSA coated (#810 tape, co"~".e--;ially available from the ~.c.ci n~e ofthis application) test tape was rolled down onto the l~min~te with a 1.82 kg rubber roller. The force required to remove this tape at 90~ and 30.5 crn/minutewas then measured was measured by a Sintech/Instron Tensile Tester System conllll~l.,;ally available from Sintech Corporation, a division of MTS Systems Co~ol~lion, Research Triangle Park, North Carolina.
2. Toner Receptivity Testin~
The toner receptivity ofthe test sarnples was aeses.sed by printing on a 21.6 cm x 27.9 cm test sarnple an asterisk pattern, i.e., (****), in an Hewlett Packard LaserJet II printer. The imaged coated sheets then sat overnight in a controllede.~virolllllent of 21~C and 50% RH. Thereafter, a 2.54 cm x 25.4 cm strip of ScotchTM Brand 810TM tape m~nllf~ctllred by the Minnesota Mining and M~mlf~ rin~ COlll~ was rolled down over the imaged test samples using two passes of a 1.82 kg rubber roller. After the two passes, the test samples were CA 0222916~ 1998-02-lO
W O 97/09388 PCT~US96/12286 allowed to sit in a controlled environment of 21 ~C and 50% RH for 24 hours. Then the ScotchTM Brand 810TM tape was l~min~ted image side up to the stage of in TIMI Release and Adhesion Tester sold by Testing ~hines 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 indicia which ~ ed anchored to the coated sheet.
Abbreviations AA - acrylic acid 10 AIBN- 2-21-azobisbutyronitrile BMA - butyl m~th~rrylate EMA - ethyl meth~çrylate IPA - isopropyl alcohol KF2001 - a ~llel-,a~Lofunctional dimethyl siloxane with 4-5 mole % mercapto functionality co,.. --el cially available from Shin-Etsu.
MA - meth~crylic acid MAA - methyl acrylate MEK - methyl ethyl ketone MMA - methyl meth~crylate 20 ODA- octadecyl acrylate Example 1 The composition of Example 1 was prepared in the following manner:
First, a solvent borne sample was plepa-ed by charging a 32 oz. reaction 25 bottle with 45 grams of mercaptofunctional dimethyl siloxane with 4-5 mole l..elcapto functionality commercially available as KF-2001 from Shin-Etsu, 169 grams of methyl acrylate, 11 grams acrylic acid, 335 grams of methyl ethyl ketone (MEK) and 0.56 grams 2-2'-azobisisobuLy~ul iL.ile (AIBN). The solution mixture was then purged with nitrogen for 2 mim-tes at a rate of 1 L/min, after which the - 30 bottle was sealed. The sealed bottle co.. l;.il.;.. g the clear solution was tumbled in a CA 0222916~ l99X-02-10 collsL~ temperature bath for 20 hours at 55~C re~ tin~ in a viscous cloudy whitesolution.
Thereafter, a waterborne solution was pl ~pal ed by filling a gallon jar with 860 grams deionized (DI) water and 9 grams NH4OH. Next, 53 7 grams of the 5 solvent borne solution (40.0 % solids) was added to the solution in the gallon jar.
The res~llting solution was placed on a shaker and shaken for one-half hour in order tG con'lplete the neutra~ation. The i~ was then stripped from the resllitin~
viscous solution on a rotary evaporator at 40~C using an aspirator vacuum to yield 19.0 % solids aqueous solution. An additional amount of DI water was added to 10 obtain 15.0 % solids solution. The ingredients utilized in forming a solvent borne solution and water borne solution and the amount of the ingredients utilized arereported in Tables 1 and 2 respectively. The ingredients of the release coating, the weight percentage of the ingredients and the test results are reported in Table 3 .
Examples 2-20 The copolymers of Examples 2-20 were prepared in accordance with the procedure oullh~ed in Example 1. The ingredients utilized in forming a solvent borne solution and water borne solution and the amount of the ingredients utilized are reported in Tables 1 and 2 respectively. The ingredients of the release coating, 20 the weight percentage of the ingredients and the test results are reported in Table 3 .
W O 97/09388 PCT~US96/12286 F.Y~mrle Ingredients Utilized in Polymerization Amount of Ingredients Utilized (~ms.) 1 RUF2001~IAIA~ EK~ ~IBN 45/169/11/335/0.56 2 RUF200L~AIA~ EK~ AIBN 25/70/10/157.5/0.52 3 ~F2001~IAJAI~EK~AIBN 50/140/20/315/0.53 4 ~F2001AhL~VL~AJ~DEK~AIBN 50/140/10/300/0.5 ~UF2001~VL~VAA/~DEK~AIBN 52/182/26/390/0.65 6 ~F2001AVL~AvL~A~DEK~AlBN 62/173/25/390/0.65 7 RUF2001rhL~VL~A~DEK~AlBN 60/140/20/330/0.55 8 ~F20011YL~ML~A/~DEK~AIBN 60/140/10/315/0.53 9 ~UF2001~YL~VL~A/~DEK~AlBN 50/120/10/300/0.5 ~UF2001~U~VU~A/O{hLAl~CK~AlBN 65/130/13/52/390/0.65 11 EUF2001D\lA/~LA,VOlbLAV~EK~AlBN 30/75/7.5/37.5/225/0.38 12 ~UF2001/~L~/~L~AVOlhlAv~EK~AlBN 37.5/60/7.5/45/225/0.38 13 K~F20011hL~AhLA~VOlhLAv~EK~AlBN 37.5/45/7.5/60/225/0.38 14 EUF2001~ XU~AVO~bLA~EK~AlBN 37.5/30/7.5/75/225/0.38 ~UF200 _ K~AIBN 39.5/71/7.9/31.6/225/0.38 16 ~F2001/~AhU~A/~ A~rE 1AlBN 35.7/78.6/7.1/28.6/225/0.38 17 ~UF2001~kLA~YLAA~Qf~lAl~EK~AlBN 34.1/81.8/6.8/27.3/225/0.38 18 EUF2001~ U~A/OD~A~EK~AIBN 32.6/84.8/6.5/26.1/225/0.38 19 ~F2001/~AhU~A~ AI~E 1AlBN 31.2/87.5/6.2/25/225/0.38 K F2001_K;/AIBN 50/100/10/40/300/1.0 W O 97/09388 18 PCTnJS96/12286 FY~mrle Ingredients Utilized In Amount of Ingredients Utilized Pl~a,~Lion of Water-borne (gms.) Solution Polymerl/NH40H/H20 537/9/860 2 Polymer/NH40H/H20 537/9.0/645 3 Polymer/NH4oH/H2o 520/8.8/650 4 Polymer/NH4oEvH2o 326/5/540 Polymer/NH4oHlH2o 320/9/500 6 Polymer/NEI40H/H20 320/8/500 7 Polymer/NH4oH/H2o 321/540/9 8 Polymer/NH40EIlH20 325/5/540 g PolymerlNH4oHtH2o 317/5/540 Polymer/NH4oHlH2o 320/4.3/500 11 Polymer/NH4oH/H2o 360/7.5/576 12 Polymer/NH4oH~H2o 345/4.6/530 13 Polymer/NH4oHlH2o 345/4-7/530 14 Polymer/NH4o~vH2o 345/4.6/520 Polymer/NH4oH/H2o 340/5/530 16 Polymer/NH4oHtH2o 340/4 4 /530 17 Polymer/NH4oH/H2o 340/4.2/530 18 Polymer/NH4oEvH2o 340/4/530 19 Polymer/NH4oHlEI2o 340/4/530 PolymertNH4oHlH2o 480/5/760 1 The polymer is the reaction product of KF2001, MA and AA and/or MAA or MI~LA
W O 97/09388 PCT~US96/12286 Table 3 Ex.Ingredients Wt % Tg~ C Tape Release Pe~ ge Ingredients g/inch Indicia rece~Livily Initial 8MA/KF2001/MAA 70/30/5 ? A - 22 9MA/KF2001/MAA/ 60/25/10/5 ? A - 58 MAA
10MA/KF2001/MAAt 50/25/20/5 40 A 14 92 MAA
11MAlKF2001/MAAt 50/20/25/5 44 A 23 78 MAA
MAA
MAA
14MA/K~2001/MAA/ 20/25/50/5 30 A 157 50 MAA
MAA
MAA
MAA
MAA
MAA
MAA
A = Acrylic B = Rubber s CA 0222916~ 1998-02-10 Fx~mrle21 The composition of Example 21 was pl ~pal ed in the following manner:
First, a solvent borne sample was prepared by charging a 4 ounce glass bottle with 4 grams of 15K silicone macromer (SiMac), the pl~palaLion of which is described in U.S. Patent No. 7,728,571, 16 grams ethyl meth~rrylate ~EMA), 30 grams methyl ethyl ketone ~MEK) and 0 06 g 2-2'-aGobi~l,u~lu~ ile (AIBN).
Thereafter, the contents of the bottle was purged with nitrogen gas for two ~ esThen the bottle was sealed and t~lmhled in a 55~C water bath for 48 hours.
The sample was then diluted to 10% solids for co~tin~ 40 grams of 40%
solids polymer solution, 96 grams oftoluene and 24 grams of isoplopanol (~A) were added to a 16 ounce wide mouth jar. The mixture was then shaken to form a homogenous rnixture. The ingredients utilized in forming a solvent borne solution and the amount of the ingredients utilized are reported in Tables 4 and 5 re~ c~,Li~ely. The ingredients of the release coating, the weight percentage of the ingredients and the test results are reported in Table 6.
FY~mples 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.
TABL;E 4 FYz-mple Ingredients Utilized in Polylll~ Lion Amount of Ingredients Utilized (~ms.) 21 15KSIMAC/EM~K/AIBN 4/16/30/0.06 22 15KSIMACt~M~K/AIBN 5/7.5/7.5/30/0.06 23 15KSIMAC/EMA/BMA/MEK/AIBN 5/7.5/7.5/30/0.06 24 15KSlMAC/ EMA/MA/~K/AIBN 5/7.5/7.5/30/0.06 15KSIMAC/ M~L9JBMA/MEK/AIBN 5/7.5/7.5/30/0.06 26 15KSIMAC/EMA/ODA/MEK/AIBN 5/11/4/30/0.06 27 15KSIMAC/EMA/ MEK/AIBN 5/7.5M.5/30/0.06 CA 0222916~ 1998-02-lO
Example Ingredients Utilized In Preparation of Amount of Ingredients Solvent-borne dilution Utilized (~ms.) 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 5 example.
Table 6 Ex. Ingredients Wt% Tg ~ Tape Release Indicia% Toner Ingredients C g/ nch RecepLivily In tial 21 EMA/15KSiMac 80/20 47 A 3~ 88 22 EMA/MMA/15K 37.5/37.5/25 84 A 70 88 SiMAC
23 EMA/BMA/15K 37 5/37.5/25 41 A 61 90 SiMac 24 EMA/MA/15KSi 37.5/37.5/25 35 A 23 87 Mac MMA/BMA/15K 37.5/37.5/25 57 A 32 88 SiMac SiMac 27 EMA/AA/15KSi 37.5/37.5/25 85 A 34 99 Mac A=acrylic Example 28 A sheet assembly particularly adapted to be printed on both sides in the 10 types of printers described above was made which had the structure illustrated in Figure 1 except that four instead of two layers 16 of pressure sensitive adhesive were placed in spaced relationship on each sheet 12 and 13. The sheets 12 and 13 CA 0222916~ 1998-02-10 were each 20 pound bond paper and were each about eight and one half by 11 inches in size, with the sheet 13 being slightly longer so that it projected about 0.1 inch past the edge 37. The layers 16 of pressure sensitive adhesive were microsphere structured copolymer adhesive described in U.S. Patent 3,691,140 (Silver) dispersed in n-heptane at 8 percent solids. The layers of release coating 40 were cro~link~cl Syl Off7676 coated at 20 percent solids in 2-butanone. The paper was first primed with a vinyl solution co.l~ g zinc oxide. The release coating 41 was a polymer described in U.S.S.N. 08/040876 Example 1, except the composition was KF2001/M~ 25/50/20/5 dispersed in 2-butanone ~Example 20) to 1.5 percent solids. The adhesive was coated to provide an adhesion comparable toPost-it(~ notes (i.e., apl)loxil-lated 0.6 N/dm adhesion to glass) in 0.75-inch (1.9 cm) wide stripes 16 e~t~n~ling the full width ofthe sheets 12 and 13. The opposing strip of release coating 40 was coated with a gravure cylinder to provide 1.25-inch (3.2 cm.) wide stripes ~ n~ling the full width ofthe sheets 12 and 13. The materials were coated on a wide web and subsequently converted and folded to form the sheet assemblies 10.
The initial release ofthe sheet was 166 g/m. Subsequently, the sheets were printed using ink jet, a xerographic, and offset printers. In each case, the test pattern was a solid block of black ink or toner. The ink jet printer was an HP
1200C color ink jet printer commercially available from Hewlett-Packard, Palo Alto, CA. The xerographic printer was a Lanier 6540 copier cornmercially available from Lanier Worldwide, Inc., Atlanta, GA.
The percent of inidicia receptivity were as follows:
~ 1200 C 100 percent Lanier 6540 92 percent The test results indicate that the release coating of the present invention anchors indicia much more effectively than the release coatings utilized in the Co.llpal~ e F.~mples Visually this is seen in a comparison of Figs. 1 and 2 wher~,;ll the samples were tested in accordance with the Toner Receptivity Test described above. The asterisk pattern in Fig. 2 was not subst~nti~lly anchored col..pal~d to Applicants' release coating shown in Fig. 1. Applicant's composition CA 02229l6~ l998-02-lO
utilized in Fig. 1 comprises ~2001 in the following amounts 50/5/20/25.
Thus, the coating of the present invention ~ignifis~ntly decreases the att~n-l~nt problems associated with indicia when printed and subsequently used as a 5 stack of pressure-sensitive notes.
In sl-mm~ry, a novel article coated with a unique toner receptive release coating is described. Although specific embodiments and examples of the present invention have been described herein, it should be born in mind that these are by way of explanation and illustration and the present invention is not limited thereby.
10 Certainly, modifications which are within the o,di,la,y skill in the art are considered to lie within the scope of this invention as defined in the following claims inC ~ ing all equivalents.
TONER RE(~ E RELEASE COATINGS
Field of the Invention The present invention relates to release coatings and articles coated with such release co~tings In particular, the present invention relates to release coatings which anchor printed indicia, even when cont~cting a repositionable pressure-sensitive adhesive.
Background of the Invention A well known note pad comprises a stack of paper sheets, each having a narrow strip of low-tack pressure-sensitive adhesive ~ cent one edge on its rearside by which the sheets can be temporarily adhered to substrates such as doc~-m~ntc or other articles (often for message-bearing purposes), by which strip of adhesive the sheets are adhered together in the pad. In one pad configuration, all of the strips of adhesive are along one side of the note pad, whereas in another pad configuration the adhesive strip on each s-lcceccive sheet in the pad is along the opposite side ofthe pad as is illustrated in U.S. Patent No. 4,416,392. Note pads in both of these configurations are currently being marketed under the trademark "Post-it" by Minnesota Mining and M~nllf~ctllring Company, St. Paul, Minnesota.
A number of conventional electrophotoconductive devices such as p~ el ~
and copiers employ dry toner. These printers and/or copiers employ toner to form a latent image ~ n~rel~ble from an im~in~ device to a substrate such as paper, tag or label stock. The toned latent image is then subjected to heat fusing in order toobtain the best print quality and toned image density.
Although the reslllting images are often of good quality, there are problems associated with the im~ging processes employed by printers and/or copiers. For example, there is the problem of backgrounding which is the ~ccumlll~tiQn of various unwanted materials such as toner particles on the substrate.
Other conventional devices for office and commercial printing employ inks co.l~;..;..g pigm~ntc or inks along with a carrier vehicle. Examples of such printing CA 0222916~ 1998-02-lO
devices are ink jet, offset, flexographic, duplicators, and electrophotographic printers. The images are applied to the substrate, and the vehicle is absorbed into the substrate and evaporates. Occasionally, the substrate may be subjected to heat to ~onh~nce evaporation of the ink vehicle.
Problems with such printers include "ghosting", in which ink transfer to the substrate is inc~mplete. Typically, the residual ink is transferred to another roller in the printer and subsequently transferred to the substrate out of register. This results in a lightly colored image. Additional problems with ink jet printing is the tendancy of ink to dewet from the substrate, and failure to absorb into the substrate or dry.
In either case, the ink is smeared when a subsequent sheet contacts the image.
When printed sheets are formed into note pads, a release coating is typically used to provide facile removal of the sheets from pads. Such a release coating must be receptive to common writing instruments and printing inks (see U.W. Patent No.
5,154,962 columns 1 and 2 related background). The release coating is s~lected to permit high quality images with specific printing technologies and ready separation from the adhesive.
It has long been industry practice for commercial printing to employ offset printing devices located in centralized production facilities. However, desktop publishing and electronic commerce is rapidly çh~nging the printing industry away from centralized production with a single printing technology to decentralized production using various and multiple printing technologies. For in~t~nce~ a printing requirement may require both offset printing (e.g., a co~ )a,ly logo) followed by xerographic ~;u~,lo~ alion (e.g., a person's name).
In any event, the release-coated substrate must accept and firmly anchor 2~ indicia. The coated substrate must first accept the inidicia without "backg,.,unding"
in electrophotographic devices, "ghosting" in some printers, or smearing in liquid ink printers. Additionally, when formed into pads, the printed indicia must firmly anchor to the substrate without transferring to the adhesive of the preceding note in the pad.
Coatings have been prepared to ~nh~nce ink or toner particle receptivity.
World Patent Application No. US/90/03286 (Josephy et al.) describes a toner , CA 0222916~ 1998-02-10 W O 97/09388 PCTrUS96/12286 receptive coating which can be applied to paper. U.S. Patent No. 5,154,962 describes indicia receptive release co~tingC which are particularly useful for writing with pens co~ g waterbased inks. However no known refernces teach the use of a release coating which accepts and firmly anchors indicia from a wide array of S devices in~ rling offset, ink jet, and xerographic printers. Frequently, customization is performed using sheetfed devices such as laser printers, ink jet printers, and xerographic copiers. This printing is useful when pl epaling printed note pads. Such pads may be prepared using the structures and methods described in U.S. Patent No. 5,382,055. Thus, there currently exists a need for a release 10 coating which will accept and anchor toner particles, offset inks, and other liquid inks and toners.
Summary of the Invention The present invention comprises articles coated release coatings that are 15 capable of accepting and anchoring printed indicia and yet, .n~ c good release plOpelLies. The release coating ofthe present invention is coated onto a substrate such as paper. The articles are of the form described in U.S. Patent No. 5,382,055 and are useful to prepare a small amount of notes or note pads. The release coating COll~ lises a polymer having at least one vinyl polymeric segm~nt having a T~
20 bt;lwt;en -10~C and 65~C and at least one siloxane polymeric segm~nt Plerel~bly, the Tg should be between 200C and 450C of the vinyl polymer se~n~nt In one embodiment of the present invention, the coating is a copolymer which comprises the formula:
(Rl)3 x IGs ~(R3)3 q (G SR2~,~Si (~~Y OSi\(R4SG4)q wherein Rl are monovalent moieties which can independently be the same or di~el ell~ and are selected from the group con.cicting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl, hydrogen, and fluoroalkyl;
CA 0222916~ 1998-02-10 R2 can independently be the same or dirrelen~ and are divalent linking groups;
R3 are monovalent moieties which can independently be the same or di~el elll and are s.olected from the group con~;sL~.Ig of alkyl, aryl, alkylaryl, alkoxy, alkylamino, hydroxyl, hydrogen, and fiuoroalkyl;
R~ 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 di~rt;l GIlL selected from the group coll~;sL"Ig of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoralkyl, hydrogen, and -WSA wherein W is a divalent linking groupand A is defined below; and G2 and G4 are A whe~ein A is a vinyl polymeric se~m~nt or block concictin~
csf-nti~lly of a polymerized free radically polymerized monomer.
In another embodiment of the present invention, the coating comprises a copolymer of D and E monomers copolymerized to form a polymeric backbone with F monomer graf'~ed 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 tbe general formula X-(Y)nSiR~, n)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 l;
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 CA 0222916~ 1998-02-lO
W O 97/09388 PCT~US96/12286 z is a monovalent siloxane polymeric moiety having a number average molecular weight above about 1,000 and is ess~nti~lly unreactive under copolymerization conditions.
The present invention also in~ des a toner receptive article comprising a 5 liner, a release coating and a substrate such as a label mounted over the liner.
Brief Description of the Drawin~s Figure 1 is a rep. ~:se ~~aLion of an embodiment of Applicants' invention tested in accordance with the procedures described below.
Figure 2 is a representation of Avery 30-up stock #5160 that has been tested in accordance with the procedures described below.
Figure 3 is an edge view of a sheet assembly according to the present invention.
Figure 4 is a reduced sectional view taken approximately along line 4-4 of 15 Figure 3.
Description of the Preferred Embodiment(s) The present invention incl~ldes an article coated with a release coating that iscapable of anchoring toner. The release coating has at least one siloxane polymeric 20 segmPnt and at least one vinyl polymeric se mlont having a Tg between -10~C and 65~C. By virtue of its çhpnnic~l composition and structure and the res llt~nt p~.,pe.~ies, the release coating is well-suited to control toner anchorage applications. In particular, it is thought that the silicone segm~nt pl esenL~ a low energy, "siliconized" release surface and the higher energy vinyl polymeric Se m~nt 25 provides the adhesion for the toner particles.
In one embodiment of the present invention, the coating is a copolymer which comprises the formula:
(G S /Si--(O~y--OSi \(R 3 q CA 0222916~ 1998-02-10 W O 97/09388 PCT~US96/12286 Rl are monovalent moieties which can independently be the same or di~rt;. t;lll 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 dirrele;ll~ sPIected S from the group consisting of Cl~ alkyl and llydlo~yl. Most preferably, R, is sPlected from the group con~ietins~ of methyl and butyl.
R2 are divalent linking groups which can independently be the same or dirr~r~llL~ Suitable divalent linking groups include but are not limited to the following: Cl to C10 alkylene, arylene, alkylarylene and alkoxyalkylene. Preferably, 10 R2 is sPIected from the group consisting of Cl 3 alkylene and C,-C10 alkylarylene due to ease of ~yllLlle~is of the compound. Most preferably, R2 is selected from thegroup consisting of-CH2-; 1,3-propylene; and CH2~CH2CH2--R3 are monovalent moieties which can indepPn~lPntly be the same or 1~ dirrt;rell~ which are selected from the group consisting of allcyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl and fluoroalkyl, and hydrogen. Preferably, R3 are monovalent moieties which can in~lepenrlPntly be the same or di~e:~ellL sPlected from the group cc n.~ ~l;..g of C~ alkyl and hydroxyl. Most plere ably, R3 is s~lectecl from the group consisting of methyl and butyl.
R4 are divalent linking groups which can independently be the same or dirrt;re,~. Suitable divalent linking groups include but are not limited to the following: C~ to C~0 alkylene, arylene, alkylarylene and alkoxyalkylene. Preferably, R4 is sPIected from the group consisting of Cl3 alkylene and C7-C10 alkylarylene for reasons of ease of synthesis. Most preferably, R4 is selected from the group 25 co~ ;g of-CH2-; 1,3-propylene; and CH2~H2CH2 G5 and G6 are monovalent moieties which can independently be the same or diLrele.l~ selçcted from the group consisting of alkyl, aryl, alkylaryl, alkoxy, CA 0222916~ 1998-02-10 alkylamino, fluoralkyl, hydrogen, and -WSA wherein W is a divalent linking groupand A is defined below.
W are divalent linking groups. Suitable divalent linking groups inr.l~lde, but are not limited to, Cl to ClO alkylene, alkarylene, arylene, and alkoxyalkylene.5 Preferably, W is selected from the group consi~Li,lg of methylene and propylene.
G2 and G4 are the same or dirrelt;"L and colllplise A. A is a vinyl polymeric seg...~ consisting ess~nti~lly of polymerized free radically polymerizable monom~r. A can comprise either a homopolymer segment or block or a copolymer segm~nt or block. The toner anchorage properties of the coating are determined by the vinyl polymeric segment content. The chemical nature or composition of the vinyl polymeric seg- I~ri " ~ can be modified independent of the release aspect to improve toner anchorage and adhesion to the substrate. Thus, the release coatingcan be chemically tailored to provide a specific level of toner anchorage. The selection of the composition of A is typically based upon the int~.ncled use of the release coating and the properties the release coating must possess in order to accomplish its int~nrled purpose.
A can in~ d~, but is not limited to, those monomers wherein the free radically polymerizable monomer or monomers are chosen such that a vinyl segm~nthas a T,~ or Tl" above about -20~C. The plere-led free radically polymerizable monolllc;l ~ are selected from the group consisting of styrene, methyl meth~r.rylate, methyl acrylate, acrylic acid, meth~t~.rylic acid, acrylonitrile, isobornyl acrylate, isobornyl meth~rylate, N-vinyl pyrrolidone, butyl meth~.rylate, isopropyl m~th~- rylate, vinyl acetate, hydroxy propylacrylate, hydroxy ethyl acrylate andmixtures thereo~
The amount and composition of the vinylic segm~nt to silicone should range from about 98 to about 2 parts preferably, from about 40 to about 60 parts by weight. It is p~c;rel~t;d that the vinyl polymeric segm~nte should have a molecular weight in the range of 2,000 to 80,000, more preferably 5,000 to 50,000.
The release p. o~el Lies of the coating are determined by both the silicone ~ 30 content (weight pelcellLage) present in the copolymer and the molecular weight of the silicone segm~nt, with higher silicone content and/or molecular weight CA 0222916~ 1998-02-10 providing easier release. A copolymer or copolymer blend can, therefore, be I-.hPmic~lly tailored to provide a specific level of release which can be reproduced with con~ictency, 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 the release coating to function properly. Preferably, the silicone polymeric se~mPnt has a number average molecular weight of about 1000 to about 20,000. Most p~trel~ly, the silicone polymeric se~mçnt has a number average molecular weight ranging from about 2,000 to about 15,000. The silicone polymeric segmPnt can comprise about 2 to 60 wt% of the release coatingin order to allow for a wide range of release pe,rc,lnlallce.
In another embodiment of the present invention, the release coating comprises a copolymer of D and E monomers copolymerized to form a polymeric backbone. Gra~ed to the backbone is an F monnm~r. The D and E monomers provide the toner anchorage properties of the coating and the F monomer providesthe release properties.
The D monomer or monomers (there may be more than one) are chosen such that the backbone Tg or Tm is above about -20~C. Representative examples ofD monomers include styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile and acrylic or meth~rylic acid esters of nontertiary alcohols or tertiary alcohols such as mPth~nnl, ethanol, propanol, iso,olopallol, butanol, isobutanol, cyslohPY~nol, benzyl alcohol, dodecanol, heY~-iec~nol, and oct~dec~nol, the alcohols having from 1 to 18 carbon atoms.
Especially ~ rt;l-~d D monomers include methyl meth~çrylate~ butyl meth~rylate~ vinyl acetate, partially hydrolyzed vinyl acetate, methyl acrylate and octadecyl acrylate.
Repl t;~e.lLa~ e E monomers useful in practicing the invention, and which may be used either individually or in co---binalion, include carboxylic acids such as acrylic acid, mPth~rylic acid, itaconic acid, maleic acid, fumaric acid, and 2-carbo~yelllyl acrylate and their ammonium or metal salts; sulfonic or phosphonicacids such as 2-sulfoethyl mpth~rylate~ 3-sulr~,prol yl acrylate, 3-sulropropyl CA 0222916~ 1998-02-10 meth~rylate, styrene sulfonic acid, and vinyl benzyl phosphonic acid and their ~mmnnil-m or metal salts; amides such as acrylamide, meth~rylamide, N,N-dimethyl acrylamide, and N-vinyl pyrrolidone; and monomers having hyd~ yl functionality (e.g., 2-hydloxycl}lyl acrylate, 2-hydroxyethyl meth~-~rylate, S llydl~xy~JIopyl acrylate, and dihydroxypropyl acrylate), ammonium functionality derived from reaction of amine-cG..~ monomers (e.g., N,N,-dimethylaminoethyl methacrylate and vinyl pyridine) with alkylating agents or protic acids, or 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)nSiR(3 m)Zm X is a vinyl group copolymerizable with the D and E monomers.
Y is a divalent linking group.
R comprises hydrogen, lower alkyl groups such as methyl, ethyl, or propyl, lS 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 ees~-nti~lly unreactive under copolymerization conditions.
The plcrcl-cd F monomer may be further defined as having an X group which has the general formula IRl 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~ r CA 0222916~ 1998-02-10 W O 97/09388 PCT~US96/12286 where R3 and R5 are independently lower alkyl, aryl, or fluoroalkyl, where loweralkyl and fluoroalkyl both refer to alkyl groups having from one to three carbonatoms 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 5 to about 700. Preferably, the F monomer has a general formula sPIected from the group consisting ofthe following, where m is 1, 2 or 3, p is zero or 1, R" may be alkyl or hydrogen, and X R, and Z are as defined above:
1~l X--C--O--(cH2)q--(O)p--Si(R)3--mZm wherein q is an integer from 2 to 6;
1~l X--C--O--Si(R)3--mZm 1~l ~}~(CH2)q~(0)p--Si(R)3-mZm wherein q is an integer from zero to 2;
Ol H O R"
X--C--O--CH2--CH2--N--C--N--(cH2)q Si(R)3--mZm wl-c-cin q is an integer from 2 to 6;
X--C--O--CH2--CH2--N--C--~Si(R)3-mZm and Ol OH R"
X--C--O--CH2--CH--CH2--N--(cH2)q--Si(R)3--mZm 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, or may comprise copolymers blended with other CA 0222916~ 1998-02-lO
co"l~ible homopolymers and/or copolymers. The low percentage of silicone cont~ined in the copolymers makes the copolymers readily conlpa~ible with polymers of similar composition to the vinyl Polymeric blocks or segm~nt~ In addition, there are several pairs of rli~imil~r polymers that yield compatible blends S due to specific interaction as described by S. Krause in Polymer Blends, ~c~dçmic Press, New York~ 1978. Introduction of a low level of silicone block onto one ofthese polymers will not infl~lçn~ e compatibility.
In addition, additives, fillers or pigment~ such as ~lllmin~, silica, tit~n~te~ or calcium carbonate may, of course, be added to the copolymer compositions.
The release coating ofthe present invention should provide sl-ffi~i~nt anchorage to anchor at least 50% ofthe toner. It is understood that "subst~ntis-lly"
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 surface release value not greater than about 10 oz./in (11 N/dm). It should be understood that this upper limit applies to use with highly aggressive pressure-sensitive adhesives (PSAs) which have peel adhesion values of 45 N/dm or higher. PSAs as a group fall into three broad categories (1) low (5-15 N/dm), (2) intern ~ te (25-50 N/dm), and (3) high (60-100 plus N/dm) peel adhesion ranges. It is appale-,~ that the degree ofrelease can be s~lected 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/m. (11 N/dm) would be sÇlecte~l Release co~ting.c for less aggressive PSAswould be selected to be correspondingly lower.
The release compositions do not require curing or cros~linking; however, if solvent ,e~ nce is desired for a particular application, cros~linking can be effected by standard methods well-known in the art, such as radiation curing (electron beam or ultraviolet light) or ~h~mic~l cros~linking The release coating compositions may be applied to any suitable backing or liner by means of conventional coating te~hniquçs such as wire-wound rod, direct- 30 gravure, offset gravure, reverse roll, air-k~ife and trailing blade co~tinp Suitable CA 02229l6~ l998-02-lO
W O 97/09388 12 PCT~US96/12286 liners include paper, non-woven fabrics and films of thermoplastic resins such as polyesters, polyamides, polyolefins, polycarbonates and polyvinyl chloride.
In addition, any substrate which can be applied to a liner by a p.es~u~e .sensitive adhesive can be ut~ ecl For example, paper is a suitable substrate.
In a prefe.. ed embodiment, the release coating ofthe present invention is utilized as a co...ponent of label stock. In this p~ t;re. I ~d embodiment, one or more non-contimlQus substrates such as labels are adhered to protective liner by a suitable adhesive. To permit the substrate to be removed from the liner, the release coating of the present invention is coated the liner.
A particularly useful configuration is a sheet assembly wherein the assembly can be described as follows and in reference to Figures 3 and 4. The sheet assembly 10 is illustrated with release coatings 40 on at least one nonadhesive bearing area of the rear surfaces 15 ofthe sheets 12 and 13. The release coatings 40 can be applied strips and are slightly wider than strips 16 of adhesive, and extend transversely of the sheets 12 and 13 parallel to the edges 30, 36 and 37 with each strip releasecoating 40 being a~ cçnt and eYten~ing along an edge of a portion 34 of the sheet 12 and 13 that will be formed by sep~Li~g the sheets 12 and 13 along the paths of weakness 31 and 33, and in a position such that when the rear surfaces 15 of thesheets are placed face to face as illustrated in Figure 3, the strip layers 16 of the 20 adhesive will contact and will be generally centered on the strip release co5~ting~ 40.
Also, as illustrated, the entire front surface 14 of each of the sheets 12 and 13 is coated with a release coating 41, althought such a coating is not necessarily required. For example, the illustrated release coatings 40 on the rear surfaces 15 and the release co~ting~ 41 on the front surface 14 ofthe sheets 12 and 13 are not 25 needed when the layers 16 of the adhesive are of low-tack or repositionable adhesive (e.g., the low-tack adhesives based on tacky, ~l~ctQm~ric copolymer microspheres t~iccl~sed in U.S. Patent Nos. 3,961,140 and 3,857,731). The use ofthe release co~tin~s 40 and 41 allows the use of layers 16 of pressure-sensitiveadhesive that are more aggressive or permanent than repositionable adhesive.
30 Suitable release co~ting~ 40 and 41 are materials and tre~tm~nts those ofthe present invention. Even with layers 16 of aggressive p. ~;s~u. ~;-sensitive adhesive the release CA 0222916~ 1998-02-10 co~ting.C 40 and 41 might not be required if the sheets 12 and 13 are of a material, or are illlpl ~A ~ ed with the release material, from which the layer 16 of adhesive readily releases.
While Figures 3 and 4 I c;preselll a particular configuration of a sheet 5 assembly, such illustrations and descriptions are merely illustrative of the present invention and other embodiments could be contemplated to be within the scope of this invention.
The following examples are illustrative in nature and are not int~nded to limit the invention in any way.
TEST SAMPLES
The polymer solutions of Examples 1 to 19 ~1iccllcced 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 15 per inch. A two roll direct gravure coating was applied to each sample. Two di~elenL roll base papers were ~ltili7ed Supercalendered CIS paper supp1ied by the Simpson Paper Colll,~)a,ly was coated with the diluted polymer solutions of Examples 1 to 4 and m~çhine glazed base paper sold by Akrosil were coated with the diluted polymer solutions of Examples 4 to 19. After co~ting, the base papers 20 were dried at 77~C.
CA 0222916~ 1998-02-10 W O 97/09388 14 PCT~US96/12286 Test Methods Release Properties The release property of an adhesive refers to ease that an adhesive separates from another surface. It is the force required to remove a ~exible adhesive tapefrom a test sample at a specific angle and rate of removal. It is measured in Newtons per clecimeter (N/dm). Two test methods are used to evaluate the releaseand indicia anchorage 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.
1. Release Value Each test sample was conditioned overnight at conct~nt temperature (22~C) and humidity (50% RH). Thereafter, a 5 .08 cm by 25 .4 cm strip of the test sample is l~min~ted to a consLa-~l 90~ angle jig commercially available as the Deltron Ball Slide from the J.R. Brass Co. of Eden Prairie, MN with double coated tape. Then a 2.54 cm strip of a PSA coated (#810 tape, co"~".e--;ially available from the ~.c.ci n~e ofthis application) test tape was rolled down onto the l~min~te with a 1.82 kg rubber roller. The force required to remove this tape at 90~ and 30.5 crn/minutewas then measured was measured by a Sintech/Instron Tensile Tester System conllll~l.,;ally available from Sintech Corporation, a division of MTS Systems Co~ol~lion, Research Triangle Park, North Carolina.
2. Toner Receptivity Testin~
The toner receptivity ofthe test sarnples was aeses.sed by printing on a 21.6 cm x 27.9 cm test sarnple an asterisk pattern, i.e., (****), in an Hewlett Packard LaserJet II printer. The imaged coated sheets then sat overnight in a controllede.~virolllllent of 21~C and 50% RH. Thereafter, a 2.54 cm x 25.4 cm strip of ScotchTM Brand 810TM tape m~nllf~ctllred by the Minnesota Mining and M~mlf~ rin~ COlll~ was rolled down over the imaged test samples using two passes of a 1.82 kg rubber roller. After the two passes, the test samples were CA 0222916~ 1998-02-lO
W O 97/09388 PCT~US96/12286 allowed to sit in a controlled environment of 21 ~C and 50% RH for 24 hours. Then the ScotchTM Brand 810TM tape was l~min~ted image side up to the stage of in TIMI Release and Adhesion Tester sold by Testing ~hines 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 indicia which ~ ed anchored to the coated sheet.
Abbreviations AA - acrylic acid 10 AIBN- 2-21-azobisbutyronitrile BMA - butyl m~th~rrylate EMA - ethyl meth~çrylate IPA - isopropyl alcohol KF2001 - a ~llel-,a~Lofunctional dimethyl siloxane with 4-5 mole % mercapto functionality co,.. --el cially available from Shin-Etsu.
MA - meth~crylic acid MAA - methyl acrylate MEK - methyl ethyl ketone MMA - methyl meth~crylate 20 ODA- octadecyl acrylate Example 1 The composition of Example 1 was prepared in the following manner:
First, a solvent borne sample was plepa-ed by charging a 32 oz. reaction 25 bottle with 45 grams of mercaptofunctional dimethyl siloxane with 4-5 mole l..elcapto functionality commercially available as KF-2001 from Shin-Etsu, 169 grams of methyl acrylate, 11 grams acrylic acid, 335 grams of methyl ethyl ketone (MEK) and 0.56 grams 2-2'-azobisisobuLy~ul iL.ile (AIBN). The solution mixture was then purged with nitrogen for 2 mim-tes at a rate of 1 L/min, after which the - 30 bottle was sealed. The sealed bottle co.. l;.il.;.. g the clear solution was tumbled in a CA 0222916~ l99X-02-10 collsL~ temperature bath for 20 hours at 55~C re~ tin~ in a viscous cloudy whitesolution.
Thereafter, a waterborne solution was pl ~pal ed by filling a gallon jar with 860 grams deionized (DI) water and 9 grams NH4OH. Next, 53 7 grams of the 5 solvent borne solution (40.0 % solids) was added to the solution in the gallon jar.
The res~llting solution was placed on a shaker and shaken for one-half hour in order tG con'lplete the neutra~ation. The i~ was then stripped from the resllitin~
viscous solution on a rotary evaporator at 40~C using an aspirator vacuum to yield 19.0 % solids aqueous solution. An additional amount of DI water was added to 10 obtain 15.0 % solids solution. The ingredients utilized in forming a solvent borne solution and water borne solution and the amount of the ingredients utilized arereported in Tables 1 and 2 respectively. The ingredients of the release coating, the weight percentage of the ingredients and the test results are reported in Table 3 .
Examples 2-20 The copolymers of Examples 2-20 were prepared in accordance with the procedure oullh~ed in Example 1. The ingredients utilized in forming a solvent borne solution and water borne solution and the amount of the ingredients utilized are reported in Tables 1 and 2 respectively. The ingredients of the release coating, 20 the weight percentage of the ingredients and the test results are reported in Table 3 .
W O 97/09388 PCT~US96/12286 F.Y~mrle Ingredients Utilized in Polymerization Amount of Ingredients Utilized (~ms.) 1 RUF2001~IAIA~ EK~ ~IBN 45/169/11/335/0.56 2 RUF200L~AIA~ EK~ AIBN 25/70/10/157.5/0.52 3 ~F2001~IAJAI~EK~AIBN 50/140/20/315/0.53 4 ~F2001AhL~VL~AJ~DEK~AIBN 50/140/10/300/0.5 ~UF2001~VL~VAA/~DEK~AIBN 52/182/26/390/0.65 6 ~F2001AVL~AvL~A~DEK~AlBN 62/173/25/390/0.65 7 RUF2001rhL~VL~A~DEK~AlBN 60/140/20/330/0.55 8 ~F20011YL~ML~A/~DEK~AIBN 60/140/10/315/0.53 9 ~UF2001~YL~VL~A/~DEK~AlBN 50/120/10/300/0.5 ~UF2001~U~VU~A/O{hLAl~CK~AlBN 65/130/13/52/390/0.65 11 EUF2001D\lA/~LA,VOlbLAV~EK~AlBN 30/75/7.5/37.5/225/0.38 12 ~UF2001/~L~/~L~AVOlhlAv~EK~AlBN 37.5/60/7.5/45/225/0.38 13 K~F20011hL~AhLA~VOlhLAv~EK~AlBN 37.5/45/7.5/60/225/0.38 14 EUF2001~ XU~AVO~bLA~EK~AlBN 37.5/30/7.5/75/225/0.38 ~UF200 _ K~AIBN 39.5/71/7.9/31.6/225/0.38 16 ~F2001/~AhU~A/~ A~rE 1AlBN 35.7/78.6/7.1/28.6/225/0.38 17 ~UF2001~kLA~YLAA~Qf~lAl~EK~AlBN 34.1/81.8/6.8/27.3/225/0.38 18 EUF2001~ U~A/OD~A~EK~AIBN 32.6/84.8/6.5/26.1/225/0.38 19 ~F2001/~AhU~A~ AI~E 1AlBN 31.2/87.5/6.2/25/225/0.38 K F2001_K;/AIBN 50/100/10/40/300/1.0 W O 97/09388 18 PCTnJS96/12286 FY~mrle Ingredients Utilized In Amount of Ingredients Utilized Pl~a,~Lion of Water-borne (gms.) Solution Polymerl/NH40H/H20 537/9/860 2 Polymer/NH40H/H20 537/9.0/645 3 Polymer/NH4oH/H2o 520/8.8/650 4 Polymer/NH4oEvH2o 326/5/540 Polymer/NH4oHlH2o 320/9/500 6 Polymer/NEI40H/H20 320/8/500 7 Polymer/NH4oH/H2o 321/540/9 8 Polymer/NH40EIlH20 325/5/540 g PolymerlNH4oHtH2o 317/5/540 Polymer/NH4oHlH2o 320/4.3/500 11 Polymer/NH4oH/H2o 360/7.5/576 12 Polymer/NH4oH~H2o 345/4.6/530 13 Polymer/NH4oHlH2o 345/4-7/530 14 Polymer/NH4o~vH2o 345/4.6/520 Polymer/NH4oH/H2o 340/5/530 16 Polymer/NH4oHtH2o 340/4 4 /530 17 Polymer/NH4oH/H2o 340/4.2/530 18 Polymer/NH4oEvH2o 340/4/530 19 Polymer/NH4oHlEI2o 340/4/530 PolymertNH4oHlH2o 480/5/760 1 The polymer is the reaction product of KF2001, MA and AA and/or MAA or MI~LA
W O 97/09388 PCT~US96/12286 Table 3 Ex.Ingredients Wt % Tg~ C Tape Release Pe~ ge Ingredients g/inch Indicia rece~Livily Initial 8MA/KF2001/MAA 70/30/5 ? A - 22 9MA/KF2001/MAA/ 60/25/10/5 ? A - 58 MAA
10MA/KF2001/MAAt 50/25/20/5 40 A 14 92 MAA
11MAlKF2001/MAAt 50/20/25/5 44 A 23 78 MAA
MAA
MAA
14MA/K~2001/MAA/ 20/25/50/5 30 A 157 50 MAA
MAA
MAA
MAA
MAA
MAA
MAA
A = Acrylic B = Rubber s CA 0222916~ 1998-02-10 Fx~mrle21 The composition of Example 21 was pl ~pal ed in the following manner:
First, a solvent borne sample was prepared by charging a 4 ounce glass bottle with 4 grams of 15K silicone macromer (SiMac), the pl~palaLion of which is described in U.S. Patent No. 7,728,571, 16 grams ethyl meth~rrylate ~EMA), 30 grams methyl ethyl ketone ~MEK) and 0 06 g 2-2'-aGobi~l,u~lu~ ile (AIBN).
Thereafter, the contents of the bottle was purged with nitrogen gas for two ~ esThen the bottle was sealed and t~lmhled in a 55~C water bath for 48 hours.
The sample was then diluted to 10% solids for co~tin~ 40 grams of 40%
solids polymer solution, 96 grams oftoluene and 24 grams of isoplopanol (~A) were added to a 16 ounce wide mouth jar. The mixture was then shaken to form a homogenous rnixture. The ingredients utilized in forming a solvent borne solution and the amount of the ingredients utilized are reported in Tables 4 and 5 re~ c~,Li~ely. The ingredients of the release coating, the weight percentage of the ingredients and the test results are reported in Table 6.
FY~mples 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.
TABL;E 4 FYz-mple Ingredients Utilized in Polylll~ Lion Amount of Ingredients Utilized (~ms.) 21 15KSIMAC/EM~K/AIBN 4/16/30/0.06 22 15KSIMACt~M~K/AIBN 5/7.5/7.5/30/0.06 23 15KSIMAC/EMA/BMA/MEK/AIBN 5/7.5/7.5/30/0.06 24 15KSlMAC/ EMA/MA/~K/AIBN 5/7.5/7.5/30/0.06 15KSIMAC/ M~L9JBMA/MEK/AIBN 5/7.5/7.5/30/0.06 26 15KSIMAC/EMA/ODA/MEK/AIBN 5/11/4/30/0.06 27 15KSIMAC/EMA/ MEK/AIBN 5/7.5M.5/30/0.06 CA 0222916~ 1998-02-lO
Example Ingredients Utilized In Preparation of Amount of Ingredients Solvent-borne dilution Utilized (~ms.) 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 5 example.
Table 6 Ex. Ingredients Wt% Tg ~ Tape Release Indicia% Toner Ingredients C g/ nch RecepLivily In tial 21 EMA/15KSiMac 80/20 47 A 3~ 88 22 EMA/MMA/15K 37.5/37.5/25 84 A 70 88 SiMAC
23 EMA/BMA/15K 37 5/37.5/25 41 A 61 90 SiMac 24 EMA/MA/15KSi 37.5/37.5/25 35 A 23 87 Mac MMA/BMA/15K 37.5/37.5/25 57 A 32 88 SiMac SiMac 27 EMA/AA/15KSi 37.5/37.5/25 85 A 34 99 Mac A=acrylic Example 28 A sheet assembly particularly adapted to be printed on both sides in the 10 types of printers described above was made which had the structure illustrated in Figure 1 except that four instead of two layers 16 of pressure sensitive adhesive were placed in spaced relationship on each sheet 12 and 13. The sheets 12 and 13 CA 0222916~ 1998-02-10 were each 20 pound bond paper and were each about eight and one half by 11 inches in size, with the sheet 13 being slightly longer so that it projected about 0.1 inch past the edge 37. The layers 16 of pressure sensitive adhesive were microsphere structured copolymer adhesive described in U.S. Patent 3,691,140 (Silver) dispersed in n-heptane at 8 percent solids. The layers of release coating 40 were cro~link~cl Syl Off7676 coated at 20 percent solids in 2-butanone. The paper was first primed with a vinyl solution co.l~ g zinc oxide. The release coating 41 was a polymer described in U.S.S.N. 08/040876 Example 1, except the composition was KF2001/M~ 25/50/20/5 dispersed in 2-butanone ~Example 20) to 1.5 percent solids. The adhesive was coated to provide an adhesion comparable toPost-it(~ notes (i.e., apl)loxil-lated 0.6 N/dm adhesion to glass) in 0.75-inch (1.9 cm) wide stripes 16 e~t~n~ling the full width ofthe sheets 12 and 13. The opposing strip of release coating 40 was coated with a gravure cylinder to provide 1.25-inch (3.2 cm.) wide stripes ~ n~ling the full width ofthe sheets 12 and 13. The materials were coated on a wide web and subsequently converted and folded to form the sheet assemblies 10.
The initial release ofthe sheet was 166 g/m. Subsequently, the sheets were printed using ink jet, a xerographic, and offset printers. In each case, the test pattern was a solid block of black ink or toner. The ink jet printer was an HP
1200C color ink jet printer commercially available from Hewlett-Packard, Palo Alto, CA. The xerographic printer was a Lanier 6540 copier cornmercially available from Lanier Worldwide, Inc., Atlanta, GA.
The percent of inidicia receptivity were as follows:
~ 1200 C 100 percent Lanier 6540 92 percent The test results indicate that the release coating of the present invention anchors indicia much more effectively than the release coatings utilized in the Co.llpal~ e F.~mples Visually this is seen in a comparison of Figs. 1 and 2 wher~,;ll the samples were tested in accordance with the Toner Receptivity Test described above. The asterisk pattern in Fig. 2 was not subst~nti~lly anchored col..pal~d to Applicants' release coating shown in Fig. 1. Applicant's composition CA 02229l6~ l998-02-lO
utilized in Fig. 1 comprises ~2001 in the following amounts 50/5/20/25.
Thus, the coating of the present invention ~ignifis~ntly decreases the att~n-l~nt problems associated with indicia when printed and subsequently used as a 5 stack of pressure-sensitive notes.
In sl-mm~ry, a novel article coated with a unique toner receptive release coating is described. Although specific embodiments and examples of the present invention have been described herein, it should be born in mind that these are by way of explanation and illustration and the present invention is not limited thereby.
10 Certainly, modifications which are within the o,di,la,y skill in the art are considered to lie within the scope of this invention as defined in the following claims inC ~ ing all equivalents.
Claims (12)
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:
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 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.
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 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.
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.
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 maleicanhydride.
6. An image receiving article comprising:
(a) a liner having a front face and a back face;
(b) a layer of release coating coated over a portion of the front face of a liner wherein the release coating comprising a polymer having at least one vinyl polymeric segment having a Tg between -10°C and 65°C present at a weight percent great enough to provide the copolymer with the capability of substantially anchoring toner particles emitted by an electrophotoconductive device and at least one siloxane polymeric segment having a number average molecular weight above about 100 and is present at a weight percent great enough to provide the copolymer with a surface release value not greater than about 11 Newtons/dm;
(c) a layer of pressure sensitive adhesive; and (d) at least one layer of substrate having a front and a back face.
(a) a liner having a front face and a back face;
(b) a layer of release coating coated over a portion of the front face of a liner wherein the release coating comprising a polymer having at least one vinyl polymeric segment having a Tg between -10°C and 65°C present at a weight percent great enough to provide the copolymer with the capability of substantially anchoring toner particles emitted by an electrophotoconductive device and at least one siloxane polymeric segment having a number average molecular weight above about 100 and is present at a weight percent great enough to provide the copolymer with a surface release value not greater than about 11 Newtons/dm;
(c) a layer of pressure sensitive adhesive; and (d) at least one layer of substrate having a front and a back face.
7. The image receiving article of Claim 6 wherein said polymer of the release coating is a copolymer comprising having the formula:
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 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
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 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
8. The image receiving article of Claim 6 wherein said polymer of the release coating 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.
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.
9. The image receiving article of Claim 8 wherein said D monomer of the polymer of the release coating 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 image receiving article of Claim 8 wherein said E monomer of the polymer of the release coating is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide, N,N-dimethylacrylamide, methacrylonitrile and maleic anhydride.
11. The image receiving article of Claim 6 wherein said substrate is labelstock.
12. A sheet assembly comprising a release coating on at least one nonadhesive bearing area of the rear surfaces of a sheet wherein the release coating comprises the formula:
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 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.
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 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52539895A | 1995-09-08 | 1995-09-08 | |
| US08/525,398 | 1995-09-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2229165A1 true CA2229165A1 (en) | 1997-03-13 |
Family
ID=24093090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002229165A Abandoned CA2229165A1 (en) | 1995-09-08 | 1996-07-26 | Articles coated with electrophotographic toner receptive release coatings |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0848737A1 (en) |
| JP (1) | JP2000500164A (en) |
| KR (1) | KR19990044418A (en) |
| AU (1) | AU6680796A (en) |
| CA (1) | CA2229165A1 (en) |
| WO (1) | WO1997009388A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6074747A (en) | 1995-06-06 | 2000-06-13 | Avery Dennison Corporation | Ink-imprintable release coatings, and pressure sensitive adhesive constructions |
| CN109627414B (en) * | 2018-12-11 | 2021-08-24 | 长春安旨科技有限公司 | High-temperature post-curing polyurethane composite material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1339225C (en) * | 1988-11-30 | 1997-08-05 | Timothy A. Mertens | Indicia-receptive low adhesion backsize |
| US5032460A (en) * | 1989-08-14 | 1991-07-16 | Minnesota Mining And Manufacturing Company | Method of making vinyl-silicone copolymers using mercapto functional silicone chain-transfer agents and release coatings made therewith |
| CA2117914A1 (en) * | 1992-05-12 | 1993-11-25 | Kanta Kumar | Polymers in cosmetics and personal care products |
| US5468477A (en) * | 1992-05-12 | 1995-11-21 | Minnesota Mining And Manufacturing Company | Vinyl-silicone polymers in cosmetics and personal care products |
| CA2156164A1 (en) * | 1993-02-16 | 1994-09-01 | Lori A. Bilski | System comprising release agent and high peel adhesion repositionable adhesive |
| CA2115329A1 (en) * | 1993-03-31 | 1994-10-01 | Joseph Thomas Bartusiak | Electrophotographic toner receptive release coatings |
-
1996
- 1996-07-26 AU AU66807/96A patent/AU6680796A/en not_active Abandoned
- 1996-07-26 EP EP96926778A patent/EP0848737A1/en not_active Withdrawn
- 1996-07-26 WO PCT/US1996/012286 patent/WO1997009388A1/en not_active Application Discontinuation
- 1996-07-26 KR KR1019980701662A patent/KR19990044418A/en not_active Application Discontinuation
- 1996-07-26 CA CA002229165A patent/CA2229165A1/en not_active Abandoned
- 1996-07-26 JP JP9511184A patent/JP2000500164A/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0848737A1 (en) | 1998-06-24 |
| JP2000500164A (en) | 2000-01-11 |
| KR19990044418A (en) | 1999-06-25 |
| AU6680796A (en) | 1997-03-27 |
| WO1997009388A1 (en) | 1997-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5154962A (en) | Indicia-receptive low adhesion backsize | |
| US6482510B1 (en) | Digital printable and releasable form construction and composition useful thereto | |
| US5744207A (en) | Articles coated with electrophotographic toner receptive release coatings | |
| US6926957B2 (en) | Water-based ink-receptive coating | |
| EP1159652A1 (en) | Image receptor medium containing ethylene vinyl acetate carbon monoxide terpolymer | |
| US6406787B1 (en) | Digital printable and releasable form construction and composition useful thereto | |
| EP0227417A2 (en) | Light-transmissive recording medium and image formation method using the same | |
| EP0618509B1 (en) | Electrophotographic toner receptive release coatings | |
| US4958173A (en) | Toner receptive coating | |
| CA2229165A1 (en) | Articles coated with electrophotographic toner receptive release coatings | |
| CA2248702A1 (en) | Electrostatically charged imaging manifold | |
| KR0159272B1 (en) | Indicia-receptive low adhesion backsize | |
| EP0415849B1 (en) | Printing sheet | |
| MXPA98001706A (en) | Articles coated with dependable coatings capable of accepting organic pigment electrofotograf | |
| EP0858005B1 (en) | Toner receptive sheet for digital offset printing | |
| ZA200200854B (en) | Digitally printable releasable coating and form construction using this coating. | |
| EP0858004A1 (en) | Toner-receptive media for digital offset printing | |
| EP0950537A2 (en) | A transparent recording sheet having an image-receptive coating, an anti-static coating, and a removable opaque anti-static adhesive strip | |
| CA2050973A1 (en) | Receptor sheet for thermal mass transfer imaging |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |