CA2178818A1 - An electrostatic toner receptor layer of rubber modified thermoplastic - Google Patents
An electrostatic toner receptor layer of rubber modified thermoplasticInfo
- Publication number
- CA2178818A1 CA2178818A1 CA002178818A CA2178818A CA2178818A1 CA 2178818 A1 CA2178818 A1 CA 2178818A1 CA 002178818 A CA002178818 A CA 002178818A CA 2178818 A CA2178818 A CA 2178818A CA 2178818 A1 CA2178818 A1 CA 2178818A1
- Authority
- CA
- Canada
- Prior art keywords
- graphic article
- imaged
- layer
- coated
- film
- 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
-
- 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
-
- 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
- G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
- G03G7/0013—Inorganic components thereof
-
- 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
- G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
- G03G7/002—Organic components thereof
- G03G7/0026—Organic components thereof being macromolecular
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24851—Intermediate layer is discontinuous or differential
- Y10T428/24868—Translucent outer layer
- Y10T428/24876—Intermediate layer contains particulate material [e.g., pigment, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
- Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Abstract
An electrostatic toner receptor layer comprised of a blend of an acrylic resin, a vinyl resin, a solution or dispersion grade rubber and a plasticizer. The resulting receptor layer provides durability and flexibility when applied to a crack resistance film for subsequent application to soft-sided vehicles.
Description
~'0 95/18992 2 1 7 8 8 1 8 PCT/US94113724 An Elec~.~sldlic Toner Receptor Layer of Rubber Modified Ther.~-oplaalic Technical Field This invention is directed to an el~ ldlic toner receptor layer 5 and more particularly to a receptor layer comprising a rubber modified Illellllopldalil~
Background of the l.,.r~ iol~
Previously, high quality ~raphics were limited to lon~ runs to rcduce cost or short runs, wherein the costs were excessive. With the 10 advent of S~,o~cl,p,i"~ graphics, production of limited quantities of high quality graphics were readily arrL~ Fu,~l,e""ore, Scotchcal 8620 and 8640 receptor-coated films have permitted the use of such high quality graphics for limited quantity ~r F' _: -ns for rigid surfaces.
These marking fiims comprise a vinyl film base that is top coated with 15 a solvent ~IIGIIIIOPId~ blend of acrylic copolymer, vinyl chloride/vinyl acetate copoly."Gr, and a pld~ er. This top coating is a non-tacky solid that is ",oderd~ly flexible at room temperature. Above 70C, the ~I IGl l l lopld nil~ melts and bonds onto r l~ "d ~i., toners that were previously printed onto a transfer media. After cooling, the marking 20 films can be separated from the transfer media and the toners are retained by the marking film.
Ideally, the ~IIGIIIIOPId:~;C layer (1) adheres well to the base film, ~2) does not adhere to untoned (unimaged) areas on the transfer media, ~3) does not destroy the physical prope, ~ies of the base film 25 (tensile, r,:o.~ld~ion, color, etc.), (4) bonds co,..~,kit~ly to the toners,permitting removal of toner from the transfer media and not p~-~"illi~1g toner removal durin~ normal ~ ion, (5) is not tacky during normal use, and (6) is con",d~iLI~ with additional ope,d~ic,ns, such as clear coating or PIGIIIaSk;I~9~
WO g5/18992 PCT/US9~/13724 --However, continuously flexed surfaces, such as the ~lailSpOI L~
and vehicles with F! .~ ed polyvinyl chloride coated fabric sides prevalent in a large portion of the world have proven to be a probiem for the receptor-coated fiims. Typicaiiy, the pl~ ed polyvinyl 5 chioride coated fabric is a ~ lllOpla~LiC material fiexed, rolied, flapped, and cold-flexed numerous times during the lifetime of the siding. Hence, any graphic image adhered or otherwise attached to such a siding must be capable of withstanding identical stresses without failure.
Summary of the l~ lio.~
Briefly, in one aspect of the present invention, the receptor iâyer Golllpli.~s a blend of an acrylic resin, 8 vinyl resin, a solution or dispersion grade rubber, and a pla~Li~ el coated on a crack resistant pressure sensitive adhesive backed film. Convenientiy, the receptor layer now allows Sc~L~ )ri"L graphics to be applied to p~ d polyvinyl chloride coâted fabric for use on soft-sided vehicles.
Advantageously, the final graphic ima~e articie, that is, the imaged feceptor layer on the crack le~ lanCe pressure sensitive adhesive backed film, together with any app,op~iaLt: protective clear coat, applied to a ~la;~ d polyvinyl chioride-coated fabric siding wiil withstand extreme env;.u"",~"lal stresses that occur on soft-sided vehicles, particuisriy at low temperatures, that present Sc~l~,llpli materiais do not v~ al~d.
D~sc,i~.liu,~ of the r~ère~ed E L
An image is generally applied to the inventive receptor layer by thermally bonding 61~ LaLic toners that were previously printed onto a transfer media as decribed for example in U.S. Patent Nos.
5,114,520 and 5,262,259 and such dr,~ ,Lion is i".,or~,o,a~t:d herein by referènce. After cooling, the receptor coated marking film can be ~0 95/18992 2 1 7 8 8 ~ 8 PCTIUS94/13724 separated from the transfer media and the toners are retained by the receptor coated marking film.
r,~rt,ably, the final graphic image article ~;ll,:.ldnds the following tests:
11~ coating a-ll,t:,e"ce; and (2) crack ,t~i~lance at -20C.
When the final graphic image article is co,,,,urised of more than one panel, for example, side-by-side panels with overlapping seams or one panel partially or totally adhered over another panel, then the final graphic imased article pl~r~ldbly ~ ;Lll~lands the following additional test: I3) overlap acll~ ,e of one layer of imaged film to an underlying layer of imaged film. A Upanel'' is defined as a sheet of an imaged receptor layer on a crack l~ lallCe pressure sensitive adhesive backed film, which may or may not include an ap~up~ial~a protective clear coat.
~Coating aJl,e,~,lce"is defined as achieving a 4B or 5B rating per ASTM test D3359, Test Method B after 16 hours of water i"""e~ion, whereby the sample is i"""edial~ly tested after removal from the water and towel drying. ''Crack l~ lance~is defined as minimum damage to the surface after repeated flexing and pl~r~aLly after 4000 double flexes in a flex tester operating at -20C per DIN
53359 Test B. ~verlap"adherence Is d~Lt:llll:.led in acco,ddnc~ with ASTM D1000, except that the imaged film to be tested is adhered to a like portion of imaged film that has been adhered to PVC-coated fabric substrate. This multilayer co",posile, that is, where at least two panels overlap each other, is aged at least 16 hours at 65C prior to testing. The overlap a.ll,erence is preferably at least 1.0 pounds per inch width for all colors and non-colored portions.
Marking films having a urethane base, such as Scotchcal 190 marking film, are used on pla~ d polyvinyl chloride coated fabrics.
While urethane based films have ouL~Lal1~" ,9 crack ~esi;.Làl1ce, W095118992 2 1 78~ 1 8 Pr~sgvl3724~
pl..~ici~t:r ,t:Di,la"ce and moisture resistance, standard ScoLcl,p,i"L
receptor coatings do not work on urethane based or other crack resistant marking films.
When e!~ ,u:ila~ic toner receptor coatings used on conventional 5 vinyl chloride based marking films are applied to crack resistant films used for marking soft sided vehicles, such coated films fail to meet the crack ~ La,1ce criteria and will often fail the coating adherence criteria. HoweYer, when a crack resistant film, such as a urethane-based film is coated with the inventive receptor, the coated film retains 10 su~Lal "y all of the plu~J~,Lit!s of the base film without such a coating and more importantly, the coated film meets the above p~rullllallce criteria. Using urethane-based films without any receptor coating generally is ullaccerjla~lc for imaging by toner transfer because hot la",i"aLion results in no release from untoned areas and 15 poor overlap adhesion in toned areas.
It is well known that the flexibility of Lllellllùpld~lic coatings can be increased by adding r~ '' ' ~ . The flexibility of the coatings used for vinyl film at room temperature can be partially attributable to pla~ ,. Increased levels of pldali~ er have been shown to improve 20 crack ,~ a"ce st low temperatures. However, with higher pla loading, particularily in an acrylic-cor, , ,g coating, the surface can become tacky at normal handling temperatures. This surface tack can cause handling difficulties, dirt pickup, less abrasion ,~ai~la,~ce, poorer internal strength, image dr,l...lli"alion, and roll blocking problems.
Publicly known flexible polyvinyl chloride substrates typicaliy contain high levels (60 to 100 parts per hundred parts resin) of monomeric pl~ r. This ~ono",eric pla;,Li..i~r tends to migrate into any graphic marking film adhered to the surface, thus resulting in the same types of problems ~OG~I~d with addition of excess 30 plaaLi~ dr.
~V095/18992 2 1 7 8 8 1 8 PCTIUS94/13724 lt has been discovered that a receptor coating co"",osilion co"".,i~ing 8 blend of acrylic resin, a vinyl resin, a solution or d;~,eraion grade rubber, and a pla~ r coated onto a urethane-based film will meet the pe~ ru, n~a,lce criteria, while ",i";",i~;"g 5 pla~ er infiuence at normal handling temperâtures~ P(ert:la~ the receptor coating cor"~û~ilion has at least 5% to 55% of a solution or d;~per~ion grade rubber, more plt:r~lably, 7% to 30% of a solution or dispersion grade rubber. It is within this range that the resultant printed graphic meets crack ~ Lu,~ce criteria.
Once the el~ u~lulic toner receptor coating has been applied to a crack resistant film, a toner image can then be thermally llar"r~"~d onto this receptor layer. A wear coat, protective layer or clear coat can then be applied by technique known to those skilled in the art, such as screen printing clear coats, or flood coating clear 1 5 coats.
Fu~ II,t:""or~, it has been found that i"co, ,~oralion of a graphics overlay colllpGaite (a premask layer adjacent to a protective layer), as described, for example in Attorney Docket No. 49516 USA 4A, assigned to the same assignee as the present rF' lion, can enhance 20 the overlap adhesion of finished graphic image panels.
Particularly useful acrylic resins for the image receptor coating include methyl methacrylate polymers and copolymers, such as Acryloids B-44 and B-48, col"",~" 'ly available from Rohm and Haas, and a methyl ",t ll,~ ylate/ethyl acrylate/N-t-butylacrylamide.
25 Particularly useful vinyl resins for the image receptor coating including vinyl chloride/vinyl acetate cOpOly,lle:,a, such as those c~"""elica:ly available from Union Carbide, under the trade d~siy,,aliul~ 'UCAR':
Any ~i~,,e,aion or solution grade rubber can be used in the present invention and suitable examples include but are not limited to solution 30 cll'~ illal~d rubbers (such as, epi~,l,lo,ul,ydrin rubber co""~,e, "y woss/lsss2 2 ~ 7 8 8 ~ 8 Pcrluss4/13724 ~
available as Hydrin CG from Zeon Chemicals) and urethane di~Jel:,;o rubbers (such as NeoPac R-9000 available from Zeneca Chemical~.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts 5 thereof recited in these e~.a",, '-~ as well as other conditions and details, should not be construed to unduly limit this invention. All materials are C~llllllt:l, "y available or known to those skilled in the art unless otherwise stated or apparent.
~'0 9S/18992 2 1 7 8 8 1 8 Pr-~lus94ll3724 Glossary A11 a methyl methacrylate polymer colllllleri~ "y available from Rohm & Haas under the trade de~;~"dliu,-"Acryloid A- 1 1 N
B44 a methyl methacrylate copolymer co"""e~ 'y available from Rohm & Haas Aromatic 150 a petroleum naphtha aromatic solvent Gor ' ~' ~9 98h C8 + aromatics, tagged closed cup flash point of 150C collllllelu;.~l:y available from Exxon Chemical Hydrin CG 70 a solution epi~ l,lo,u~,ydrin rubber collllllèr Ily rubber available from Zeon Chemicals MMA/EA/t- Methyl methacrylate(CAS#80-62-6)/ethyl acrylate BAM (CAS#140-88-5)/N-tert-butylacrylamide; 55/20/25 terpolymer ratio, 40.88% solids in MEK ~(ool~f;~l~ viscosity 7120 cps. with LV4 @ 60 rpm, Mw of 186,326, polydispersity, Mw/Mn=3.7479 (based on one lot).
Monomers available from Aldrich Chemical.
NeoPac an aliphatic polyurethane-acrylic latex copolymer R-9000 ~ispe,:.ioll rubber coi~""en :~:'y available from Zeneca with a Sward hardness of 36 and a free film alion of 620%
Palatinol 71 1- a C7- 1 1 phthalate ester Fila:.li. i~er co" " "e, i "y 9 available from BASF
UCAR 525 a 54% solids acrylic-vinyl chloride modified latex collllllèli~ ly available from Union Carbide Uniflex 312 a ~Id~ e( cor"",e,ica:!y available from Union Camp VAGH a hydroxyl functional vinyl chloride/vinyl acetate uol~.ner c~llllllèli. ~:!y available from Union Carbide under the trade de~i~lldLioll ~UCAR VAGH'V
VYES a hydroxyl functional vinyl chloride/vinyl acetate terpolymer co,~",leri 'y available from Union Carbide under the trade de lalion lJCAR VYES"
VYHH a vinyl chloride/vinyl acetate copolymer available from Union Carbide under the trade de~i!JlldliOn 'lJCAR
VYHHN
VYNC a vinyl chloride/vinyl acetate copolymer available from Union Carbide under the trade desi~nation 'UCAR
VYNC"- 40% solids in isopropyl acetate as supplied -Vinyl Cl.~ lics Resin ChVIOrY~.de AcentaYte Hydroxy vnjheOSe~ntt T~, (C) AvMrage VAGH 4n' 2. ~ . 2 ~C
VYE ~ ~ 3.
VY~ 0 ~ 2, VY~ O ~' , ' 1_, (11 ASTM D- .~3 Acrylic Ch . ~ .lics Acrylic T~ (C) Har~ness (KHN) Chemical A-11 100 18-19 MMA polymer copolymer E ,~0O
Example J
A receptor coating was prepared by blending the Golllpoll~rlL:i in the amounts s~ ali~tzd in Table 1. This blend was then coated onto 10 a pressure sensitive adhesive backed film cons; ,li"g esse"Li..lly of titanium dioxide, Zeneca Chemicals R-9000, and Zeneca Chemicals R-962 in ~upo,lions of 33141/26. Coating wei~ht of the receptor layer was 19.4 grams/ square meter. This coated film was imaged and passed the coating adherence and crack resistant tests.
Table 1 Amount Used (Ib.~ C- ~n~
1 1.49 MMA/EAlt-BAM L" ~.oly~, Id~
37 97 methyl ethyl ketone ~MEK) 14 65 toluene 5.17 Hydrin CG 70 rubber ~pO 9S/18992 2 1 7 8 8 1 8 PCT/US94/13724 g 11 .40 Palatinol 7 11 -9 Example 2 A receptor coating was prepared by blending the components in the amounts s~""",u,i~d in Table 2. This blend was then coated onto a pressure sensitive adhesive film conD;Dli"g ess~"i 'V of titanium dioxide, Miles Bayhydrol 123, and Zeneca Chemicals R-9000 in p~upoilions of 33145122. Coating weight of the receptor layer was 19.4 ~qrams/ square meter. This coated fiim was imaged and passed the coating adherence and crack resistant tests. Table 5 su."",a,i~es the film p,up~ s of the Zeneca and Miles products.
Table 2 Amoun~ Used (Ib.~ C~
4.28 Rohm & Haas B-44 52.75 methyl ethyl ketone (MEK) 1 0.32 toluene 1 2.56 WNC
5.02 WHH
4.70 Hydrin CG 70 rubber 1 0.37 Palatinol 7 11 -P
Ex~mple 3 A clear coat/premask was prepared by coating a premask backing of a paper having a basis weight of 94 Ibs per ream ~3000 15 sq. ft.) with high density polyethylene on both sides (13 Ibs. on gloss side and 11 Ibs. on matte side, ~ o"""e~ 'y available from HP Smith) first with a layer consiDLi"g ess~"li3:'y of the formulation described in Table 3 and secondly with a layer as described in Table 4. The first layer was coated to yield a dry coating weioht of 4.5 grams/sq. meter.
20 The second layer was coated to yield a dry coating weight of 10.3 ~rams/sq. meter.
W09Stl8992 PCT/US94/13724--2~788l~
Table 3 Amount Used ~Ib.) Component 19.5 Acryloid A-11 60.0 MEK
4.9 VAGH
13.4 Uniflex 312 T~blo 4 Amount Used (Ib.) Co~ o.~ t 1 0.0 VYES
42.7 MEK
38.2 toluene 6.1 Hydrin CG 70 rubber 3.3 Palatinol 711-P
Table 5 - Film C~ ?O~ a Physical r.~,p~
Product r ~ Pac R-sooo Ns~nez R-962 BaY~ydrol 123 Tensile ~psi) ~ 0 35_ ~ 5 .
Elon~ation ~ 8 3 100% Modulus ~psi) o 9 8 The material from Example 2 (having a pressure sensitive adhesive layer protected by a release liner) was placed in contact with the dru,e",~"Lioned premask/clear coat and passed through a hot roll laminator operating as follows: one-9" steel roll, one-9" rubber roll with a 58 Shore D hardness, with a nip pressure of 55 pounds per lineal inch, and with a speed of 46 c~"li",t:L~,:, per minute. The resulting co"".o~ was adhered to a flexible Polvvinyl chloride coated fabric by (11 removing the liner ~ru~ g the pressure sensitive adhesive, (2) placing the adhesive in contact with the polyvlnyl coated fabric, (3) adhering the graphic to the flexible polyYinyl coated fsbric by pressing the pressure sensitive adhesiYe firmly against the polyvinyl coated fabric, and (4) removing the premask backing thus leaving the finished graphic with a clear coating on the flexible polyvinyl coated ~095/18992 2 1 7 8 8 1 8 PCTIIJS94/13724 fabric. This coated film was imaged and tested and met the three pe,rullllal~ce criteria.
Example 4 A clear coat/premask is prepared by coating a premask backing 5 of 2 mil polyester first with a layer conai~lillg ess~"i "y of the formulation as described in Table 3 and secondly with a layer as described in Table 4. The first layer is coated to yield a dry coating weight of 4.5 ~rams/sq. meter. The second layer is coated to yield a dry coating weight of 10.3 grams/sq. meter. The material is laminated 10 as described in Example 3 and tested as described in Example 1. This coated film was imaged and tested and met the three pt:l ru""~nce criteria.
Ex~mple !i A receptor coating was prepared by blending the col",uol1e"L~ in 15 the amounts su,,,,,,c,,iG~d in Table 6. This blend was then coated onto a pressure sensitive adhesive backed film ~,ol,Si~ g esse"; "y of titanium dioxide, Zeneca Chemicals R-9000, and Zeneca Chemicals R-962 in p~upo,liù~1s of 33141126. Coating weight of the receptor layer was 19.4 grams/ square meter. This coated film was imaged and 20 tested and met the three pe.tullllaoce criteria.
Table 6 Amount Used (Ib.) Co~ron~nt 79.5 UCAR 525 10.0 NeoPac R-9000 10.0 Uniflex 312 0.5 (;I;~olo- y~u,u,u~ y;,il~.ne The coated article was clear coat screen printed using 230 mesh screen, with a one (1) pass coating, and then oven-dried for 10 minutes at 1 50F. The clear coat composition was diluted with 25 cycloh~,~d,1one to a viscosity of 700 c~ntipoise, using a Brouhridld WO 95/18992 PCTNS94113724 ~1 V; .l O~ , LV-2, RPM-60. The clear coat consisted e~t "i ly of the following c~,,,uo~iliù,~:
Table 7 Amount Used (Ib.) Component 21 .7 C~lul ,c ~c., .~,)e 17.6 Ethyl ~:llloAyf~-uuid.. al~
9.5 Butyl cellusoive acetate 12.2 Aromatic 150 20.1 A-1 1 5. 1 VAGH
13.8 Uniflex 312 Various Illodiricaliolls and all~laLions of this invention will become apparent to those skilled in the art without departing from the scope and principles of this invention, and it should be.~"de,~luod that this invention is not to be unduly limited to the illustrative tlllbc. ~ , set forth l-el~:.,aLù~e. All pll " ns and patents are i"co,~uordl~d herein by reference to the same extent as if each individual pll : ~ or patent was :-~ue~iri 'y and individually indicated to be illl ~luulal~d by reference.
Background of the l.,.r~ iol~
Previously, high quality ~raphics were limited to lon~ runs to rcduce cost or short runs, wherein the costs were excessive. With the 10 advent of S~,o~cl,p,i"~ graphics, production of limited quantities of high quality graphics were readily arrL~ Fu,~l,e""ore, Scotchcal 8620 and 8640 receptor-coated films have permitted the use of such high quality graphics for limited quantity ~r F' _: -ns for rigid surfaces.
These marking fiims comprise a vinyl film base that is top coated with 15 a solvent ~IIGIIIIOPId~ blend of acrylic copolymer, vinyl chloride/vinyl acetate copoly."Gr, and a pld~ er. This top coating is a non-tacky solid that is ",oderd~ly flexible at room temperature. Above 70C, the ~I IGl l l lopld nil~ melts and bonds onto r l~ "d ~i., toners that were previously printed onto a transfer media. After cooling, the marking 20 films can be separated from the transfer media and the toners are retained by the marking film.
Ideally, the ~IIGIIIIOPId:~;C layer (1) adheres well to the base film, ~2) does not adhere to untoned (unimaged) areas on the transfer media, ~3) does not destroy the physical prope, ~ies of the base film 25 (tensile, r,:o.~ld~ion, color, etc.), (4) bonds co,..~,kit~ly to the toners,permitting removal of toner from the transfer media and not p~-~"illi~1g toner removal durin~ normal ~ ion, (5) is not tacky during normal use, and (6) is con",d~iLI~ with additional ope,d~ic,ns, such as clear coating or PIGIIIaSk;I~9~
WO g5/18992 PCT/US9~/13724 --However, continuously flexed surfaces, such as the ~lailSpOI L~
and vehicles with F! .~ ed polyvinyl chloride coated fabric sides prevalent in a large portion of the world have proven to be a probiem for the receptor-coated fiims. Typicaiiy, the pl~ ed polyvinyl 5 chioride coated fabric is a ~ lllOpla~LiC material fiexed, rolied, flapped, and cold-flexed numerous times during the lifetime of the siding. Hence, any graphic image adhered or otherwise attached to such a siding must be capable of withstanding identical stresses without failure.
Summary of the l~ lio.~
Briefly, in one aspect of the present invention, the receptor iâyer Golllpli.~s a blend of an acrylic resin, 8 vinyl resin, a solution or dispersion grade rubber, and a pla~Li~ el coated on a crack resistant pressure sensitive adhesive backed film. Convenientiy, the receptor layer now allows Sc~L~ )ri"L graphics to be applied to p~ d polyvinyl chloride coâted fabric for use on soft-sided vehicles.
Advantageously, the final graphic ima~e articie, that is, the imaged feceptor layer on the crack le~ lanCe pressure sensitive adhesive backed film, together with any app,op~iaLt: protective clear coat, applied to a ~la;~ d polyvinyl chioride-coated fabric siding wiil withstand extreme env;.u"",~"lal stresses that occur on soft-sided vehicles, particuisriy at low temperatures, that present Sc~l~,llpli materiais do not v~ al~d.
D~sc,i~.liu,~ of the r~ère~ed E L
An image is generally applied to the inventive receptor layer by thermally bonding 61~ LaLic toners that were previously printed onto a transfer media as decribed for example in U.S. Patent Nos.
5,114,520 and 5,262,259 and such dr,~ ,Lion is i".,or~,o,a~t:d herein by referènce. After cooling, the receptor coated marking film can be ~0 95/18992 2 1 7 8 8 ~ 8 PCTIUS94/13724 separated from the transfer media and the toners are retained by the receptor coated marking film.
r,~rt,ably, the final graphic image article ~;ll,:.ldnds the following tests:
11~ coating a-ll,t:,e"ce; and (2) crack ,t~i~lance at -20C.
When the final graphic image article is co,,,,urised of more than one panel, for example, side-by-side panels with overlapping seams or one panel partially or totally adhered over another panel, then the final graphic imased article pl~r~ldbly ~ ;Lll~lands the following additional test: I3) overlap acll~ ,e of one layer of imaged film to an underlying layer of imaged film. A Upanel'' is defined as a sheet of an imaged receptor layer on a crack l~ lallCe pressure sensitive adhesive backed film, which may or may not include an ap~up~ial~a protective clear coat.
~Coating aJl,e,~,lce"is defined as achieving a 4B or 5B rating per ASTM test D3359, Test Method B after 16 hours of water i"""e~ion, whereby the sample is i"""edial~ly tested after removal from the water and towel drying. ''Crack l~ lance~is defined as minimum damage to the surface after repeated flexing and pl~r~aLly after 4000 double flexes in a flex tester operating at -20C per DIN
53359 Test B. ~verlap"adherence Is d~Lt:llll:.led in acco,ddnc~ with ASTM D1000, except that the imaged film to be tested is adhered to a like portion of imaged film that has been adhered to PVC-coated fabric substrate. This multilayer co",posile, that is, where at least two panels overlap each other, is aged at least 16 hours at 65C prior to testing. The overlap a.ll,erence is preferably at least 1.0 pounds per inch width for all colors and non-colored portions.
Marking films having a urethane base, such as Scotchcal 190 marking film, are used on pla~ d polyvinyl chloride coated fabrics.
While urethane based films have ouL~Lal1~" ,9 crack ~esi;.Làl1ce, W095118992 2 1 78~ 1 8 Pr~sgvl3724~
pl..~ici~t:r ,t:Di,la"ce and moisture resistance, standard ScoLcl,p,i"L
receptor coatings do not work on urethane based or other crack resistant marking films.
When e!~ ,u:ila~ic toner receptor coatings used on conventional 5 vinyl chloride based marking films are applied to crack resistant films used for marking soft sided vehicles, such coated films fail to meet the crack ~ La,1ce criteria and will often fail the coating adherence criteria. HoweYer, when a crack resistant film, such as a urethane-based film is coated with the inventive receptor, the coated film retains 10 su~Lal "y all of the plu~J~,Lit!s of the base film without such a coating and more importantly, the coated film meets the above p~rullllallce criteria. Using urethane-based films without any receptor coating generally is ullaccerjla~lc for imaging by toner transfer because hot la",i"aLion results in no release from untoned areas and 15 poor overlap adhesion in toned areas.
It is well known that the flexibility of Lllellllùpld~lic coatings can be increased by adding r~ '' ' ~ . The flexibility of the coatings used for vinyl film at room temperature can be partially attributable to pla~ ,. Increased levels of pldali~ er have been shown to improve 20 crack ,~ a"ce st low temperatures. However, with higher pla loading, particularily in an acrylic-cor, , ,g coating, the surface can become tacky at normal handling temperatures. This surface tack can cause handling difficulties, dirt pickup, less abrasion ,~ai~la,~ce, poorer internal strength, image dr,l...lli"alion, and roll blocking problems.
Publicly known flexible polyvinyl chloride substrates typicaliy contain high levels (60 to 100 parts per hundred parts resin) of monomeric pl~ r. This ~ono",eric pla;,Li..i~r tends to migrate into any graphic marking film adhered to the surface, thus resulting in the same types of problems ~OG~I~d with addition of excess 30 plaaLi~ dr.
~V095/18992 2 1 7 8 8 1 8 PCTIUS94/13724 lt has been discovered that a receptor coating co"",osilion co"".,i~ing 8 blend of acrylic resin, a vinyl resin, a solution or d;~,eraion grade rubber, and a pla~ r coated onto a urethane-based film will meet the pe~ ru, n~a,lce criteria, while ",i";",i~;"g 5 pla~ er infiuence at normal handling temperâtures~ P(ert:la~ the receptor coating cor"~û~ilion has at least 5% to 55% of a solution or d;~per~ion grade rubber, more plt:r~lably, 7% to 30% of a solution or dispersion grade rubber. It is within this range that the resultant printed graphic meets crack ~ Lu,~ce criteria.
Once the el~ u~lulic toner receptor coating has been applied to a crack resistant film, a toner image can then be thermally llar"r~"~d onto this receptor layer. A wear coat, protective layer or clear coat can then be applied by technique known to those skilled in the art, such as screen printing clear coats, or flood coating clear 1 5 coats.
Fu~ II,t:""or~, it has been found that i"co, ,~oralion of a graphics overlay colllpGaite (a premask layer adjacent to a protective layer), as described, for example in Attorney Docket No. 49516 USA 4A, assigned to the same assignee as the present rF' lion, can enhance 20 the overlap adhesion of finished graphic image panels.
Particularly useful acrylic resins for the image receptor coating include methyl methacrylate polymers and copolymers, such as Acryloids B-44 and B-48, col"",~" 'ly available from Rohm and Haas, and a methyl ",t ll,~ ylate/ethyl acrylate/N-t-butylacrylamide.
25 Particularly useful vinyl resins for the image receptor coating including vinyl chloride/vinyl acetate cOpOly,lle:,a, such as those c~"""elica:ly available from Union Carbide, under the trade d~siy,,aliul~ 'UCAR':
Any ~i~,,e,aion or solution grade rubber can be used in the present invention and suitable examples include but are not limited to solution 30 cll'~ illal~d rubbers (such as, epi~,l,lo,ul,ydrin rubber co""~,e, "y woss/lsss2 2 ~ 7 8 8 ~ 8 Pcrluss4/13724 ~
available as Hydrin CG from Zeon Chemicals) and urethane di~Jel:,;o rubbers (such as NeoPac R-9000 available from Zeneca Chemical~.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts 5 thereof recited in these e~.a",, '-~ as well as other conditions and details, should not be construed to unduly limit this invention. All materials are C~llllllt:l, "y available or known to those skilled in the art unless otherwise stated or apparent.
~'0 9S/18992 2 1 7 8 8 1 8 Pr-~lus94ll3724 Glossary A11 a methyl methacrylate polymer colllllleri~ "y available from Rohm & Haas under the trade de~;~"dliu,-"Acryloid A- 1 1 N
B44 a methyl methacrylate copolymer co"""e~ 'y available from Rohm & Haas Aromatic 150 a petroleum naphtha aromatic solvent Gor ' ~' ~9 98h C8 + aromatics, tagged closed cup flash point of 150C collllllelu;.~l:y available from Exxon Chemical Hydrin CG 70 a solution epi~ l,lo,u~,ydrin rubber collllllèr Ily rubber available from Zeon Chemicals MMA/EA/t- Methyl methacrylate(CAS#80-62-6)/ethyl acrylate BAM (CAS#140-88-5)/N-tert-butylacrylamide; 55/20/25 terpolymer ratio, 40.88% solids in MEK ~(ool~f;~l~ viscosity 7120 cps. with LV4 @ 60 rpm, Mw of 186,326, polydispersity, Mw/Mn=3.7479 (based on one lot).
Monomers available from Aldrich Chemical.
NeoPac an aliphatic polyurethane-acrylic latex copolymer R-9000 ~ispe,:.ioll rubber coi~""en :~:'y available from Zeneca with a Sward hardness of 36 and a free film alion of 620%
Palatinol 71 1- a C7- 1 1 phthalate ester Fila:.li. i~er co" " "e, i "y 9 available from BASF
UCAR 525 a 54% solids acrylic-vinyl chloride modified latex collllllèli~ ly available from Union Carbide Uniflex 312 a ~Id~ e( cor"",e,ica:!y available from Union Camp VAGH a hydroxyl functional vinyl chloride/vinyl acetate uol~.ner c~llllllèli. ~:!y available from Union Carbide under the trade de~i~lldLioll ~UCAR VAGH'V
VYES a hydroxyl functional vinyl chloride/vinyl acetate terpolymer co,~",leri 'y available from Union Carbide under the trade de lalion lJCAR VYES"
VYHH a vinyl chloride/vinyl acetate copolymer available from Union Carbide under the trade de~i!JlldliOn 'lJCAR
VYHHN
VYNC a vinyl chloride/vinyl acetate copolymer available from Union Carbide under the trade desi~nation 'UCAR
VYNC"- 40% solids in isopropyl acetate as supplied -Vinyl Cl.~ lics Resin ChVIOrY~.de AcentaYte Hydroxy vnjheOSe~ntt T~, (C) AvMrage VAGH 4n' 2. ~ . 2 ~C
VYE ~ ~ 3.
VY~ 0 ~ 2, VY~ O ~' , ' 1_, (11 ASTM D- .~3 Acrylic Ch . ~ .lics Acrylic T~ (C) Har~ness (KHN) Chemical A-11 100 18-19 MMA polymer copolymer E ,~0O
Example J
A receptor coating was prepared by blending the Golllpoll~rlL:i in the amounts s~ ali~tzd in Table 1. This blend was then coated onto 10 a pressure sensitive adhesive backed film cons; ,li"g esse"Li..lly of titanium dioxide, Zeneca Chemicals R-9000, and Zeneca Chemicals R-962 in ~upo,lions of 33141/26. Coating wei~ht of the receptor layer was 19.4 grams/ square meter. This coated film was imaged and passed the coating adherence and crack resistant tests.
Table 1 Amount Used (Ib.~ C- ~n~
1 1.49 MMA/EAlt-BAM L" ~.oly~, Id~
37 97 methyl ethyl ketone ~MEK) 14 65 toluene 5.17 Hydrin CG 70 rubber ~pO 9S/18992 2 1 7 8 8 1 8 PCT/US94/13724 g 11 .40 Palatinol 7 11 -9 Example 2 A receptor coating was prepared by blending the components in the amounts s~""",u,i~d in Table 2. This blend was then coated onto a pressure sensitive adhesive film conD;Dli"g ess~"i 'V of titanium dioxide, Miles Bayhydrol 123, and Zeneca Chemicals R-9000 in p~upoilions of 33145122. Coating weight of the receptor layer was 19.4 ~qrams/ square meter. This coated fiim was imaged and passed the coating adherence and crack resistant tests. Table 5 su."",a,i~es the film p,up~ s of the Zeneca and Miles products.
Table 2 Amoun~ Used (Ib.~ C~
4.28 Rohm & Haas B-44 52.75 methyl ethyl ketone (MEK) 1 0.32 toluene 1 2.56 WNC
5.02 WHH
4.70 Hydrin CG 70 rubber 1 0.37 Palatinol 7 11 -P
Ex~mple 3 A clear coat/premask was prepared by coating a premask backing of a paper having a basis weight of 94 Ibs per ream ~3000 15 sq. ft.) with high density polyethylene on both sides (13 Ibs. on gloss side and 11 Ibs. on matte side, ~ o"""e~ 'y available from HP Smith) first with a layer consiDLi"g ess~"li3:'y of the formulation described in Table 3 and secondly with a layer as described in Table 4. The first layer was coated to yield a dry coating weioht of 4.5 grams/sq. meter.
20 The second layer was coated to yield a dry coating weight of 10.3 ~rams/sq. meter.
W09Stl8992 PCT/US94/13724--2~788l~
Table 3 Amount Used ~Ib.) Component 19.5 Acryloid A-11 60.0 MEK
4.9 VAGH
13.4 Uniflex 312 T~blo 4 Amount Used (Ib.) Co~ o.~ t 1 0.0 VYES
42.7 MEK
38.2 toluene 6.1 Hydrin CG 70 rubber 3.3 Palatinol 711-P
Table 5 - Film C~ ?O~ a Physical r.~,p~
Product r ~ Pac R-sooo Ns~nez R-962 BaY~ydrol 123 Tensile ~psi) ~ 0 35_ ~ 5 .
Elon~ation ~ 8 3 100% Modulus ~psi) o 9 8 The material from Example 2 (having a pressure sensitive adhesive layer protected by a release liner) was placed in contact with the dru,e",~"Lioned premask/clear coat and passed through a hot roll laminator operating as follows: one-9" steel roll, one-9" rubber roll with a 58 Shore D hardness, with a nip pressure of 55 pounds per lineal inch, and with a speed of 46 c~"li",t:L~,:, per minute. The resulting co"".o~ was adhered to a flexible Polvvinyl chloride coated fabric by (11 removing the liner ~ru~ g the pressure sensitive adhesive, (2) placing the adhesive in contact with the polyvlnyl coated fabric, (3) adhering the graphic to the flexible polyYinyl coated fsbric by pressing the pressure sensitive adhesiYe firmly against the polyvinyl coated fabric, and (4) removing the premask backing thus leaving the finished graphic with a clear coating on the flexible polyvinyl coated ~095/18992 2 1 7 8 8 1 8 PCTIIJS94/13724 fabric. This coated film was imaged and tested and met the three pe,rullllal~ce criteria.
Example 4 A clear coat/premask is prepared by coating a premask backing 5 of 2 mil polyester first with a layer conai~lillg ess~"i "y of the formulation as described in Table 3 and secondly with a layer as described in Table 4. The first layer is coated to yield a dry coating weight of 4.5 ~rams/sq. meter. The second layer is coated to yield a dry coating weight of 10.3 grams/sq. meter. The material is laminated 10 as described in Example 3 and tested as described in Example 1. This coated film was imaged and tested and met the three pt:l ru""~nce criteria.
Ex~mple !i A receptor coating was prepared by blending the col",uol1e"L~ in 15 the amounts su,,,,,,c,,iG~d in Table 6. This blend was then coated onto a pressure sensitive adhesive backed film ~,ol,Si~ g esse"; "y of titanium dioxide, Zeneca Chemicals R-9000, and Zeneca Chemicals R-962 in p~upo,liù~1s of 33141126. Coating weight of the receptor layer was 19.4 grams/ square meter. This coated film was imaged and 20 tested and met the three pe.tullllaoce criteria.
Table 6 Amount Used (Ib.) Co~ron~nt 79.5 UCAR 525 10.0 NeoPac R-9000 10.0 Uniflex 312 0.5 (;I;~olo- y~u,u,u~ y;,il~.ne The coated article was clear coat screen printed using 230 mesh screen, with a one (1) pass coating, and then oven-dried for 10 minutes at 1 50F. The clear coat composition was diluted with 25 cycloh~,~d,1one to a viscosity of 700 c~ntipoise, using a Brouhridld WO 95/18992 PCTNS94113724 ~1 V; .l O~ , LV-2, RPM-60. The clear coat consisted e~t "i ly of the following c~,,,uo~iliù,~:
Table 7 Amount Used (Ib.) Component 21 .7 C~lul ,c ~c., .~,)e 17.6 Ethyl ~:llloAyf~-uuid.. al~
9.5 Butyl cellusoive acetate 12.2 Aromatic 150 20.1 A-1 1 5. 1 VAGH
13.8 Uniflex 312 Various Illodiricaliolls and all~laLions of this invention will become apparent to those skilled in the art without departing from the scope and principles of this invention, and it should be.~"de,~luod that this invention is not to be unduly limited to the illustrative tlllbc. ~ , set forth l-el~:.,aLù~e. All pll " ns and patents are i"co,~uordl~d herein by reference to the same extent as if each individual pll : ~ or patent was :-~ue~iri 'y and individually indicated to be illl ~luulal~d by reference.
Claims (7)
1. A graphic article comprising an electrostatic toner receptor layer of comprising a blend of an acrylic resin, a vinyl resin, 5 to 55% by weight chlorinated rubber or polyurethane rubber and a plasticizer coated onto a urethane-based crack resistant film.
2. The graphic article according to claim 1 further including a pressure sensitive adhesive layer adhered to a second major surface of the urethane-based crack resistant film, wherein the second major surface is opposed to the first major surface.
3. The graphic article according to claim 1 wherein the acrylic resin is a terpolymer of methyl methacrylate/ethyl acrylate and N-t-butyl acrylamide.
4. The graphic article according to claim 1 wherein the article further includes an imaged layer overlaying the electrostatic toner receptor layer, thereby providing an imaged graphic article.
5. The graphic article according to claim 4 wherein the imaged graphic article further includes a clear coat layer overlaying the imaged layer.
6. An applied graphic article comprising an imaged graphic article according to claim 5 adhered to a plasticized polyvinyl chloride-coated fabric.
7. The applied graphic article according to claim 6 further including a protective clear coat overlaying the imaged graphic article.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17864594A | 1994-01-07 | 1994-01-07 | |
| US08/178,645 | 1994-01-07 | ||
| PCT/US1994/013724 WO1995018992A1 (en) | 1994-01-07 | 1994-11-30 | An electrostatic toner receptor layer of rubber modified thermoplastic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2178818A1 true CA2178818A1 (en) | 1995-07-13 |
Family
ID=22653339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002178818A Abandoned CA2178818A1 (en) | 1994-01-07 | 1994-11-30 | An electrostatic toner receptor layer of rubber modified thermoplastic |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US6322874B1 (en) |
| EP (1) | EP0738401B1 (en) |
| CN (1) | CN1141089A (en) |
| AU (1) | AU691544B2 (en) |
| BR (1) | BR9408476A (en) |
| CA (1) | CA2178818A1 (en) |
| DE (1) | DE69432902T2 (en) |
| NZ (1) | NZ277412A (en) |
| WO (1) | WO1995018992A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2330782A (en) * | 1997-11-01 | 1999-05-05 | Autotype Int Ltd | Film product for use in printing |
| EP1077394A1 (en) * | 1999-08-12 | 2001-02-21 | Zimmer, Michael | Process for transfer of toner and toner containing vulcanizable rubber material and/ or rubber material |
| US20020139498A1 (en) * | 2001-01-05 | 2002-10-03 | Jim Matheson | Method of producing microcrystalline |
| DE10132884A1 (en) * | 2001-07-06 | 2003-01-16 | Buelent Oez | Process for printing substrates |
| US7316832B2 (en) | 2001-12-20 | 2008-01-08 | The Procter & Gamble Company | Articles and methods for applying color on surfaces |
| US7709070B2 (en) | 2001-12-20 | 2010-05-04 | The Procter & Gamble Company | Articles and methods for applying color on surfaces |
| AU2003213689A1 (en) * | 2002-03-05 | 2003-09-22 | 3M Innovative Properties Company | Marking film, receptor sheet and marking film for vehicles |
| JP4290700B2 (en) | 2003-02-14 | 2009-07-08 | ザ プロクター アンド ギャンブル カンパニー | Discoloration resistant article applying color on surface and method for reducing discoloration in article applying color on surface |
| US20040161564A1 (en) | 2003-02-14 | 2004-08-19 | Truog Keith L. | Dry paint transfer laminate |
| US20050196607A1 (en) | 2003-06-09 | 2005-09-08 | Shih Frank Y. | Multi-layer dry paint decorative laminate having discoloration prevention barrier |
| US20090023834A1 (en) * | 2006-02-09 | 2009-01-22 | Ralf Norenberg | Method for treating polypropylene textiles |
Family Cites Families (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB736998A (en) * | 1952-07-22 | 1955-09-21 | Greengate And Irwell Rubber Co | Improvements relating to conveyor belts |
| US2753322A (en) * | 1954-11-02 | 1956-07-03 | Goodrich Co B F | Rigid vinyl halide polymer compositions adapted for vacuum forming |
| US2984583A (en) * | 1956-10-05 | 1961-05-16 | Degussa | Process for the coating of surfaces and objects |
| GB826540A (en) * | 1957-05-10 | 1960-01-13 | Us Rubber Co | Improvements in thermoplastic compositions |
| US3065120A (en) | 1960-08-29 | 1962-11-20 | Mask Off Company Inc | Dry transfer decals |
| US3276933A (en) | 1962-09-17 | 1966-10-04 | Radiant Color Company | Transfer sheet and method |
| FR1479358A (en) | 1966-03-16 | 1967-05-05 | Trentesaux Toulemonde Sa | Transfer printing process, especially on plastic |
| GB1218058A (en) | 1968-10-14 | 1971-01-06 | Whiley Ltd George M | Improvements in or relating to transfers |
| US4081583A (en) * | 1969-11-15 | 1978-03-28 | Japan Synthetic Rubber Co., Ltd. | Electrostatic recording material |
| US3928710A (en) | 1970-04-29 | 1975-12-23 | Letraset International Ltd | Heat activated transfers |
| JPS4945734A (en) * | 1972-09-05 | 1974-05-01 | Japan Synthetic Rubber Co Ltd | Seidenkirokutai no seizoho |
| US3907974A (en) | 1973-11-08 | 1975-09-23 | Dennison Mfg Co | Curable decorating systems for glass or metal containers |
| NL7414576A (en) * | 1973-11-14 | 1975-05-16 | Dow Chemical Co | LATEX COATED ELECTROSTATIC SHEET. |
| JPS6130258B2 (en) * | 1974-12-27 | 1986-07-12 | Canon Kk | |
| US4064285A (en) * | 1975-12-22 | 1977-12-20 | Xerox Corporation | Electrophotographic decalcomanias |
| US4085245A (en) * | 1976-04-15 | 1978-04-18 | Xerox Corporation | Transparencies for color xerographic copies |
| JPS5348740A (en) * | 1976-10-15 | 1978-05-02 | Ricoh Co Ltd | Pressure sensitive adhesive electrostatic photographic toner |
| US4737224A (en) | 1980-06-27 | 1988-04-12 | Minnesota Mining And Manufacturing Company | Process of dry adhesive-free thermal transfer of indicia |
| JPS5852374A (en) * | 1981-09-24 | 1983-03-28 | Sakura Color Prod Corp | Ink composition acting as indicator for vulcanization of rubber |
| US4505976A (en) * | 1983-02-15 | 1985-03-19 | Johnson & Johnson Products, Inc. | Stoma seal adhesive |
| US4851468A (en) * | 1984-12-10 | 1989-07-25 | Exxon Research & Engineering Company | Dynamically cured thermoplastic olefin polymers |
| JP2618705B2 (en) | 1989-03-17 | 1997-06-11 | 富士写真フイルム株式会社 | Image receiving sheet material and transfer image forming method |
| US5064717A (en) * | 1989-04-28 | 1991-11-12 | Kanzaki Paper Manufacturing Co., Ltd. | Adhesive sheet |
| DE3926275A1 (en) * | 1989-08-09 | 1991-02-14 | Bayer Ag | ABS MOLDS WITH IMPROVED STRETCH TENSION |
| US5262259A (en) * | 1990-01-03 | 1993-11-16 | Minnesota Mining And Manufacturing Company | Toner developed electrostatic imaging process for outdoor signs |
| US5106710A (en) * | 1990-03-01 | 1992-04-21 | Minnesota Mining And Manufacturing Company | Receptor sheet for a toner developed electrostatic imaging process |
| US5202205A (en) * | 1990-06-27 | 1993-04-13 | Xerox Corporation | Transparencies comprising metal halide or urea antistatic layer |
| JP3132840B2 (en) | 1991-03-22 | 2001-02-05 | コニカ株式会社 | Image receiving sheet for thermal transfer recording and thermal transfer recording method |
| US5114520A (en) * | 1991-09-27 | 1992-05-19 | Minnesota Mining And Manufacturing Company | Image transfer apparatus and method |
| US5484844A (en) * | 1992-04-14 | 1996-01-16 | Mitsubishi Chemical Mkv Company | Vinyl chloride resin elastomer composition |
| US5254403A (en) * | 1992-04-23 | 1993-10-19 | Xerox Corporation | Coated recording sheets |
| US5330823A (en) * | 1993-03-19 | 1994-07-19 | Xerox Corporation | Transparent recording sheets |
| US5391625A (en) * | 1993-03-19 | 1995-02-21 | Arjunan; Palanisamy | Compatibilized elastomer blends containing copolymers of isoolefins |
| US5363179A (en) * | 1993-04-02 | 1994-11-08 | Rexham Graphics Inc. | Electrographic imaging process |
| US5483321A (en) * | 1993-04-02 | 1996-01-09 | Rexam Graphics | Electrographic element having a combined dielectric/adhesive layer and process for use in making an image |
-
1994
- 1994-11-30 NZ NZ277412A patent/NZ277412A/en unknown
- 1994-11-30 BR BR9408476A patent/BR9408476A/en not_active IP Right Cessation
- 1994-11-30 AU AU12624/95A patent/AU691544B2/en not_active Ceased
- 1994-11-30 CA CA002178818A patent/CA2178818A1/en not_active Abandoned
- 1994-11-30 CN CN94194777A patent/CN1141089A/en active Pending
- 1994-11-30 WO PCT/US1994/013724 patent/WO1995018992A1/en active IP Right Grant
- 1994-11-30 EP EP95903636A patent/EP0738401B1/en not_active Expired - Lifetime
- 1994-11-30 DE DE69432902T patent/DE69432902T2/en not_active Expired - Fee Related
-
1995
- 1995-05-24 US US08/449,204 patent/US6322874B1/en not_active Expired - Fee Related
-
1997
- 1997-06-09 US US08/871,177 patent/US5852121A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0738401B1 (en) | 2003-07-02 |
| NZ277412A (en) | 1997-07-27 |
| EP0738401A1 (en) | 1996-10-23 |
| WO1995018992A1 (en) | 1995-07-13 |
| AU1262495A (en) | 1995-08-01 |
| CN1141089A (en) | 1997-01-22 |
| US6322874B1 (en) | 2001-11-27 |
| US5852121A (en) | 1998-12-22 |
| JPH09507309A (en) | 1997-07-22 |
| DE69432902T2 (en) | 2004-05-06 |
| AU691544B2 (en) | 1998-05-21 |
| BR9408476A (en) | 1997-08-26 |
| JP3537823B2 (en) | 2004-06-14 |
| DE69432902D1 (en) | 2003-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3080662B2 (en) | Toner developed electrostatic image forming method for outdoor signs | |
| CA2178818A1 (en) | An electrostatic toner receptor layer of rubber modified thermoplastic | |
| CA1326977C (en) | Transparent sheet material for electrostatic copiers | |
| US5601959A (en) | Direct transfer electrographic imaging element and process | |
| US6171422B1 (en) | Imaging element having a conductive polymer layer | |
| US4489122A (en) | Transparencies for electrostatic printing | |
| AU706152B2 (en) | Film composite for electrostatic recording | |
| US11590749B2 (en) | Flexible packaging material | |
| CA2321978A1 (en) | Method of forming a thermoplastic layer on a layer of adhesive | |
| JP3080674B2 (en) | Electrostatic multicolor toner image forming method and receptor sheet | |
| US5688581A (en) | Electrographic image transfer element having a protective layer | |
| EP0695973A1 (en) | Removable nonporous opaque thin film layer | |
| JP3537823B6 (en) | Graphic article including an electrostatic toner receiving layer | |
| EP0858005B1 (en) | Toner receptive sheet for digital offset printing | |
| JP4006248B2 (en) | Image recording medium and image display sheet | |
| EP0858004B1 (en) | Toner-receptive sheet for digital offset printing | |
| JP2005329725A (en) | Thermal transfer image receiving sheet | |
| WO2019011399A1 (en) | Printed rigid plastic substrates | |
| WO1999036833A1 (en) | Receiver sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |