CA2197992A1 - Ink jet printing sheet - Google Patents

Abstract

This invention relates to an ink jet printing sheet(s) suitable for use in signing applications, archiving and other applications comprising a plastic substrate, including a particulate as means to produce smear-resistant images with ink jet inks.

Description

21 q7992 09610~377 r~ "~

~k Jet Printing Sheet Technic~ll Field This invention relates to ink jet printing sheets suitable for use in signing 1~ l ' and in particular to a printing sheet having a release surface in contact with an adhesive layer. This invention further relates to a method of printing using the printing sheet of this invention.
n..~ of the lnvention Various processes suitable for producing outdoor durable signs are 10 known to the art, e.g. by ele~,tlv~l~Lc printing processes, receptors and methods of transfer to signing materials. These processes have produced materials usefulin a whole variety of ,, ' such as advertising, billboards, vehicle signing.However, they suffer from the disadvantage that the machinery ItlJllD~ t:~ for these processes and articles are expensive and the machinery requires relatively high and operator skiD.
The ink jet printing process is now well known. Examples of its a" " are as computer printers for the production of documents and overhead L. , ~...,;~. Recently wide fortnat printers have become ~.v.~ available, and therefore the printing of larger articles such as large 20 engineering drawings, blueprints and color posters and signs has become feasible. These printers are relatively , ~., as compared with many other hardcopy output devices, for exarnple, digital ~ v~i~Li~. printers. However, the printers have all the usual advantages of computer addressed hardcopy output devices, wherein the image as a positive I ' g , ' i , ~ .y or 2~ print can be scanned using scanner devices known in the art, stored on computer disc, ~ n .1, restored, and printed etc.
Generally, ink jet inks are wholly or partially water-based and receptors for these inks are typically plain papers or preferably specialist ink jet receptor SUBSTITUTE S~EET ~RULE 26) 2 ~ 9 ~ ~ q~2 =: :~
~.VO 9C~OR377 ~ . 13 :: O
papers, which are treated or co~ted to improve their receptor properties or thc quality of the irnages resulting therefrom.
Many inic jet receptor ~ ,u~ suitable for ~application as overhead ~,.~;_0 are also icnown in the art. The,se nre composed of transparent S plastic materials such as polyester, which aione will not accept the aqueous inks and are coated with~receptor layers. Typically these receptor layers are connposed of mixt~res of water soluble polymers that can absorb the aqueous mLcture from the irk jet inlc.
Examples af ink jet receptor ~ , ~ used for overhead ~ D ;11 J ~i~lus~ in U.S. Patent No. 4,935,307 (Tqbal et ai.~, U.S.
Patent No. S,208,:W2 ~Iqbai), U.S Patent No. 5,~42,688 (Kitchin et al.); and EPO Pubiication v 4~4 016 A1.
A c:mn~n problem Ysith images produced by ink jet is the subsequent spread of the dyes~, ~often particularly bad~under warm and humid conditions.
15 Therefore, many receptor materials contain moieties that re~act wi~h, or otherwise immobilize the dycs after printmg. Allt~ernative approaches to prevent the spread of dyes are to modlfy inic r. " .... s .. :.... ~
Another disadvantage with many current ink jet ~ v~ is caior shift or fad;ng of the dyes in the in ages with subsequent loss of the a~lf. ~alJii;;y~
20 change in image quality with time, and a short iifetime for r~latively high-quality images in direct sunlight. This is not a problem in a~ I t~ such as short-term signing, for example for a~h~ ,..t~. HoweYer, these ' l~a~
make the images un~suitable for longer term ~ such as archivable prints orexteriord~.rPIth.~ ~ arld si~ns. ~ ~
Other inlc Jet recording materials are disclosed in U.S. Patent No 5~132,146 ~laruyama et al.) and U.S. Patent No. 5,302,4~7 (Idei et al.).
There is a need for ink~et receptor materials that prwide high density, low dye bleed ima~es with dye-based inl~ jet inks and at the same time prûvide smear-resistant images with pigmented ink jet inks.

~ --2-SUBSTITUTE SHEET (RULE 26) ~ 1 979~2 ~VO 9G/08377 PCTIUS95/10013 Summar~ of the Invention Briefly, in one aspect of the present invention, an ink jet printing sheet is provided comprising a substrate and an image receiving layer contacting the substrate, wherein the image receiving layer is comprised of at least one S protective penetrant layer of one ~ i...1 and at least one ink jet receptor layer of a second c ~ , and wherein both the protective penetrant layer and the ink jet receptor layer contain dispersed particles or p.ll i ' ' of a size large enough to roughen both a surface of the protective penetrant layer and a surface ofthe ink jet receptor layer.
Optionally, on the side of the substrate opposite from the image receiving layer, in sequential order, is an adhesive layer and a release liner. The sheet is useful in ink jet printing processes using substrates that may be used in signing, archiving or other imaging ,, " ' Ad~ , the image receiving iayer (either comprised of a single 15 layer or multiple layers~ can be used with a wide variety of substrates, such as ~h. ~ , thermoset, plastic-coated papers, fabrics, plastic-coated fabrics, thick or thin substrates, provided the coated substrates are capable of being loaded into an ink jet printing system.
The printed receptor sheet, either u~. ' J with a protective film or 20 coating or otherwise treated to provide a durable surface can be used for commerciai signage, archivai or imaging al, '' ' An advantage of the present invention is an ink jet printing sheet wherein the substrate and adhesive are durable for periods of severai years in an exterior c,,~ where the materials and images can be exposed to rain, sun, and 25 such variations in It~ Uln as are found in exterior environments and on surfaces in exterior e~.;.UIul.~dS. Typically, the article ofthe present invention have some flexibility such that it may be adhered onto surfaces having some curvature or non uniformity e.g. walls or surfaces with screw heads or rivets, without easily ripping the material or cracking or ~ ... ofthe image SUBSTITUTE SHEET (RULE 26) 9 ~ 2 ~ ~
wo ~377 : Pcrn3sss/l00l3 receiving layers, o~ ' , layers, other coatings or ima~e or 'itenting" of the material oYar th~ protrusiorL
A degree of water resi$ance, additional imags protecl~on to scratches, splashing and the like and a high gloss finish can be supplied optionally to the5 printed sheet, e.g. by:~he u . . ' ' ' of a clear protecd~ layer.
Finally, the ar~icla of the presem invention maintain other desirable properties of an idea] ink jet printing sheet, such as, dye bleed resistance and low 1,i.44. I color. G~ ood color saturalion and density are also observed in tha printed images. The printad articles do not curl excessively on exposure to 10 humidity or during the ink jet print;ng process, and printed unages exhibit quick ink drying times follo~}ing printing with good image sharpness.
As used in this application: ~ ~
"coloranP' means any substrate that imparts color to another material or mixture and maybe e:it:her, dyes or pigments;
~'durable" rneans the sub$rates used in the present invcnùon are capable of w' ' ' the wear and tear assocrated with signage and may be 2 to 5 years in exterior e.. ~ iu.~ b, ~
"pbstic" means a material that is capable of bein~ sha~d or molded with or without application of heat and include Lh~ plas~iui, types, thermosets 20 types, both of which may be ne~ible~ sen~i-rigid or rigid, bnttle or ductile;
'~smear-resistant" as used in this application means resistant of the ink jet ink to smear as descr~ed in the following tat, prin~ng an ima~ge with black lines, allowing a minimum of five minutes time to dry, rubbing the line with tne pad ofthe f njger with a light to moderate pressure, such as might be:used during normal 25 handling of images, and observing whether spread of the lirle occurs.
~ Brief DescrilJtion of the ~Drawin~s Figure I is a p~lan end view of a two-layer image receiving layer J.. after prmting and u.. ' SUBSTITUTE SHEET ~RULE 26 2 ~ 9 7~

Descrintion of the Preferred r ~ 5) Referring to Figure I an ink jet printing sheet ofthe present invention is iliustrated comprising (a) an image receiving layer (11-12) on (b) a substrate (10), wherein the sheet may optionally have (c) a layer of adhesive (13) coated 5 or iaminated to the substrate (10) on the surface away from the image receiving layer ( 11 - I 2) . The adhesive layer ( I 3 ) may or may not be backed with release iiner (14). In this . b~ ' (Figure 1), the image receiving layer (11-12) comprises at least two layers, wherein one layer is a protective penetrant layer(12) and one layer is an ink jet receptor layer (I l).
Once the ink jet printing sheet has been imaged (15) using an ink jet printing process, the printed sheet (100) may be u ._,' ' with a transparentprotective layer (16). The transparent protective layer (16) may be a transparent piastic sheet bearing on one side a pressure-sensitive adhesive or hot-melt (thermal) adhesive, or a clear coat, or a processing technique that will affect the 15 surface ofthe printed sheet (lû0).
Typical release liner (14) comprise a paper or plastic or other suitable sheet materiai coated or otherwise treated with a release materiai such as a silicone or Iluu~Gc~b-)n type material on at least one surface in contact with adhesive layer such that adhesive layer adheres to release layer but is easiiy 20 removed from the release liner when desired so that the adhesive layer is exposed.
Substrates are preferably adurable materiai that resists deleterious effects of exterior signing ~,... ;.~ including large ambient t~ tu~t: ranges -60~C to + 107~C. direct exposure to sun and is optionally ~ ' ' for fixing 25 to exterior surfaces wherein it may be adhered over surfaces with some curvature or non uniformity e.g. walls or surfaces with screw heads or rivets slightly proud of the surt'ace without easily ripping the material or "tenting".However, the invention need not be limited to these, a less durable plastic is useful for interior signing l~, ' such as might be used when images 30 printed have been printed with dye-based ink jet inxs.

SUBSTITUTE SHEET ~RULE 26J

~ ~7q~2 ~
w0 96/08377 ~ u~.~Y 13 Substrates aan be ciear, translucent, or opaque: dependin~ on the application ofthe inv~ention. Opaque substrates are usefi~l ~r view~ing an imagefrom the image side oEthe printed sheet in lighting conditions such as artificial lighting or suniight Tr~msiucent substrates are particularly useful for backiit 5 usages, for exampiS~a luminous si~n.
Substrates useful in the practice of the present imfention are ".~, availabie and many are designed to be exterior dwrablc, which is preferred. ~ examples of such substrates rnciude ~cotchcal~ hlarking Films and Scotchca!'~M Series 9000 Short-Term Removable ~STR) Film avaiiable.
10 from 3M Company, AveryT~ GLTM Series Lon~ Life Films, Aver~ XLr'U
Series i-,ong Life Fi~ns, Avery~M SXrM Series Long Llfe Films, suitable films from the FasCalT'l ~r T;asFlex~ range of films or any other suitable mari~n~, graphic or ~JIUIIIV~ ~1 filrns available from Fasson, Avery or Meyercord.
However, other ~ of suitable materiais exist and the invention shall 15 not be iimited to the above. Alm~ost any rnateriai composed of a plasùc sheetcould be used depeuding on the use of'the finai image, for ex~ample, whether outdoor durabiiity i5 required, and providtn~ that the mk jet~receptor bottomcoat can adhere to the film surface sufficientiy well.
Useful substrates can have a variety of surface finishes such a matte finish 20 as pros~ided with ScotchcalT~ Series 9ûOO Short-Term Removable (ST.R) Film orglossy tinish as proYided with Scotchca~ ~650 Marking Film. Piastic films can be e~truded, calendared or cast different plastic materials may be used, such asthose exemplified by~the ScotchcalTM piasticized poly(vinyi chloride) or Surlyn, a polyolefin. Any suitable plastic material can be employed. ~ examples 25 include poiyester materials exempGfied by MyiarlM availab]e from E.l. Du Pont de Nemours & Company, MclinexTM aYaiiable from Impa7~ Ch=Nds, IQC., and Celanar'M avaiiable from Celanese Corporation. Other examples inciude polyolefins such as ~ .h~l"..~, and puly~JIulJJh,llt~ p~l,rClllbulldt~ pul~.~..,.'~l acrylates, polystyrene, pul~ lru"~,." polyether sulfones, cellulose triacetate, 30 ceDophane, poly~vinyl fluoride), polyin~ides, PeslinT~ available from PPG
Industries, rubbery p~lymers such as styrene-butadiene cûpclymers, nitrile or SUB5TITUTE SHEET (RUL~ 26) 2 1 9~
W096/08377 r~ ,,s;l: ~.3 butyl rubbers, polybulaJ;~....s. Preferred materials for substrates can include those that are piasticized poly(vinyl chloride)s or ionomers although the invention is not iimited to these. Preferred materials are white opaque or translucent materiais but transparent materials and colored opaque, translucent 5 or transparent materials could be useful in special ~
Typical thicknesses of the substrate are in the range of 0.05 to 0.75 mm.
However, the thickness can be outside this range and almost any thickness can be useful provided the film resists tearing or splitting during the printing andapplication process. Given ail ~ ;o ~, any thickness is useful provided 10 the substrate is not too thick to feed into an ink jet printer of choice.
The image receiving layer is comprised of at least two layers, such that at least one of the layers functions as an ink jet receptor. When the image receiving layer is comprised of at least two layers, the uppermost layer functions as a protective penetrant layer and the bottomcoat layer functions as the ink jet 1 5 receptor.
Preferred is a two layer ~,u.,~l, u~,liûll as shown in Figure I . Although an image receiving layer is described as a multilayer constructions, the use of theterm "multilayer" does not necessarily imply that the layers are wholly distinct, that is, there is a discernible ~ .,..l;..g interface, although they may be. There 20 may be, for example, some interlayer mixing especially at the interface during a coating procedure.
Typical hydrophilic or water soluble or water absorbent polymers or binders used in the art are poly(vinyl pyrrolidone), copolymers of vinyl pyrrolidone e.g. with ethylene or styrene, poly(vinyl alcohol), polyacrylic acids, 25 pul~ L~ ;_ acids or (I-alkyl) acrylic acid copolymers and the inorganic saltssuch as alkali metal salts derived therefrom, poly(alkylene oxides) or polyglycols, ~ .,~I,uh~J.. ~,~, alicyl and hydroxylalkyl cellulose derivatives, starch and starch derivatives such as hydroxyalkyl starches, carboxyaiikyl celluloses and their salts, gum arabic, xanthan gum, carageenan gum, proteins and poly~,~,"lid~,.. One or 30 more polymers can be crosslinked by employing other reactants or cataiysts.

SUBS~ITUTE SHEET (RULE 26) 2~q9~ : :
6108377 ~ r~ ~ 3 Preferred, .. ~ .... " ~, of the bottomcoat la~er include copolymers as disclosed m EP 04~4~16 A i ~ poiy (vinyl i,~ , poly(dhyiene oxide), and mordants such as ~IC d~ i in IJ.S. Patent No. 5,342~68~to hir~ier dye migration in ~ ::A printing. E~owever, mordznts are not rec~iuire~i in S printing sheet designt~i for use with pi~nent-based ink jet inks.
Preferred rl ~ . oi s ~ - of tho tapcoat layer are hydrophilic or ~ater-soluble polymers, g~ns and surliactants ~bich are less sensi~e to humidity ar,d moisture from the touch than ru. .,A,ul,yL. is poly(viny~i.y.~ ' ). These include poly~vinyl al~c~ohol)~ ~'ù, ~,.~,tiù.~d particulates such as corn starch or =~ 10 their derivatives or modified corn starches, Xanthan gum~ and surfactants such as Triton X- 100. A silnliar topcoat is described in U. S . Patent No. 4,935,307 and such description is illcv.i,ul~.t"d hereu~ by reference.
It is preferable to use an image receiving layer having a two layer rf. .n ~,~.u~. . wherein both the bonomcoat and topcoat layers c~ontairl a dispersed 15 particle or particula:t~, such that the surface ofthe ink jet printin~ sheet is roughened. The roughened surfacc is ~ .1 h~ l r. ~ ~- J by dispersed particles andlor particulates #uch that ~images printed us;ng pigment-based ink 3et inks in the ink jet printing process are essentially non s...~...~'., or srnear~resistant. ~illing the bottomcoat with parlicuiate matter can achieve a roughened~ receptor surface.
20 Other advantages may also be ga~ined such as improved grip in the ink jet printer and improved transp~rt of the ar.icle of the invention through the printer and the prevention of"bloci~cing." However~ srnoother materials are~also useful, vhen the intended use i~ with dye-based ink jet inks. Flil Ih~ 1. IVI ~ ~uOI~ L;~,....
- having at least two layers are also useful when the layers are~not loaded with 25 dispersed particles w ~ . ' ~ , andfor only one of the layers cont~uns the particles or ~
ru~ llwi~the thickness of the topcoat layer is much thin~ner than the bottomcoat layer. D~ epending on the printirlg application~ the thicknesses may vary. Relative to ea~ch other, the particles and/or p.ll i ' contained in the 30 bottomcoat layer pre~ferably should be larger than the thickness of t:he t~opcoat layer. ~

SUI~STITUTESHEET(RULE26) 2 i ~7'~q2 WO 96/08377 Pcr/Usss/10013 Preferred materials for such dispersed particles and particulate material include materials that are insoluble or of sufficient low solubility in the rest of the ink jet coating mixture that is typically aqueous. Preferred are materials that have some water absorbency. ~( ' , examples of particulate material 5 include corn starch or modified corn starches, silica, alumina, titanium dioxide or other white inorganic oxide or hydroxide materials, cotton or flock particles and other cellulose or modified cellulose particulates, calcium carbonate or calciumsilicate and other white inorganic silicates, sulfides and carbonates, clays, and talc. The size of the dispersed particles or particulates are typically in the range 10 of a~ I to 40 IlliCIu....~ in diameter, preferably in the range of a~ 2 to 20 Vlll.,a,l ~ in diameter. However, it is not intended that the invention be limited to this range, provided there are sufficient particles have sizes large enough to roughen the surface of the bottomcoat and topcoat layers.
The enumerate size distribution is a typical range, although it permissible to use 15 particles or pal ' that are outside the above-stated range of sizes.
Particles and/or particulates are added into the image receiving layers in the range of 10 to 60 ~/0 by weight of total solids, preferably in the range of 15 to 25 O/D by weight of total solids. r~ Lh~ uu~ e~ dispersed particles and particulates are generally available in a distribution of sizes, although it is not intended to 2û forclose the use of a single sized particle or particulate, provided the size is large enough as described above.
Adjuvants to the receptor coatings include but are not limited to water soluble polymers or mixtures of water-soluble polymers acting as absorbent materials or binders or both, crosslinked materials or other polymers, and 25 optionally other materials such as surfactants, ~ , mordants to preventdye bleed or other dye migration in the printed image, other moieties for the prevention of dye-bleed, and dispersions or emulsions. Ultraviolet radiation ~ absorbing materials, free radical scavangers and ' may also be used.
The amounts used of any of the adjuvants are those typical for the adjuvant 30 selected and known to those skilled in the art.

SUBSTITUTE SHEET ~RULE 26) WO 96/083~7 ~ r{TnJS~!;110013 Although it is preferable ts use a pressure-sensitive adhesive, any adhesive that is parti~ilarly suited to the particular substrate sdected and end-use application can be used on the ink jet printing sheet ~Such adhesives are those known in the~art any may includc adhesives that ala ~ tacky S adhesives, pressureDensitive adhesives, .. ~,u~;r~ and/or pm : ... 7.1~
adhesives, hot melt aF.7hesives and the l~ce. I~u, ~h~ lulc, it is permis:s~ible to fabricate an ink jet r~c~eptor sheet withûut the addition of an adhesive layer, for e~ample~ short-run interior signage loaded into a sign box. ~
In this application, u~_' layer refers to any sheet material that 10 can be adhered to the surface af any existing coated or uncoated sheet material "Os . ' - " re~èrs to any process of achiev;ng this adherence, particularly without the entrapment of air bubbles. creases or other defects that might spoilthe appearance ofthe finished article or image. ~ ~
The deleterio~us effects of arnbient humidity may be s7owed by the 15 o.. ' - of a transparent protec ive coat or sheet herei~n referred to as an u .. ' ' . 0~ ' has the iihrther advantage 7hat the images are protected from scratching, splashes, and the ~,.. ' can supply a high gloss finish or other desir~ed surface fn7sh or design, and provide a~degree of desired optical dot-gain The u .. ' layer may also absorb ultraviolet radiation or 20 protect the underlayers and imagc from deleterious effects ol direct sunlight or other srJurces of radiations. 0 . ' is, for example, daon ed in US
patent 4,966,8Q4.
After printinS an image or design onto the receptor layers of the present invention, the image is preferably o.. ' ' ' with a transparent colorless or 25 neariy colorless material. Suitable u.. ' ~ ~ layers include any suitable transparent plastic rnaterial bearing on onc surface an adhesive. The adhesive of the o.wt ~ layer could be a hot-melt or other thermal adhesive or a pressurc-sw.. ~eadhesive. Thesurfaceoftheu.~.' ' layercanprovide hi~h gloss or matte or other surface texture. Preferred u~ ' layers are~0 designed for externa~:graphics ~ 1, - and include matçrials such as those '1~. availabb from 3M Company as ScotchprintT~ g910 Exterior -10-- ' SUBSTITUTE SHEET (RULE 26) 2 1 (~7f~q~

WO 9C108377 PCI'NS9~110013 Protective Film, 8911 Exterior Protective Film, and 8912 Exterior Protective Film. However, other f Ims are available or could be fabricated and the invention is not limited to those . "'' An example of a printing process used in the present invention comprises S feeding the material in either sheet form or dispensed from a roll into an ink jet printer, printing a desrred color or n,unu.,l,. u...~, image, retrieving the image from the printer and, optionally, u . ~ . .g the image with an os .,. ' ~ _ layer to protect the receptor coatings and image from water, scratching and other potential sources of damage to the image, and then removing the release 10 liner, and affixing the printed image to a wall, vehicle side, banner, page or other surface for viewing.
Ad~ . ut~g~,ol.~ly the articles of the present invention accept pigment-based ink jet inks when the substrate is comprised of ~ hcl~ . plastic materials, allowing for heat and light stable image uu..sl~u~,liull~ under such 15 .,;.~ as are found in exterior signing ~
The ink jet printing sheet provide useable images using both dye-based and pigment-based ink jet inks suitable for use, for example, in wide-format inkjet printers wherein both narrow or wide images can be made by ink jet printing process used in signing a,, ' The resultant printed sheet is easily 20 handleable without easy smearing of the image and can be applied, when an adhesive layer is part of the ink jet printing sheet, to a wall, vehicle side or other surface for signing and other ,, ' using techniques well known in the art without use of other devices such as spray adhesives.
Examples The invention is further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All materials are, , "~, available or known to those skilled in the art unless otherwise stated or apparent.

SUBSTITUTE SHEET (RULE 26) 21 q7'~2 w096108377 1l r~Jlla~

In the examples described herein, densitv and optical densities were re'dection densities measured using a Gretag SPM-50 ' , subtracting the density of the unprinted sheet as i,..~,l~ . ' For reference the following example densities were obtained printing onto Hewlett-Packard E~P5163 lE
S Special Ink 3et Pa~r using the E~ewlett-Packard Designjet 650C fitted ~ith theHP51650seriescartridges(includingtheHP51640Ablack)~as,~.. ,.. ~dfor the printer: 1.365 ~ an), 1.154 ~magenta~, 0.967 (yellow,~ and 1.247 (black3.
For reference the following densities were obtained~phn~ onto Hewlett-PackardHP51631ESpeciailnkJetPaperusingthet~Pw1pn-plrlr~rdDesignjet 650CfittedwithtkèHP51640seriescartridges(includingtheHP53k40Ablack):
1.247 (cyan), I .I~:l~magenta}, 0.686 (yeDow) and 1.242 (black3.

Example I
Ink jet pririting sheets for dye and pigment-based ink-jet inks were prepared by coating tise foliowing ~ ' onto ScotchcsllTr's ~arking ~llm Series 3650 available from 3~ Company. A formulation was made up by thoroughiy n~ixing until I ~ 810 grams of a 20~/:o aqueoLss soiution of copolymer as descn~d in EP 0484015 Al, 469 grams of soiid poly~Yinyl " ' ), Kga~ ~wuiable from ISP Te~ ,gj~ Inc.), 162 grants of Carbowax rul~th~ ~ Glycol 600 (available from Union ~rbide Chemicais and Plastics Company Inc.), 108 grams of a 15% solution of mordan~t (mordrsnt wjth chioride coun~erions as described in U.S. Patent No. 5,~42:,688, and PCT
Publication WO 94120304, PCT Publication WO g4/203~5, and PCT Pubiication W094/20306, 35~0grannsofdeionizedwaterand 1638grams ~ofethanol.To ~ the mixture was ad~ded 167 grams of LOK-SIZE~9 30 CatiQ:nic Corn Starch ~avaiiable from A. E. Staley 1' ' ~ ; ,, Company). The solution was rnixed using an overhead stirrer for four hours, and then h. ~tlf'~ ,. ' '' .1 for thirty minutes in a five gallon pail using a Silverson high-speed Multi-Purpose Lab mr~er, fitted with a:D " _ Head.
Before co~t~ng, 3.3 grarns of 30% aqueous ammonia ~avaiiable from Aldrich ChQnicats ~mpanyj and then 24.3 grarns of ~}ama 7, (an aziridine SU~STITUTESHEET~RULE26) 2, ~7~2 ~096/0X377 r~ 13 crosslinker available from Hoechst Celanese Corporation) were mixed in thoroughly The above r~,, was coated on an automated pilot coater at a web speed of 0.10 meters per second onto 0.3048 meter wide ScotchcalTU Marking 5 Film Series 3650: a ~ d~l.,.ltbh, white vinyl product composed of, in order, awbite vinyl layer, a pressure-sensitive adhesive layer, and release paper; available from 3M Co. A knife coater ~ lJ set at a 127 lllil.lUlll~,tl" gap was used and the dried coating weight measured at 14.90 grams per square meter.
The material was passed at 0.10 meters per second through four drying zones;
3 66 meters at 65.6~C, 3.66 meters at 79.4~C, 3.66 meters at 93.3~C, and 7.32 metersat 121~C.
In a second pass~ a topcoat was overcoated onto the product of the above coating operation onto the previously described coated layer using the pilot coater with knife coater set at a 76 micrometer gap. The topcoat similar to that described in U.S. Patent No. 4,935,307 was composed of 66% by weight (of the total mixture) deioni~ed water; I .64% by weight Airvol 540 poly(vinyl alcohol) (available from Air Products) 31.17% by weight of denatured alcohol;
0.61% by weight of LOK-SIZE~ 30 Cationic corn starch (available from A. E.
Staley ~ ~ r ' hlg Company), 0.28% by weight of Xanthan gum, a pOI r ' ' - gum known as KELTROL TF 1000 (available from Kelco Division of Merck & Co. Inc.). and 0.3 & by weight of Triton X-100 surfactant (available from Union Carbide Chemicals and Pla.,tics Company Inc).
Tbis coated article was passed at 0.10 meters per second through four drying zones; 3.66 meters at 65.6~C, 3.66 meters at 79.4~C, 3.66 meters at 93.3~C, and 7.32 meters at 93.3~C. Images were printed directly onto the receptor coating side of the coated material using a Hewlett-Packard HP650C
Design jet ink jet printer fitted ~ ith the standard 51650 series of ink cartridges giving excellent densities, quick drying time, smear-resistant colors including the black (printed from the HP5 1 640A cartridge containing a black pigment-based ink.) SUBSTITUTE SHEET (RULE 26) ~ ~ 9 ~ ~ 9 2 - ~
L I
V~O96/08377 One image ~s u~ d using Scotch~rint~ $910 Exterior Protecti~re Clear Fil~, lustre gloss available from 3M Co usin~ techniques known in the art, giving a gloss irnage protected against spil}s.: The ~
also suppiies additional resistance to dye bleed from humid .,..~;.u~ tril S conditions. ::~ ~
l~xamples of optical densities obtained on sarnples without e,~;. ' by ...~il . ' w'lthp a Gretag SPM-50 hand-held 1~ ~i were 1.2g4 (cyan), 0.969 ~mllaeD~), 0.654 ~yellow), and 1.450 (~lack). ~ ~
This ~ . ' was also pri.rited on an Encad Nova~et ~ide format l0 printer fitted with l ~1~A~Ctr-r Corp. inks ~all d~e-based). Yery high densities were obtained, alth~gh drying times were loneer - on the order of ten minutes to touch dry. Exam~les of optical densities obtained were 1.857 ~cyan~, 1.802 (magenta~, 1.044 (ydlsw), and 1.937 ~blaGk).

Ex~mple 2 The article p oduced w follows iL'ustrates a different type of adhesi~e backed substrate ailo~rng for sfwrt-te:rrn lCi~lU~ ' ' ty of images. ~ .:
solution of the ~ c~ as described in Example I was coated on a pilot coater at a web speed of Q. 10 meters per second onto roll of 0.30 meter wide ScotchGalTM Seri:es soao Short-Torn Removable (STR~ Film, a~railable 20 from 3M Co. and G~mprising tn order, a white virtyl layer, an adhesive layer (which allows removal for up to t~o years with litt'e or no adhesive residue from most surfaces), and a release backing. ~ ~
The bottomcDat was coated onto the vinyi using a ~nife coater set at a gap of il~"~lU~i. hly 127 Ull..,.l,i ~ g a dried coating weight measured at 25 lS.Slgrams per square meter. The material was passed at 0. r meters per second through four dryin~ zones; 3.66 meters at 65.6~C, 3.66 meters at 79.4~C, 3.66 meters at 93 3~C, arld 7.32 meters at 121~C. ~
The i-r ' hi.. as described in Example 1 except ti~iat it was further diluted to 1% so'ids with deionized water. In a second pass~ the diluted tOpGOilt 30 was overcoated onto the product of the above coating orerition orto the ~SUBSTITUTE SHEET(RULE~26 ~ 1 979q2 WO ~6/08377 PCTIUS95110013 previously coated layer using the pilot coater with knife coater set at a 127 ~ ~ gap. For the topcoat the web speed was ~ 0.076 meters per second. The topcoat was applied using a crossflow knife. The material was passed at alJIn ~ 0.076 meters per second through four drying zones; 3.66 meters at 65.6~C, 3.66 meters at 79.4~C, 3.66 meters at 93.3~C, and 7.32 meters at 121~C.
Color test patterns were printed onto 21.6 by 27.9 centimeter samples of these materials using the Hewlett-Packard Designjet 650C giving fast drying images with and smear-resistant images including pigment black. Test patterns and larger full color images were also printed using the Hewlett-Packard Designjet 650C fitted with Hewlett-Packard 51640 series cartridges, giving fast drying smear-resistant images.
Examples of optical densities measured for 100% color areas are: for HP51650 inks (including the E-IP51640A black) printed on the Hewlett-Packard ~ 15 Designjet E~P650C printer: 0.970 (cyan), 1.013 (magenta), O.581 (yellow), and 1.125 (black).
Examples of optical densities measured for ] 00% color areas are: for HP51640 inks printed on the Hewlett-Packard Designjet HP650C printer: 1.367 (cyan), 0 987 (magenta), 0.991 (yeOow), and 1.185 (black).

F,'xample 3 The following example illustrates printing sheet acting as receptors for pigment-based inks alone and thus not requiring any mordanting method to slow or prevent dye-bleed. A formulation was made up by thoroughly mixing until 59.8 grams of a 20% aqueous solution of copolymer as described in No. EP 0484016, 34.6 ~rams of solid poly(vinyl ~J yl l ~ " ' ) K90 available from ISP Te~ .'.. l.~,;. Inc., 12 grams of Carbowax Poly~th~ . Glycol 600 available from Union Carbide Chemicals and Plastics Company Inc., and 263 grams of deionized water. To the mixture was added 121 grams of ethanol and 12.3 grams of LOK-SIZE~ 30 Cationic Corn Starch (available from A. E. Staley 30 1~ If- 1 ; g Company). The corn starch was 1-....l~,. l;, ~1 using a Silverson SUI~STITUTE SHEET (RULE 26~

7 a ~
f ~ i ~
W096/08377 ~ 1~.l~.. ,,.,, L4R r ~ ~ P~ .os~:Laboratory Mixer fitted with a D' ' " ~ Head for a period of ten minutes.
To 50 grama of the above solution was added one dro~let of 30%
ammonia ~L.. ~' ' ' JiUIII Aldrich Chemical Co.) and 0.18 gramS of Xama 7 S (available from Hoechst Celanese Corporation ~ were added~and thoroughly rmixed in. The resulting mixture was hand coated using a knife or notch bar sct at a gap setting of a~yl~ , 127 ' ' , and dried in an oven at 93.3~C for four mir~.
The above coatings ~ere overcoated with the topcoat solution dcscribed inExample I onthe~knifeusingagapsettingof~ odJ~l~ly76 ul~
and dried at 93.3~~ for three rninutes. Imagc arcas printed by the Hewlett-Packard Designjet E3P640A black were smear-resictant and a sarnple without 8910 o . . ' ' ~le. the least protected from the effects of hurrlid air), was placed in an ~ ' charnber for 90 hours at 40~C and 85%
humidity, and showed ~no bleeding of the black or other obvious detrimental effects to the black nnage areas or sheet. Four irnages were rnade and three were o . . ' ~' with ScotchprintlM 89 lO Exterior Protective Clear Film, lustre g DSS availablc from 3M Co. using techniques known in the art giving glossy images.

~cample 4 The followi~ procedure illustrates ~ r at ddifferent bottomcoat ~I :~knPcc~c A boLtomcoat formulation was made up as descnbed in Example I
(but twice the quanthies of each rnaterial), The material was coated on an automated pilot cortter at a web speed of 0.10 meters per second onto a rol- of 0.30meterwideScotchcal~larkingFilmSeries3650~ailablefrQm3M
Company). For 15 ~minutes, a knife coater hp~l u~u:kly set at a 51 micrometer gap was used and the dried coating weight measured at 5.60 grams per square meter. Then for a ~rther 15 minutes, the knife coater was set ~ at a 76 micrometer gap,~ and the dried coating weight measured at 9.16 ~rams per square meter. Then for rnother 15 mirutes, the knife co~at~er WaS s'et SUBSTITUTE S~IEET ~RULE 26) 2 ~ ~79~2 WO gl;J0~377 PCT/US9S/10013 ~".., ' '~, at a 102 micrometer gap, and the dried coating weight measured at 13.3 and again at 13.S grams per square meter. All material was passed at 0.10 meters per second through four drying zones, 0.37 meters at 65.6~C,3.66 meters at 79.4~C,3.66 meters at 93.3~C, and 7.32 meters at 121~C.
S In a second pass. the topcoat (fo~ ~lqfinn as described in Example 1) was overcoated onto the product of the above coating operation onto the previously desaibed coated layer using the pilot coater with knife coater set at a 76 miaometer gap at a web speed of 0.10 meters per second through four drying zones; 3.66 meters at 65.6~C,3.66 meters at 79.4~C,3.66 meters at 93.3~C, and 7.32 meters at 121~C.
Test pattern images were printed using the Mewlett-Packard Designjet 650C fitted with Hewlett-Packard 51640 series cartridges, giving fast drying smear-resistant images at all coating weights. The following table illustrates the optical densities:

r~. ~6 m 9. 1 -p/micron 0.7~ r,._ o. _ o.~ . o. ~
'' 0.7 o 1 Exumple S
A bottomcoat fnnn~ inn containing silica was prepared by thoroughly mixing until h. ~.. ,. ",. . ,- u~, 11.95 grams of a 20% aqueous solution of copolymer as described in 3M patent application no EP 0484016 Al, 6.92 grams of solid poly~vinyl I~Jl~ul;Jù~c) K90 (available from ISP T ' ' ~g Inc.), 2.39 grams of Carbowax Pu:~cll~yl~ Glycol 600 (available from Union Carbide Chemicals and Plastics Company Inc.), 1.59 grams of ] 5% aqueous polymeric 25 mordant solution (mordant with chloride counterions as described in Example 1, 52.6 grams of deionized water and 24.2 grams of ethanol. The mixture was ~ stirred with an overhead air-driven stirrer and 2.46 grams of Aerosil 380 silica (available from Degussa Corporation Silica Division). 0.05 grams of 30%
ammonia (available from Aldrich Chemical Co.) and 0.36 grams of Xama 7, SUBSTITUTE SHEET (RULE 26) WO ~6/1)8377 ~ l'Cl'IUS95~10013 :~:
~available from Hoechst Cdancse Corporation ) were added to the above solution, and thorou=ghly mixed in.
The resulting mixture ~,vas hand coated us;ng a knife or notch bar set at a ,~
gap setting of ~ 127 ..u.,.u.~ .s, and dried in an ovcn at 93.3~C
5 for four minutes.
The above coatings were overcoatcd with the topcoat solution described in Example 1 on the~ if e using a gap setting of ~ , 51 r.
and dried at 93.3~C for three minutes.
Tesl patterns were printed on a Hew1ett-Packard HP650C fitted vith the HP5 1650 series ink cartridges and the HP5 1640A black ink cartridge. Good smcar-resistant images and quick inlc drying wcre obtained. Examples of densities are 0.7181tcyan), 0.663 (magenta), 0.509 (yellow~, and 1.007 ~black).

~m, ' Ex~mple ~
The following example iDustrates a different mordant7 and bottomcoat 15 without a dispersed ~particulate. This formulation gives excdlent images withdye-based ink jet inks~ but ima~es or parts of images printed usin pigmcnt-based inlc}et inlcs remain smearable for an u,..~ ~le timc, e.g. in excess of 48hours. A bottomcoat f,..,...lùi;u., was rnade up as described~in Example 1 with twice the quantitiesiof each material. However, a differen~t rnordant was used 20 than in EXAMPLE 1. The mordant used was a 15~o solution of mordant with one equivalent of chloride ion and one equivalent of t. ~ ion as described in Example 1. The material was cQated on an automated pilot coater at a web speed of 0.043 meters per second onto a roll of 0.3~ meter wide Scotchcal~ Markin~ Film Serics 36~0 ~available from 3M ~ompany). A knife 25 coater ~ set at a 127 micrometer gap was used and the dried coating weight measured at 10.84 grams per square meter. ~
All coated articles were p~ssed at 0.043 meters per second through three heated drying zones, 3.66 meters at 79.4~C, 3.66 meters at 121~C, and 3.66 meters at 121"C. ~

SU8STITUTE SHEET ~RULE 26 21 97q~2 0 96/08377 P~ ) ,3, 13 In a second pass, the topcoat (ru., ' as described in Example 1) was overcoated onto the product of the above coating operation onto the previously described coated layer using the pilot coater with knife coater set at a 5 I micrometer gap at a web speed of û.043 meters per second through three heated drying zones; 3.66 meters at 65.6~C, 3.66 meters at 79.4~C, and 3.66 meters at 93.3~C.
Test plots were directly printed onto the resulting materiai (aqueous coating side) on a Hewleff-Packard HP650C Designjet printer fitted with the 51650 series color cartridges (cyan, magenta and yellow) and the 5164ûA
cartridge (for black ink). Good images were obtained, but not as good as those obtained with materials of the type exemplified in examples 1, 2, 3, 4, 5 and 6 in the respect that black areas ofthe images (i.e. those areas printed with the pigment-based ink from the HP51640A cartridge) could be easily smeared using the described method for an u...taOullalJlc time after printing herein deemed as in excess of 48 hours. Exarnples of densities obtained are 0 820 (cyan), 0.667 (magenta), 0.591 (yellow) and 1.31û (black).

Example 6 The following example illustrates a different plastic material, adhesive and release paper ~U~ l u~liw.. On the same occasion as outlined in Example 4, 20 the same r.." ~-U. ."~ were coated using the same piiot-scaie coating apparatus onto a web ~ 'y 0.41 meters wide comprising a layer of white Surlyn~U piastic, a layer of removable adhesive and a release paper as describedin U.S. Patent Nos. 5,198,301; 5,196,246 and 4,994,322. The material was coated on an automated pilot coater at a web speed of 0.10 meters per second.
25 Various coating weights were used, but in this e~cample the knife coater gap was set at a 102 , ~ O gap a~ u~..l~L~ . This coated material was passed at 0.10 meters per second through four drying zones; 3.66 meters at 79.4~C, 3.66 meters at 79.4~C, 3.66 meters at 93.3~C, and 7.32 meters at 93.3~C.
In a second pass, the topcoat (r~ ' ' as described in Example I and 30 Example 4) was overcoated onto the product of the above coating operation _19_ SUBSTITUTE SHEET ~RULE 26) 2~1 ~7~9~
W096/08377 ~ .._.11,~.,~ D13 onto the previously described coated layer using the pilot coater ~th knife coater set at a 76 ~ at a web speed of 0 10 meters per second through four dryin~ zones; 3.66 mcters at 79.4~C, ~ S~s rn~ at 79.i5C, 3 ~66 meters at 93.3~C, and 7.32 meters at 93.3~C.
Test pattern~images were printed using the Hewlett-Packard Designjet 650C fitted with Hewlett-Packard 51650 series cartridges, giving fast drying smear-resistant images. Examples of densities obtained areqO.978 ~cyan), 0.834 (magenta3, 0.624 ~1ow3 and I .117 (~lack).

l~nple B
The followmg exemplifies that plastic materials ~tll a~ " ~/c and release support without the:receptor iayers of the invention do not behave s~ , ily as ink jet receptor materials with aqueous ink jet inks. Letter size sheets (21.6 X
27.9 cent;meter) of ffle following materiais were fed into a Hewlett-Packard HiP650C Designjet ink jet printer. Printing was attempted with the printer fftted with the HP51640 set of ink cartridges ~with the HP~ 1640A black caTtndge)~
and then attempted with the HP51650 set of cartridges ~including the HP5164QA
black cartridge).
Materiais tesf ed were ScotchcallM Marking Film Series 3650, ScotchprintTA' 8620 ~arking Film, Scutchprinl~ 8640 Markmg Film aii available from 3M: C:o. and a material comprising a layer of white Surlyn~
plastic, a layer of ad lesiYe ailowing for .o.~ , and a rdease paper as described in ll.S. Pa ~ent Nos. ~,198,301; 5,196~246 and 4,9~4,322. The coating oftbis latter materiai to allow ink jet ;nk reception ;s described in Exarnple 6. ~ ;~

~ ~ -20-SUBSmU I E SHEET (RULE 26 2 ~ q 7qq~
WO 96~0g377 PCTIUS95/10013 Inks beaded on the surface of the plastic i.e. did not penetrate to any great extent or at all, and did not wet the plastic surface giving an !" '-image and low densities. The slightest touch of the finger caused the image to smear. This was still true after 18 hours after printing. The above Gb.,~liU~
5 were true of both the dye-based inks and the HP5 1 64ûA pigment-based black.
For an ~ Jl~;dtlUll ofthe scope ofthe invention, the claims follow.

SUBSTITUTE SHEET (RUI E 26)

Claims (5)

1. An ink jet printing sheet comprising a substrate and an image receiving layer contacting the substrate, wherein the image receiving layer is comprised of at least one protective penetrant layer of one composition and at least one ink jet receptor layer of a second composition, and wherein both the protective penetrant layer and the ink jet receptor layer contain dispersed particles or particulates of a size large enough to roughen both a surface of the protective penetrant layer and a surface of the ink jet receptor layer.

2. The ink jet printing sheet according to claim 1 wherein the dispersed particulate is a cornstarch or modified cornstarch.

3 The ink jet printing sheet according to claims 1 or 2 wherein the protective penetrant layer is thinner than the largest size of dispersed particulate in the ink jet receptor layer.

4. The ink jet printing sheet according to claims 1-3 wherein the substrate is an opaque or translucent poly(vinyl chloride)-based plastic sheeting.

5. The ink jet printing sheet according to claims 1-4, further including an adhesive layer adjacent to the substrate and on the surface of the substrate opposite the image receiving layer.