CA2334314C - Cellulose substrates with transparentized area - Google Patents

Cellulose substrates with transparentized area Download PDF

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Publication number
CA2334314C
CA2334314C CA002334314A CA2334314A CA2334314C CA 2334314 C CA2334314 C CA 2334314C CA 002334314 A CA002334314 A CA 002334314A CA 2334314 A CA2334314 A CA 2334314A CA 2334314 C CA2334314 C CA 2334314C
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Prior art keywords
substrate
transparentizing
cellulosic substrate
catalyst
formula
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CA002334314A
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French (fr)
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CA2334314A1 (en
Inventor
Rajendra Mehta
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Standard Register Co
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Standard Register Co
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/26—Agents rendering paper transparent or translucent
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/18—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with itself, or other added substances, e.g. by grafting on the fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • 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.]
    • Y10T428/24934—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including paper layer

Abstract

A cellulosic substrate which is suitable for use as a mailer or envelope and which has at least one transparentized portion is provided. Further, these transparentizing materials may be applied without the need for solvents. These features thus permit continuous, in-line transparentization.

Description

-1~
C!'LLULOSE SU85TRATES WITH TRANSPARENTIZED ARFr4 The present invention relates to a cellulosic substrate, and method of making it, suitable for use as an envelope or mailer, and more particularly, to one having at 3 least one transparentized portion.
As is known, various types of envelopes or mailers with transparent windows exist where the window consists of a cut-out opening in the mailer substrate which is covered by a transparent patch. The transparent patch is usually secured aver the cut-out opening by means of an adhesive, and may consist of any suitable film of 1v transparent material such as glassine, cellophane, or polymeric materials including polyester, polyethylene, polycarbonate, polystyrene, and polyethylene terephthalate.
The adhesive is generally applied to the mailer substrate around the perimeter of the cutout opening to join the outer perimeter of the transparent patch thereto.
The transparent patch can be secured to either the inside or outside surface of the mailer t5 substrate.
In some modem mailing systems, a mailer is formed from a single sheet after it has been imaged by a non-impact printer. These sheets are stacked in an input hopper and 'Fed as single plies through the printer, after which the sheets are folded to form a mailer. A window is provided to permit the name and address to show 0 through. Added thickness caused by such window patches over die-cut window openings causes mis-shapen stacks and prevents trouble-tree feeding.
The typical arrangement of such patches is disadvantageous as the transparent patch is layered on top of or below the substrate making tfie thickness of the window portion of the sheet greater than that of the remainder of the sheet. As a 25 consequence, such sheets form unstable and uneven stacks, and th~rs limit the maximum height to which they can be stacked. This stack-height limitation is burdensome to large scale printing operations.
Another disadvantage with mailers having a cut-out opening covered by a transparent patch is that the edges of the transparent patch often get caught by 3o process machinery, such as sheet transport mechanisms in printers. This results in the destruction of the mailer and usually requires thg machinery to be stopped so that RrV,.~vn!~y;,~Pn.:~:~3UE1VCHEN 05 :28- 8- 0 : .: io,~r,~:~~;,~~":,ii,.
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-a-the destroyed mailer can be removed. Moreover, when heat is employed in such process machinery, the adhesive holding the transparent patch to the mailer substrate can soften, causing the patch to become detached from the mailer substrate.
One aitemative to the cut-outltransparent patch type of arrangement is to apply a transparentizing material to a predetermined portion of the cellulosic mailer substrate to thereby form a window. See, for example, U.S. Pat. No. 5,418,205 to Mehta. Such a method entails the impregnation of the cellulosic mailer substrate with transparentizing material comprising a monomer selected from acrylic esters and methacrylic esters of polyhydric alcohols and vinyl ethers. The spaces between the fibers of the substrate are filled by the transparentizing material. in order to make the impregnated portion transparent, the transparentizing material must have a refractive index close to that of cellulose (1.5).
EP 76363a also teaches a W curable transparentizing material for paper which may comprise vinyl ethers and epoxies.
In order to produce high quality cellulosic mailers on a large, industrial scale by employing a transparentiz~ng material, it is desirable that the transparentizing material be capable of achieving at least three important functions:
1 ) the ability to produce a transparentized portion which possesses a number of physical and chemical properties;
2) the ability to be converxed quickly from a penetrating liquid to a solid after impregnation has occurred; and 3) the ability to quickly penetrate the celluiosic mailer substrate in order to fully impregnate the substrate in the shortest time possible.
The drawback to producing mailers in fihis manner, however, is that most transparentizing materials can perform, at most, only one of the aforementioned functions.
Physically, the transparenYized portion of a celiulosic mailer substrate should be physicaliy strong and flexible (i.e., not brittle) end be receptive to inks. Chemically, the transparentizied portion should meet U.S. Postal Service specifications for reflectance (sufficient transparency to read the printing beneath the transparentized portion) and PCR (°Print Contrast Ratio"-sufficient contrast between the printing and :::::::::::::::::::::::::...:::.:::::::::::::. AMENDED SHEET .:::..
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_g_ background beneath the transparentized portion) and should have sufficient resistance to migrafion andlvr volatilization of the transparentizing material from the place where applied on the mailer substrate such that it does not lose its transparency over time.
Conventional transparentizing materials are not capable of producing transparentized window portions which possess all of the aforementioned physical and chemical properties. U.S. Patent No. 5,0T6,489 to Steidinger, for example, discloses using either wax or oil as the transparentizing material. Wax produces a brittle transparentized area which is easily marred by physical contact therewith to cause a loss of transparency. 1n addition, wax is not receptive to inks and therefore cannot be printed upon. Oll tends to migrate andlor volatilize easily, thus resulfing in a loss of transparency over time.
In an attempt to overcome these problems, certain l9quid polymerizable transparentizing compositions have been utilized. When utilizing polymerizabte transparentizing compositions, the paper substrate is first rendered transparent by impregnating it with the liquid polymerizable transparentizing composfion. The liquid polymerizable transparentizing composition is then cured in situ to solidify the transparentized portion. These polymerizable transparentizing composifions offer several advantages over conventional transparentizing materials, such as wax and zo oil, in that the end-product is usually strong and flexlbie and does not lose it transparency aver time due to migration orlor volatilization. However, there are problems associated with the use of these poiymerizable transparentizmg compositions. For example, the rate at which some of the liquid polymeriizable transparentiztng compositions penetrate a celluiosic substrate is so slow that, after applying the transparentizing composition to the substrate, the substrate must be wound up in a tight roll for a period of lime to allow the material to impregnate the substrate. See for example, U.S. Pat. tVo. 4,416,950 to Muller et al. Such materials are not conducive to the high-speed production of mailers having transparentized windows. in an attempt to overcome the slow rate of penetration associated with known poiymerizable transparentizing compositions, solvents have been included with the polymerizabfe transparentizing composition to lower the viscosity thereof and thereby speed the rate of penetration of the transparentizing composition into the ::::::::.: :._:::.~::.::::::.:. :.:::.~:.~::.~:::::::::. ,~, ~P.! ,''~ ~,_'~r ~ ,.....
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cellulosic mailer substrate (see, e.g., U.S. Pat. No. 4,513,056 to Vemois et alb.
However, the use of solvents with transparentizing materials is undesirable dus to the added process machinery required to evaporate the solvent from the substrate surtace and to recover the evaporated sohrent. It is also known to include water yr water alcohol mixtures with the transparentizing material to increase their wetting capabiiities and thus increase the rate of penetration into a cellulosic substrate. See, for example, U.S. Pat. No. 3,813,261 to Muller et al. However, the use of water with transparentizing material is typically not considered conducive to high-speed production due to the time associated with removing the water from the cellulosic substrate surface. In addition, most transparentizing agents are non-polar and are not soluble in water. Therefore, they form emulsions which are not suitable for uniform distribution of the transparentizing material onto the cellulosic substrate.
In addition, since most poiymerizable transparentizing agents are non polar, they exhibit limited toner adhesion properties, making it difficult to use high speed '15 laser printers to image the transparentized areas on the mailers. This limits the amount of transparentizing material which can be loaded auto the cellulosic substrate and therefore, limits the degrne of transparency in the final transparentized cellulasic product.
Further, although many of these polymerizable transparentizing compositions are therm211y cured, radiation curing is preferable for reasons of both accuracy and economy. Radiation-curable, solventless liquid paper transparentizing compositions are known, but suffer from one or more of the above-mentioned problems. For example, U.S. Pat. No. 5,418,205 discloses a solventiess liquid transparentizing material which quickly penetrates the cellulosic substrate and results in a high quality transparentized portion which is strong and flexible, printable, and which does not lose transparency over time. However, the transparentizing material is non-polar.
Therefore, it is insoluble in water and its wetting capabilities cannot be increased by the addition of water due to the formation of emulsions. In addition, since the transparentizing material is non-polar, it exhibits limited toner adhesion properties.
Therefore, the degree of transparency in the final product is limited.
In addition, many polyrnerizable transparentizing compositions suffer from incomplete andlor slow crosslinking reactions. Incomplete cross-linkiing results :::::::::::::::.-..-.::::::::::::::::.-::::::::::::::. DED S~~ :::::.
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sTO a0a Pg in a product in which unreacted monomer or oligomer remains in the cured transparentized layer. Unreacted monomer or oligomer in the cured transparentized layer may result in tackiness. Uncured or partially cured transpanentized layers which are tacky present various problems, such as blocking (i.e., when two or more forms or transparentized window areas join together and result in problematic printer feeding) and material transfer of uncured constituents to fuser toilers. In addition, unreacted monomer or oligomer in the cured transparentized layer may result in degradation of opacity of the transparentized area.
Other problems associated with polymerizable, 100~/o salids transparentizing composkions are odor and skin irritation on contact.
Accordingly, it is seen that a need exists in the art for a substrate suitable for use as a mailer or envelope having at least one transparentized portion which can be placed in tall, stable stacks and which does not have equipment-catching edges around the window area. Further, the transparentized portion should be capable of being produced at a rate of speed conducive to high-speed production of mailers without the need for solvents or water. In addition, the liquid polymerizable transparentizing compositions should exhibit good toner adhesion properties.
Also, they should be amenable to curing by radiation rather fan by thermal polymerization and such radiation curing should occur both rapidly and completely. In addition, such liquid polymerizable transpan=ntizing compositions should exhibit minimal odor and skin-irritating qualities.
Those needs are met by the present invention. Thus, the present invention provides a cellulosic substrate, and method of making it, which has at least one transparentized portion and preferably, wherein a smooth interface exists befinreen the transparentized portion and the remainder of the substrate. In addition, the transparentized portion preferably has a thickness which is no greater than the thickness of the remainder of the substrate. Thus, no machine-catching edges are present, and mailers made from the substrate will form tall, stable stacks due to the ability to form transparent windows without adding thickness to the substrate.
3o Mcreover, the present invention also provides a salventiess transparentizing material which penetrates the mailer substrate very quickly and cornpietefy. and forms a cured polymeric transparentized portion which not only possesses the aforementioned :::::::::z:::::::'~v%023343142000-12-07 ~'~' l~rl~~,.t:.:::::<..-..:...-..::..-....-~.:T..:._..:: IVIEIV~JED SHEEC

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-G-physical and chemical properties, but also exhibits an improved degree of transparency. in this manner, a very high-~qua~ity transparenfiized portion can be formed on cellulosic mailer substrafies in a fast, continuous. in-line process, without the need for recovering a solvent. Further the present invention provides a liquid polymerizable transparentizing compositions whir:h exhibits good toner~adhesion properEies and is cured by radiation rather than by thermal polymerization and which cure both rapidly and completely. in addition, the liquid polymerizable transparentizing compositions of the present invention exhibit minima! odor and skin-irritating qualities.
1p The present invention provides a cellulosic substrate suitable for use as an envelope or mailer. The cellulosic substrate has at least one transparentized portion which comprises an area on the substrate which has been impregnated with a polymerized transparentizing material, in certain embodiments, the transparentized portion is thinner than the remainder of the substrate. Preferably, the transparentized portion has a smooth interface between itself and the remainder of the substrate, and the transparentized portion has a thickness which is no greater than the thickness of the remainder of the substrate. "Smooth interface" means one in which no loose or sharp edges are present which could get caught in process equipment and cause j2:rns or tears. "Transparentized"means that there is sufficient transparency to read printing beneath the transparentized portion of the substrate (reflectance of at least 50°/o in the red spectrum and at least 4~% in the gr~sen spectrum). and sufficient contrast between the printing and background portion beneath the transparentized portion to provide a print contrast ratio of at least 30%.
The radiation curable transparerrtizing composition of the present invention 25 comprises a free-radical catalyzable constituent; a cafionic catalyzabie constituent;
and a catalyst. As used herein, the term "cationic catalyza.ble constituent"
refers to a vinyl ether, a polyepoxide, a mixture of vinyl ethers, a mixture of pofyepoxides, or a mixture of at least one of a vinyl ether and at least one of a polyepoxide. As used ........:.............................................. , ~ '' ~ ~~~~-~t :...
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herein, the term ufree radical catalyzable constituent° refers to compounds or Formula I or mixtures at compounds of Formula l:
R
R"-~--~-[~GHCHZ] DR'l n Jz wherein R" is any mono- or polyfunctional organic radical which comprises at least one and no more than four functional groups which are reactive with ethylene or propylene oxide;
R is H or CH3;
R' is H or -C(O)C(R)=CH2 with the proviso that at least one R' is -C(O)C(R)=CH2;

z is an integer from 1-4;
n is an integer from 0-20 and is independent of z.
As used herein, the term "catalyst" refers to a photocatalyst comprising at least one free radical catalyst and at least one living cationic catalyst.
Thus, in accordance with one aspect of the present invention, a cellulosic substrate having at least one transparentized portion is provides, the transparentized portion comprising an area of the substrate which has been impregnated with a polymerizabte transparentizing material comprising:
a cationic catalyzable constituent selected from 1 ) a vinyl ether, 2) a palyepvxide, 3} a mixture of vinyl ethers, 4) a mixture of polyepoxides, or 5) a mixture of at least one vinyl ether and at least one polyepoxide;

ii) a free radical catalyzable oonstituant selected from at least one compound of the Formula !:
R"~-~--~OGHCH2]~ OR'~Z
wherein, R" is any mono- or polyfunctional organic radical which comprises at least one and no more than four functional groups which are reactive with ethylene or propylene oxide;
R is H or CH3;
R' is H or -C(O)C(R)=CH2, with the proviso that at least one R' is -C(O)C(R)=CH2 z is an integer from 1-4;
n is an integer from 0-20 and is independent of z; and iii a catalyst constituent r~omprising at least ore free radical catalyst and at least one living cationic catalyst; and,v~erein the transparentizing material has been cured with radiation.
The present invention also provides the cellulosic substrate as defined above, wherein the substrate is in the form of an envelope or mailer having at least a first ply and a second ply, with at least one transparentized portion on the first ply.
Nn advantage of the use of the above-recited polymerizabla transparentizing compositions is that the transparentized portion produced by the coating is a high quality one. Priysically, the transparer~zed portion Is strong and flexible and is highly recepthre to intcs andlor toner. One advantage of such good receptivity to inks andlor toner is that it allows a reverse image fio be printed on the lower surface of the transparentized portion. In this manner, the reverse image is visible as a normal image through the upper-surFace of the transparentized portion.
Ghemirally, the transparentized portion of the present invention meets U.S. Postal Service specifications for reflectance and PCR. This is believed possible due to 'the fact that the transparentizing material penetrates ttye substrate F,fxY::: ~/l~l~...>.:F~'.A:~.(yj[,'r?VC:HFN U5 : 28- 8- 0 F;F:.v:::~x:
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_g_ substantially completely. Additionally, the resulting trransparentized portion has sufficient resistance to migration andlor volatilization of the radiation cured material that it daes not lose its transparency over time. While not wishing to be bound by any specific theory, this advantage is believed due to the fact that the tcansparentizing material is applied is 100% solids and t<we fact that the transparentizing material can be radiation cured almost immediately after it has been applied to the substrate since it penetrates the substrate so quickly.
Although the radiation curable transparentizing materials of the present invention penetrate the fastest when used without oligomers or prepolymers, there 40 may be occasions when the need for specific physical andlor chemical properties in the transparentized portion outweigh the need for high speed penetration. In such circumstances, oligomers andlor prepolymera may be included in the coating.
For example, it may be desirable to include one or more prepolymers in the transparentizing material if, due to the nature of the cellulosic substrate, for instance, 1s it were necessary to adjust the refractive index of the transparentizing material in order to ensure that the cured transparentizing material has a refractive index close to that of the cellulosic substrate. The preferred prepolymers for ibis purpose are selected from the group consisting of styrene-malefic anhydride prepolymer, styrene-acrylic acid prepolymer, and styrene-methacryiic acid prepolymer. Similarly, it may ZO be necessary in certain situations to have a transparentized portion with extra flexibility. In such situations, an oligomer may be included in the transparentizing material. The preferred aligomers are styrene-acrylic acid oligomers or urethane acrytate oligomers. Whether or not a prepolymer andlor oligomer is included in the transparentizing material, however, it is preferable that the transparentizing material 25 have a refractive index of about 1.5 after the transparenfizing material hays been cured. Further, the transparentized portion of the substrate preferably has a thickness in the range of from about 0.0005 to about 0.002 inches (i.e., about 1.~7 x 10"~ cm to about 5.08 x 10~' cm).
In addition to the foregoing, the present invention provides a meti~od of 3o transparentizing a predetermined portion or portions of a celiulosic substrate, preferably such that a smooth interface exists between the transparentized pofion and the remainder of the substrate, and preferably such that the transparent'~zed :::.:::::..~:::.:::.:.:::.:.:::::._:::::: :.::::: :::.:: ::...::. n h HEM
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portion has a thickness which is no greater than the thickness of the remainder of the substrate. In some embodiments, the method comprises making a predetermined portion of the substrate thinner than the remainder of the substrate such that the predetermined portion is rendered substantially transparent, and applying a transparentizing material to the predetermined portion. !n other embodiments, the method comprises heating the transpar~ntizing material prior to application to the predetermined portion of the substrate, heating the predetermined portion of the substrate prior to application of the transparentizing material, or heating both the transparentizing material and the predetermined portion of the substrate prior to ~0 application of the transparentizing material.
As mentioned, the speed at which the above-recited transparentizing material penetrates allows transparentizing to occur in a continuous, in-line process.
Such a process may be a continuous flexographic printing process, gravure, or roll-metering process, with tlexographic being preferred, in which the step of applying the transparentizing material to the predetermined portion occurs in the continuous printing process. The polymerizable transparentizing compositions of the present invention have a viscosity which makes them suitable as "inks" to be applied by printing techniques. The transparentizing composition is th~n cured immediately thereafter as a subsequent step in the continuous process. Preferably, those steps occur at a speed of about 75 to about 1000 linear feet (i.e., about 22.8fi linear meters to about 304.8 linear meters) of substrata per minute.
To provide even faster penetration of the transparentizing material into the substrate, the step of applying the transparentizing material to the predetermined portion can occur simultaneously to both the upper and lower surfaced of the predetermined portion.
In the embodiment wherein the predetermined portion of the substrate is made thinner than the remainder of the substrate, this thinning may be accomplished by removing a portion of the thickness therefrom. The removal is preferably accomplished by mechanically grinding the portion. Preferably, the predetermined 3Q portion has a thickness ranging from about 0.0005 inches to about 0.002 inches (i.e., about 9 .27 x 10'' cm to about 5.08 x 10'' cm) following the grinding operation.
Aitematively, the predetermined portion can be made thinner by compressing, such ,,,". .,. - r~.~.
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_11_ as by calendaring the predetermined portion to a predetermined thickness.
Preferably, such predetermined thickness ranges from about 0.0005 inches to about 0.002 inches (i.e., about 1.27 x 10'~ cm to about 5.tJ8 x 10~ cm) following the compression of the predetermined portion.
S Accordingly, it is a feature of the present invention to provide a celluiosic substrate which is suitable for use as a mailer or envelope and which has at least one transparentized portion. Further, these transparentizing materials may be applied without the need for solvents. Moreover, the present invention also provides a solventless iransparsntizing material which penetrates the mailer substrate very 1o quictdy and completely, and farms a cured polymeric transparentized portion which not only possesses the aforementioned physical and chemical properties, but also exhibits an improved degree of transparency, in this manner, a very high-qualify transparentized portion can be farmed on ceilulosic mailer subsfirates in a fast, continuous, in-line process, without the need for recovering a solvent.
Further the 95 present invention provides liquid polymerizable transparentizing compositions which exhibit good toner adhesion properties and are cured by radiation rather than by thermal polymerization and which cure both rapidly and completely. tn addition, the liquid polymerizable transparentizing compositions of the present invention exl?ibit minima( odor and skin-irritating qualities. These features thus permit continuous, in-20 tine transparentization.
In order that the invention may be more readily understood, reference is now made, by way of example, to the accompanying drawings in which:
FIG. Z is a front etevationat view of a mailer having a transparentized portion showing addressee information;
FIG. 2 is a cross-sectional view of the celluiosic substrate after the predefiermined portion has been thinned by grinding or cpmpression;
i=iG. 3 is a cross-sectional view of the cellulosic substrate after the thinned portion has been impregnated with a transparentizing material;
FIG. 4 is a cross-section view of the cettulosic substrate which has been 30 impregnated with a transparentizing material without any thinning of the substrate;
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FIG. 5 is a front-elevational view of the cellulosic substrate of 1=IG. 3 or hIG. 4 in which a reverse image is printed on the tower surface of the transparentized portion; and FIG. fi is a rear view of the lower surface of the cellulosic substrate shown in FIG. 5.
Referring now to FIG. 1, a mailer or envelope 10 is formed from the cetlulosic substrate 12 of the present invention_ Substrate 12 includes a transparenttzed portion 14. Transparentized portion 14 allows the addressee information 16, on the inside of mailer 10, to be viewed from the outside of mailer 10. Examples of addressee information 16 on the inside of mailer 10 include 1 ) printing on a separate insert, 2) printing the rear inside surface of the mailer 10, or 3) printing on the rear inside surface of the tran5parentized portion 14. Mailer 10 can be any type of mailer or envelope. For example, mailer 10 could be an interrofftce mailer or one which is mailed through the U.S. Postal 5ecvice. In addition, mailer 10 could be designed to accept a facsimile transmission sheet direrny from a facsimile transmission device in order to keep information contained within the facsimile transmission sheet confidential, except for addressee information.
Referring now generally to FIGS_ 2 arid 3, the features of the cellulosic substrate of the present invention which utilizes a thinning of the substrate 12 wilt be described, where like reference numerals refer to like features.
Trenspan:ntized portion 1a of substrate 1Z has an upper surface 18 and a lower surtace 24.
When substrate 12 is used to form a mailer, upper surface 18 will be on the outside of the mailer, while lower surface 20 will be in the inside of the mailer.
Transparentized portion 14 preferably has a smooth interface 22 between:
1 ) the upper surtace 18 and the lower surFace ZO of the transparer~tized portion 14 and 2) the remainder of substrate 12.
In this manner no loose or sharp edges are present on the substrate to get caught in printers or other process machinery.
In addition, in FIGS. 2 and 3, firansparenteed portion 14 has a thickness which is less than the thickness "t" of the remainder of the substrate. As a consequence, :::::::....:;::::...:::::::::::::;:::::::;:::::::...:::......; A ~
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transparentized portion 14 does not increase the thickness of substrate 92.
Thus, numerous ones of mailers yr envelopes formed from substrate 92 can be placed into tall, stable stacks. As mentioned, such tall stacks are more convenient than short stacks and facilitate manufacturing and printing operations.
Referring now to FIG. 2, fransparentized porfion 14 of substrate 12 comprises an area 24 of substrate 12 which is sufficiently thinner than the remainder of the substrate 12. Area 24 can be any predetermined portion of substrate 12 whereat it is desired to place a transparentized portion.
Area ~4 may be made thinner than the remainder of substrate 12 by removing a section of the thickness therefrom or by compressing it. It is pr~ferred that transparentized portion 14 have a thickness ranging from about 0.0005 inches to about 0.002 inches (1.e., about 1.27 x 10,' cm to about 5.08 x 90-3 cm) following the removal or of compression of the section from area 24. Although FiG. 2 shows the reduction in thickness as having bean performed on the upper surface 1 B of transparentized portion 14, it can also be performed to the lower surtace 20, or to both surfaces. In addition, although FlG. 2 shows a reduction of the thickness of area 24 by removal of a section of the thickness therefrom or compression wherein there is a gradual sloping to area 24, one of ordinary skill in the art will readily realize that such compression or removal of tfiickness of area 24 may also be done such that 2o there is a more abrupt sloping to area 24 (not shown).
In one embodiment, thinning of area 24 is accomplished by mechanically grinding away the section. A preferred means of grinding away the section of area 24 is by passing substrate 12 between a large roil and a smaller, grinding roll.
Raised projections of the desired size and shape of the transparentized portion 14 are placed upon the large roll. In this manner, substrate 12 will be ground away by the grinding roll in the shape of the raised projection. Such grinding equipment is readily available commercially. An example of a suitable grinding apparatus is illustrated in U.S. Pat.
No. 4,814,043 to Rousing et al. It is preferred that the shape of the raised projections allow small hoses to be formed in transparentized portion 14. The preferred hole size is 0.10 mm Or larger.
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Area 24 can also be made thinner than the remainder of substrate 12 by compressing substrate 12 at area Z4 to a predetermined thickness. Preferably, such predetermined thickness ranges from about D.0005 inches to about O.OD2 inches (i.e., about 9 .27 x 10'3 cm to about 5.08 x 10-~ cm~ following the compression of substrate .5 12 at area 24. More preferably, the predetermined thickness is 0.002 inch or less (i.e., 5.D8 x 10'~ cm or less. The preferred technique for compressing substrate 12 at area 24 is by calendaring substrate 12, using calendaring equipment, but only at area Z4. In this mannor, area 24 will be thinner, and have a higher density, than the remainder of substrate 12. Compression In selected area may be accomplished by a pair of rotating cylinders, one of which has raised areas on its surface corresponding to areas to be compressed.
FIG. 4 depicts the embodiment wherein no thinning of area 24 is required to result in the transparentized portion 14 which does not increase the thickness of substrate 12. This may be accomplished by either heating area 24 by the application of localized heat which is 5Q°C to about 100°C for about 1 tv about 2 minutes prior to the application of the transparentazing material to area 24, heating the transparentizing material to a temperature of about 34°C to about 50°C priarto application to area 24, or heating area 24 by the application of localized heat which is 50°C to about 10D°C for about 1 to about 2 minutes and also heating the transparentizing material to a temperature of about 30'C to about 50°C
prior to application to heated-area 24.
As shown in FIG. 3 and FiG. 4, a portion 14 of substrate 12 is then impregnated with a radiation curable transparentizing composition of the present invention. Portion 14 can be any predetermined portion of substrate 12 where it is desired to place a transparentized port'on.
The radiation curable transparentizing composition of the present invention comprises a free-.radical catalyzable constituent; a cationic catalyzable constituent;
and a catalyst. As used herein, the term °cationic catalyzable constituent° refers to a vinyl ether, a polyepoxide, a mixture of vinyl ethers, a mixture of polyepoxides, or a mixture of at feast one of a vinyl ether and at least one of a polyepoxide.
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As used herein, the term °free radical catalyzaE~le constituent"
refers to compounds or Formula 1 or mixtures of compounds of Formula 1:
R
R"~-~-[OCHGH~] OR' n wherein R" is any mono- or polyfunctional organic radical which comprises at least one and no more than four functional groups which are reactive with ethylene or propylene oxide;
R is H or CH3;
R' is H or -C(O)C(R)=CHZ, with the proviso that at least one R' is -C(O)C(R)=CH2;
z is an integer from 1-4;
n is an integer from 0-20 and is independent of z.
As used herein, the term "catalyst" refers to a photocatalyst comprising at least one free radical catalyst and at least one living cationic catalyst.
Thus, in one embodiment, there is provided a method of transparentizing a celhrlosic substrate which comprises the steps of a) providing a cellulosic substrate;
b) applying to at least one surtace of the substrate a transparentizing composition comprising: 1 ) at least one of a polyepexide; 2) and at least one of a compound or mixture of compounds of Formula l; and 3) at least one of a ft~ee radical catalyst; and c) curing the transparentizing campasitian with radiation.
1n another embodiment, there is provided a method of tran~parentizing a cellulosic substrate which comprises the steps of: a) providing a cellulasic substrate;
2~ by applying to at least one sur~Ge of the subs~ate a transparentizing composition comprising: 1) at feast one of a Vinyl ether in admixture with at least one of a R~'';..:~'~~:;:~FA.;,-iHUENCHEN US :28- $- 0 : .~;.~'.,.;:~:.,'.~.. ' ,::.9:37 22 .~.,..nr. .rr.~.,.~.,. -.
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poiyepoxide; 2) at least one of a compound of Formula 1; and 3) at least one of a free radical catalyst; and c) curing the transparentizing composition with radiation.
In another embodiment, there is provided a method of transparentizing a cellulosic substrate which comprises the steps of: a) providing a cellutosic substrate;
b) applying to at least one surface of the substrate a transparentizing composition comprising: 1 ) at least one of a polyepoxide; 2) at least one of a compound of Formula I; and 3) at least one of a living cationic catalyst; and c) curing the transparentizing composition with radiation.
In another embodiment, there is pro~rided a method of transparentizing a ceUulosic substrate which comprises the steps of: a) providing a cellulosic substrate;
b) applying to at least one surface of the substrate a transparentizing compositian comprising: 1 ) at least one of a vinyl ether; 2) at least one of a compound of Formula I; and 3) at feast one of a living cationic catalyst; and c) curing the transparentizing composition with radiation.
i~ In another embodiment, thane is provided a method of transparen~zing a cellulosic substrate which comprises the steps of: a) providing a cellulosic substrate;
b) applying to at least one surtace of the substrate a transparentizing composition comprising: 1 ) at least one of a vinyl ether in admixture with at least one of a polyepoxide; 2) at least one of a compound of Formula I; and 3) at least one of a living cationic catalyst; and c) curing the transparentizing composition with radiation.
In another embodiment, there is provided a method of transparentizing a cellulosic substrate which comprises the steps of: e) providing a cellulosic substrate;
b) applying to at least one surface of the substrate a transparentizing composition comprising: 1 ) at least one of a polyepoxide; 2) at least one of a compound of 28 Formula I; and 3) at least one of a free radical catalyst in admixture with at least one of a living cationic catalyst; and C) curing the transparentizing composition with radiation.
In another embodiment, there is provided a method of transparentizing a cellulosic substrate which comprises the steps of: a) providing a ceilulosic substrate;
b) applying to at least one surface of the substrate a transparentizing composition comprising. 7 ) at least one of a vinyl ether, 2) at feast one of a compound of Formula %_.<::~:'::_,: ~::::::~::~ :'::-~<:::::~: ;::::::;.:
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t; and 3) at least one of a free radical catalyst in admixture with at least one of a living cationic catalyst; and c) curing the transparentlzing composition with radiation.
!n another embodiment, there is provided a method of transparentizing a celiulosic substrate which comprises the steps of: a) providing a cellulosic substrate;
b) applying to at least one surface of the substrate a transparentizing composition comprising: 1 ) at least one of a vinyl ether in admixture with at least one of a polyepoxide; 2) at least one of a compound of Formula I; and 3) at least one of a tree radical catalyst in admixture with at least one of a living cationic catalyst;
and c) curing the transparentizing composition with radiation.
1fl As stated above, the free radical catalyzable constituents for use in the present invention may be represented by Formula I:
R"~-~-jOCHCHZJ OR'~z n wherein R" is any mono- or polyfunctional organic radical which comprises at least one and no more than four functional groups which are reactive with ethylene or propylene oxide;
R is H or CH3;
R' is H or -C(O)C(R)=CH2, with the proviso that at least one R' is -C(O)C(R)=CH2;
z is an integer from 1-4; and 2o n is an integer from 0-20 and is independent of z.
As used hes~in, the tern "any organic radical" refers to any organic radical 25 which can be attached to a hydroxyl moiety. Typical examples include mono-or multifunctional aromatic or aliphatic fdrnctionalfies, wherein the aliphatic .r..~t. .~~!a.,:;: ~A ..~..MUENC N 05 8- ... ;:~, ~~. ~. ;~ :~.;.::,;rt.... ~
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functionalities may be unsaturated, saturated, straight, branched, or cyclic in configu rafion.
Examples of compaunds of Formula 1 wherein n = 0 include ethylene glycol diacrylate, ethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hydroxy pentacrylate, perrtacry4ate, diethyiene glycol dimethacrylate, 1,6-hexane diacrylate, trimethylolpropane triacrylate, and tripropyieneglycol diacrylate, all of which are commercially available or readily prepared by techniques and procedures well known bo one of ordinary skill in the art. For example, tripropyfene glycol diacrylate is available from Sartomer or Radcure and pentacrylate is available as SR-2041 from Sartomer.
In addition, compounds of Formula I wherein n is an integer 1-20 may be prepared essentially as shown in Scheme A wherein ail substituents are as previously defined unless otherwise specified.
SCHEME A

~" R
R"~OIi~Z 3 ~ R°-~-[OCHCHZJ~, OH~=
SfBp 8 1_ R
R'~[OCHCHz] ~ OR'~Z
n step b Scheme A, step a, a polyhydric alcohol of formula 1 is reacted with an excess of an oxide of formula 2 to give a polyhydroxy polyether of formula 3. In step b, at least one of the hydroxy functionalities of the polyhydroxy polyether of formula 3 is esterified with acryloyl chloride or methacryloyl chloride to glue the compounds of 2a Formula 1. Although depicted in Scheme A as complete esterification of ail hydroxy functionaiit[es of compounds of formula 3, it is understood that by varying the .:,CA 02334314 2000 12 07 ~i~v'::::::::::::~::::::::~.::: ~::: - - MENDED SHEET ~~g>>

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proportion of reagents, reactions times, and reaction temperatures, that some hydroxy functianalities of the compounds of formula 3 will not be esterified.
The compounds of Formula I may be used in the polymerizable transparentizing composition as individual compounds selected from Formula I
or as mixtures of compounds selected from Formula I.
Suitable polyepoxides for use in the present invention are cycloaliphatic polyepoxides and include, but are not limited to the following:
O
O O
G O ~ and a a a ~~R

wherein R is a straight or branched chain, saturated or unsaturated C,-G6 alkyl, These cycloaliphatic polyepoxides are either commercially available or readily .prepared by methods welt known to those sidlled in the art. For example, cycloaliphatic pofyepoxide 1 is available as UVR-B' 10 from Union Carbide.
These cycioaliphatic polyepoxides may be used in the polymerizable transQarentizing composfion as individual cycloaliphatic polyepoxides or as mixtures of cycloaliphatic paiyepoxides. The linear cycloaliphatic diepoxides 3_ are available from UCB
1~ Chemical Group, under the tradename E-LADE. The methyl hydroxy cyctoatiphatic epoxide 2 is available as ETHB from UCB Chemical Group.
Suitable vinyl ethers for use in the present invention include, but are not limited to, vinyl pyrrolidone, hydrvxybutyl vinyl ether, cyclohexandirnethanoi divinyl ether, polyester vinyl ether, fluoroalkyl vinyl ether, urethane divinyl ether, triethyleneglyool divinyl ether, vinyllether tem~inated urethane monomers and oligomers, and vinyl :.>.::::::::::::::::::::..:::>::~.::::::::::::> _ . . T~ ::::.r~::.
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ether terminated ester monomers and oligomers. These vinyl ethers may be used in the polymerizabie transparentizing composition as iridividuai vinyl ethers or mixtures of vinyl ethers.
A wide variety of free-radical catalysts can be used provided they do not deleteriously affect the desired physical and chemical properties of the resultant transparenfized portion. Suitable free radical catalysts far use in the present invention include, but are riot limited to, xanthones, such as benzoin, ether, benzyldimethoxy ketone, acetaphenones, such as 2,2 diethoxyacetophenone and t-butyl tdchloroacefioPhenone, alkyl benzdin ethers, such as benzoin ether benzophenone, a 'la benzophenone with an amine, such as rr~ethyl diethanolaminedimethylquinaxiline, 4,4'-bis{dimethylamineiaenzophenonej and chloroacetophenone. A preferred class of useful free radical photocataiysts are haloalkyl substituted aryl ketone compounds.
A1l such photocatalysts, useful in the practice of this invention, are either readily available commercially or are easily prepared using known techniques. For example, free radical catalyst 2-hydroxy 1-[4-{hydroxy-ethoxyjphenyiJ-2-methyl-1-propane is avatlabfe as lracure 295~'from Ciba Geigy. The free radical catalysts may be used in the potyrnerizable transparentizing composition as individual free radicat catalysts or as mixtures of free radical catalysts.
Suitable living cationic catalysts for use in the present invention include may be chosen from the family of triarylsulfonium salts or the family of diaryl iodonium salts which may be expressed by the general formula ill:
[Ar,~t~~y Z,; Where Ar is an aromatic radical, each independently having optional substitution;
Q is a sulfur atom or iodine atom;
x is 3 when Q is a sulfuf atom;
x is 2 when Q is an iodine atom;
y is 1 or 2; and Z is SbF'd or P>'s.
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Representative living cationic catalysts of Formula ill fvr use in the present invention include the following:
_ PF4 a s sbl= ' sues'" ~6 ~F; and off These living cationic catalysts are either commercially available or readily prepared $ by one of ordinary skill in the art. For example, a triarytsutfoniumhexafluoroantimonate salt is available as UVI 6974 from Union Carbide and a triaryisulfonlurnhexaftuonaphosphate salt is available as UVI
6990 from Union carbide or as CD-1011, available from Sartomer. These living cationic catalysts may be used in the polymerizable transparentizing composition as individual 1o Living cationic catalysts or as mixtures of living cationic catalysts.
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As one of ordinary skits in the art will recognize, the polyepoxide and vinyl ether constituents of the polymerizable transparentizing agents are particularly amenable to cationic catalysis whereas the acrylate and methacrylate esters of Formula I
are particularly amenable to free radical catalysis. Therefore, when a dual catalyst system (i.e., both free radical and living cationic) is utilized, the polymerizable transparentIzing composition may include approximately equal amounts of free radical catalyzable oanstituent and cationic catalyzable constituent. However, when only a free radical catalyst is utilized, for optimum results, the predominate monomer in the transparentizing composition should be the free radical catalyzable constituent.
~o And when only a living cationic catalyst is utilized, for optimum results, the predominate monomer in the transpasentizing composition should be the cationic catalyzable constituent.
Although the radiation curable transparent'~zing materials of the present invention penetrate the fastest when used without oligomers or prepolymers, there may be occasions when the need for spec>f c physical andlor chemical properties in the transparentized portion outweigh the need for high speed penetration. In such circumstances, oligomers and/or prepolymers may be included in tfie coating.
For example, it may be desirable to include one or more prepolymers in the transparentizing material if, due to the nature of the cellulosic substrate, for instance, it were necessary to adjust the refractive index of the transparentizing material in order to ensure that the cured transparentizing material has a refractive index close to that of the cellulosic substrate. The preferred prepolymers for this purpose are selected from the group consisting of styrene-malefic anhydride prepolymer, styrene-acrylic acrd prepolymer, and styrene-methacryiic acid prepolymer. Similarly, 'rt may also be necessary in certain situations to have a transparentized portion with extra flexibility. In such situations, an oligomer may be included in the polymerizable transparentizing composition as part of the free radical catalyzable reactant.
material.
Suitable oligomers are aromatic yr non-aromatic acrylates or methacrylates and Include, fQr example, urethane acrylates, such EBECRYLT"" 6700 and EBECRYL~
2?0, available from Rad-Cure, urethane methacrylates, epoxy acrylates, such as EBECRYLT'" 3500 EBECRYL~" 3201, available from Rad-Cure, epoxy methacrylates, polyester accylates, polyester methacrylates, and mixtures thereof.
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These oiigomers are commercially available or readily prepared by techniques and procedures well known to one of ordinary skits in the art. Whether or not a prepoiymer andlor oligomer is included in the transparentizing material, however, it is preferable that the transparentizing matertai have a refractive index of about 1.b after the transparentizing material has been cured. Furthe:, the transparentized portion of the substrate preferably has a thickness in the range at from about O.~Ofl05 to about 0.QQ2 inches (i.e.; about 1.27 x 10'~ cm to about 5.08 x 1 Q'3 cm). As used herein, the term °otigomar andlar prepotyrner component" refers to en individual otigomer, an individual prepalymer, a rriixture of individual oligomers, a mixture of individual prepotymers, and a mixture of at least one of an aligomer and at least one of a prepolymer Without oiigomers or prepoiymers, the radiation curable transparentizafiion material of the present invention penetrates a ~Itufosic substrate quite rapidly and can be applied as a ~l0gplo solidsu and still achieve a rapid rate of penetration. "140°~
'i5 SOtidS~ means a liquid material which can be converted 100°f° to a solid upon curing (i.e., crossiinking or polymerization). Thus, it contains no residual volatiles or solvrents. However, if even faster penetration is desired, a polar organic solvent can be added to the coating to lower the viscosity thereof. Preferred solvents are solvents which are polar and miscible with water and include methanol, ethanol, isopropanot, acetone and the like.
The palymerizabte transparentizing composition may further include tram about 0.2% to about 1 °/° of an additive to reduce surface tension of the polymerizzable liauid transparentizing material in order to increase the rate of penetration into the substrate, thus increasing production speed. These additives may be used in the poiymerizable transparentizing composition as individual additives or as mixtures of additives. Suitable additives are fluorocarbons, such as 1=C-171 and FC-129, available from 3M or silicon prepolymers, such as SlLftET 77 Qr DC-9a, available from Union Carbide.
The radiation curable transparentizing composition of the present invention, 3D without aligomers, prepolymers, or additives, comprises from about 10°!o to about 50% of a cationic catalyzable constituent; from about X10°lo to about 80% of a free radical catalyzabie constituent; snd froom about 5°!o to about 76°!O of a catalyst *Trademark .'.1!.~:11,f.,~'.,~1..~..,.r',,.PF!; ;..11~~J .~! I ~ OS -~.rrrcr:b~..'.:.,.a,~r,.: ;..,. "x : ..k r. . ~ , t - . . .._.___ r.;,:
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constituent. Thus, a typical transparentizing composition of the present invention, without oligorners, prepolymers, or additives comprises 1 ) from about 10% to about 50% of any of a vinyl ether, pofyepoxide, mixtures of vinyl ethers, mixtures of polyepoxides, or mixture of apt least one of a vinyl ether and at least one of a polyepoxide; 2) from about 40% to about 80°/° of at feast one of a compound of Formula t; and 3) from about 5 to about 18% of at least one of a free radical catalyst, at least one of a living cationic catalyst, or a mbcture of at least one of a free radical catalyst and at least one of a living cationic catalyst.
Thus, according to the above, typical radiation curable transparentizing 9o compositions, without oligomers, prepolymers, or additives, are exemplified by the following examples 1 ~8:
Example 1 a) from about 25~o to about 40% of at least one of a polyepoxide;
b) from about 409 to about 80% of at least one of a compound of Formula I; and 1s c) from about 5% to about 10°!° of at feast one of a free radical catalyst.
am 1e 2 a) from about 309~o to about 35~ of at least one of a polyepoxide;
b) from about 55~o to about 60% of at least one of a compound of Formula I;
and c) from about 8% to about 10% of at least one of a living cationic catalyst.
20 F~cample 3 a) from about 30% to about 40% of at least one of a potyepaxide;
b) from about 509'° to about 60% of at least one of a compound of Formula f;
c) from about 3% to about 8% of at least one of a free radical catalyst; and d} from about 3% to about 8% of at least one of a living cationic catalyst.
25 Exam~ie 4 a) from about 10% to about 30% of at least one of a vinyl ether;
b) from about 60% to about 70°l0 of at least one of a compound of Formula I; and c) from about S% to about 12% of at least one of a living cationic catalyst.
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Exam 1e i a) from about 1 Q% to about 20% of at least one of a vinyl ether;
b) from about 60% to about 709~o of at least one of a compound of Form~la t;
c) from about 5% to about fi% of at feast one of a free radical catalyst; aid d) from about 596 to about 7% of at least one of a living cationic catalyst I
Exam to t a) from about 24°lo to about 30% of at least one of a polyepoxide; f b) from about 10% to about 1 a% of at least one of a vinyl ether, c) from about ~40% to about 50°!0 of at least one of a compound of Formula l; and 1 o d} from about 5°~6 to about 10% of at least one of a living cationic catalyst.
Example 7 a) from about 20% to about 300 of at least one of a polyepoxide;
b) from about 10% to about 15% of at feast one of a vinyl ether;
c) from about 40% to about 50% of at least one of a compound of Fomlula I; and d} Pram about 8% to about 10% of at least one of a free radical catalyst.) f Example 8 j a) from about 20°!o to about 30% of at least one of a palyepoxide;
b) from about 10% to about 15% of at least one of a vinyl ether, c) from about 409'° to abflut 45% of at least one of a compound of Farrrdula !;
d) from about 4% to about 6% of at feast one of a free radical catalyst; f nd e) from about 8% to about 10% of at least one of a living cationic catalyst.
The radiation curable transparen4zing composition of the present without oiigomers or prepotymers, but with additives, comprises from abou 109'o to about 50% of a cationic catalyzable constituent; from about 40% to about % of a free radical catalyzable constituent; from about 5°~ to about 13% of a constituent; and from about 0.5% to about 3% of an additive constituent. thus, a typical transparentizing composition of the present invention, without oligo I
ers or re o1 rners but with additives com rises 1 } from about 7 Q% to about 50% of any of P P Y , P , t:::::::;..-.::::::!;:..::::::....:::::...::...:::::::;> ~ ~ ' , ' ::::>::.
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2&
a vinyl ether, polyepoxide, mixtures of vinyl ethers, mixtures of polyepoxides, or mixture of at least one of a vinyl ether and at least one of a pofyepoxide; 2) from about 40°~ to about 80°f° of at least one of a compound of Formula !; 3) from about 5 to about 13% of at (east one of a free radical catalyst, at least one of a living cationic catalyst, or a mixture of at feast one of a free radical catalyst and at least one of a living cationic catalyst; and 4) from about 0.5% to about 3% of an additive or mixture of additives.
Thus, according to the above, typical radiation curable transparentizing compositions, without oligomers or prepolyrners, but with an additive are exempi~ed 1o by the following examples 9-16:
Example J
a) from about 25% to about 35% of at least one of a polyepoxide;
b) from about 50% to about 70% of at feast one of a compound of Formula t;
c) from about 5% to about 10°l° of at least one of a free radical catalyst; and d) from about 1 to about 3°.~° of an additive or mixture of additives.
Example 10 a) from about 30% to about 35% of at least one of a polyepoxide;
b) from about 50% to about 55% of at least one of a compound of Formula !;
c) from about 8% to about 10°/° of at least one of a living cationic catalyst; and d) from about 1 % to about 2% of an additive or mixture of additives, ~campie 19 a) from about 26% to about 40% df at least one of a polyepoxide;
b) from about 40°~o to about 64°1° of at least one of a compound of Fomrtula I;
c) from about 2% to about 5% of at least one of a free radical catalyst;
d) from about 4% to about 6% of at feast one of a living cationic catalyst;
and e) from about 1 % to about 2% of an additive or mixture of additives.
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Examole 12 a) from about 10% to about 20% of at least one of a vinyl ether, b) from about 60°I° to about TO°~ of at least one of a compound of Formula I;
c) from about 8% to about 10% of at least one of a living cationic catalyst;
and d) from about 1 % to about 2°Yo of an additive or mixture of additives.
Example 13 a) from about 9 0% to about 20°~ of at least one of a vinyl ether;
b) from about 60°fo to about 70% of at least one of a compound of Formula I;
c) from about 5°~ to about 6~0 of a free radical catalyst;
90 d) from about 5% to about 7% of at least one of a living cationic catalyst;
and e) from about 1 % to about 2% of an additive or mixture of additives.
Example 14 a) from about 20°!° to about 30°~ of at least one of a polyepoxide;
b) from about 10R~o to about 15% of at least one of a vinyl ether, c) from about ~0% to about 50~° of at least one of a compound of Formula I;
d) from about 5°~ to about 10% of at leas# one of a Wing ca5onic catalyst; and e) from about 0,5°l° to about 1% of an additive or mixture of additives, Exa m is a 15 a) from about 209'° to about 30% of at least one of a polyepoxide;
2o b) from about 10% to about 15% of at least one of a vinyl ether;
c) from about 40% to about 50°J° of at least one of a compound of Formula I;
d) from about 5% to about 10% of at least one of a free radical catalyst; and e) from about 0.5~'a to about 1 °!° of an additive or mixture of additives.
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Exam ID a 16 a) from about 20~° to about 30% of at least one of a polyepoxide;
b) from about 10% to about 15% of at least one of a vinyl ether, c) from about 40% to about 450 of at least one of a compound of Formula i;
d) from about 3% to about 5% of at least one of a free radical catalyst;
e) from about 6% to about 8% of at least one of a living cationic catalyst;
and f) from about 0.5% to about 1 % of an additive or mixture of additives.
The radiation curable transparentizing composition of the present invention, with oligamers and/or prepolymers, but without additives, comprises from about 10%
to about 50% of a cationic catalyzable cons~tuent; from e~bout 40% to about 80°r6 of a free radical catalyzable constituent; from about 5% to about 13% of a catalyst constituent; and from about 2% to about 50%, preferably frvrr~ about 2% to about 12% of an oligomer andlor prepolymer component. Thus, a typical transparentizing composition of the present inrrention, with oligomers andlor prepolymers, but without '15 additives comprises 1 ) from about 1 t?% to about 5D% of any of a vinyl ether, polyepoxide, mixtures of vinyl ethers, mixtures of polyepoxides, or mixture of at least one of a vinyl ether and at least one of a polyepoxide; 2) from about 40% to about 80% of at least one of a compound of Formula I; 3) from about 5 to about 13°~ of at least cane of a free radical catalysts, at least one of a living cationic catalyst, or a mixture of at least one of a free radical catalyst and at least one of a living cationic catalyst; and 4) from about 2% to about 50%, preferably from about 2% to about 12%
of an oligorner andlor prepolymer component.
Thus, according to the above, typical radiation curable transparentizing compositions, with oligomers, prepolymers, but without an additive component are exemplified by the following examples 17-24:
Examote 17 a) from about 25% to about 35% of at least one of a polyepoxide;
b) from about a0% to about 70% of at feast one of a compound of Formula I;
c) from about 4°~6 to about 6% of at least one of a free radical catalyst; and d) from about 3 to about 6% of an oligomer andlor prepoiymer component.
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szo aao Pa _z~_ Exam~ie 18 a) from about 30% ba about 35% of at least one of a polyepoxide;
b) from about 50% to about 5~% of at least one of a compound of Formula 1;
c) from about 5% to about 10% of at least one of a living cationic catalyst;
and d) from about 5% to about 890 of an oligomer andlor prepolymer component.
Exar~,~le 1,9-a) from about 309° to about 40% of at least one of a polyepoxide;
b} from about 50% to about 60% of at least one of a compound of Formula i;
c) from about 3% to about 4% of at least one of a free radical catalyst;
d) from about 49~o to about 6% of at least one of a living cationic catalyst;
and e) from about 3% to about 4% of an oligomer andJor prepolymer component.
Examr~le 20 a) from about 12% to about 20% of at least one of a vinyl ether;
b) from about 60% to about 70°!° of at least one of a compound of Formula !;
c) from about ~% to about 10% of at least one of a living cationic catalyst;
and d) from about 5% to about 10% of an oligomer andlor prepolymer component.
Example 21 a) from about 14°/° to about 20% ~f at least one of a vinyl ether;
b) from about fi0~o to about 70% of at least one of a compound of Formula 1;
c) from about 5% to about 6°~ of at least one of a free radical catalyst;
d) from about 5% to about 7°r6 of at feast one of a living cationic catalyst; and e) from about 4°lo to about 5% of an oligamer andlor prepolymer component Example 22 a) from about 20% to about 30% of at least one of a polyepoxide;
b) fnam about 10% to about 9 5°/a of at least one of a v9ny1 ether, c) from about 40°~ to about 45% of at least one of a compound of Formula I;
d) from about 5°~ to about 10°!° of at least one of a living cationic catalyst; and e) from about 4% to about 5°~ of an oligomor andlor prepolymer component.
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~cam~fe 23 a) from about 20°~ to about 30R~o of at least one of a polyepoxide;
b) from about 10% to about 15°y° of at (east one of a vinyl ether;
c) from about 40°~ to about 459r° of at least one of a compound of Formula l;
d) from about 8% to about 10% of at least one of a free radical catalyst; and e} from about 4~o to about 5% of an oligomer and/or prepotymer component.
E m 1 24 a) from about 20% to about 30% of at least one of a polyepoxfde;
b} from about 10% to about 95% of at least one of a vinyl ether;
~t o c) from about 40% to about 45°/° of at least one of a compound of Formula I;
d) from about 39~o to about 5% of at least one of a free radical catalyst;
e) from about 6% to about 890 of at least one of a living cationic catalyst;
and from about 3% to about 5% of an aiigorner andlor prepolymer component.
The radiation curable transparentizing composition of the present invention, 1S with oligomers andlor prepolymers, and with additives, comprises from about 10°~ to about 50% of a cationic catalyzable constituent; from about 30% to about 80%
of a free radical catalyzable constituent; from about 59~o to about 13°fa of a catalyst constituent; from about 1 % to about 50%, preferably from about 1% to about 10% of an oligomer andlar prepolymer component; and from about 0.2°,6 to about 2% of an 20 additive. Thus, a typical transparentizing composition of the present invention, with Oligomers andlor prepolymers, and with additives comprises 1) from about 10%
to about 50% of any of a vinyl ether, polyepoxide, mixtures of vinyl ethers, mbctures of poiyepoxides, or mlxiure of at feast one of a vinyl ether and at least one of a polyepoxide; 2) from about 309° to about 80% of at least one of a compound of 25 Formula I; 3) from about 5% to about 13% of at least one of a free radical catalyst, at least one of a living cationic catalyst, or a mixture of at least one of a free radical catalyst and at least one of a living cationic catalyst; ~) from about 1 % to about 50%, preferably from about 19~o to about 10% of an otigorner andlor prepolymer component; and 5) from about 0.2% to about 2°~ of an additive or mixture of 30 additives.
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Thus, according to the above, typical radiation curable transparentizing compositions, with oligomers and/or prapolymers and with an additive component are exempl~ed by the following examples 25-32:
Example 25 a) from about 25% to a~~ 35% of at (east one of a polyepoxide;
b) from about 50% to about 70% of at least one of a compound of Formula I;
c) from about 4°!o to about 6% of at least one of a free radical catalyst;
d) from about 3 to about 5°!° of an oligomer andlor prepolymer component; and e) from about 0.5% to about 2% of an additive or mixture of additives.
Eoarn~_ . 1e 26 a) from about 30% to about 35% of at least one of a polyepoxide;
b) from about 50% to about 55% of at least one of a compound of Formula l;
c} from about 5°!° to about 90°~ of at least onE of a living cationic catalyst;
d) from about 5°~° to about 8% of an oligomer andlor prepolymer component; and e} from about 1 % to about 2% of an additive or mixture of additives.
Exa mpl~
a) from about t 0% to about 30°fo of at least one of a polyepoxide;
b) from about 30% to about 60°!° of at least one of a compound of Formula 1;
c) from about 3°!° to about 690 of at least one of a free radical catalyst;
2c d) from about 2% to about 0°!° of at least one of a living cationic catalyst;
e) from about 1 % to about 10% of an oligomer andlor prepolymer component;
and f) from about 0.2% to about 't% of an additive or mixture of additives.
Exam t 2 a) from about 10% to about 20% of at least one of a vinyl ether;
b) from about 60% to about 70°!° of at least one of a compound of Formula f;
c) from about 89~o to about 10% of at least one of a living cationic catalyst;
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and e} from about 1 ~o to about 2% of an additive or mbchrre of additives.
Example 29 a) from about 10% to about 20~° of at least one of a vinyl ether, b) from about fig°~ to about 70°/0 of at feast one of a compound of Formula I;
c) from about 5% to about 6% of at least one of a free radical catalyst;
d) from about 5% to about 7% of at least one of a living cationic catalyst;
e) from about 4% fix about 5°~ of an oiigomer andlor prepolyrner component; and 1o f) from about 7 % to about 2°!0 of an additive or mixture of additives.
Example 30 a) from about 20% to about 30% of at least one of a palyepoxide;
b} from about 90% to about 15°/0 of at least one of a vinyl ether, c) from about 40% to about 45% of at least one of a compound of Formula 1;
d) from about 5°lo to about 10% of at feast one of a living cationic catalyst;
e) from about 4% to about 6% of an oHgarner andlor prepolyrner component; and fij from about 0.5% to about i'°~ of an additive or mixture of additives.
F~camole 31 a) from about 20°~ to about 30% of at least one of a polyepoxide;
2o b) from about 10% to about 15°!0 of at least one of a vinyl ether;
c) from about 40r'° to about 45% of at (east one of a compound of Formula i;
d) from about 5% to about ~0% of at least one of a free radical catalyst;
e) from about 4% to about 6~° of an oligomer andlor prepoiyrner rornponent; and f) from about 0.5% to about 1 % of an additive or mixture of additives.
Example 32 a) from about 20% to about 30°~ of at least one of a polyepaxide;
b) from about 9 0% to about 15°~ of at least one of a vinyl ether, c} from about 4b% to about 45% of at least one of a compound of Fomnula i;
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d) from about 3% to about 5% of at least one of a free radical catalyst;
e) from about 6% to about 8°/a of at least one of a living cationic catalyst;
f) from about 3% to about 596 of an oligomer and/or prepalymer component; and g) from about 0.5°~ to about ~ % of an additive or mixture of additives.
A prefierred radiation-curable transparentizing composition of the present invention comprises:
a) from about 30°~ to about 444/° of a polyepoxide of the formula O,T r-rp O
b) from about 50% to about 60% of tripropyleneglycvl diacrylate;
c) from about 3% to about 6°~ of pentaarylate;
90 d) about 4.5% of 2-hydroxy-1-[~-(hydroxy..ethoxy)phenyl]-2-methyl-1-propane;
and e) about 5.5°t° of a triarylsulfonium hexafluorophosphate salt of the formula r +S / ~ S
PFg A more prefen-ed radiation-curable transparentiang composition of the present invention comprises:
~s a} from about 3p% to about 32~° of a polyepoxide of the fom~uta O p '~'~O
j~O
b} from about 52% to about 55% of tripropyieneglyooi diacryiate;
AMEiV~7El~ SHEET
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., ~~' : .. . . .: '. ..:: :........::~:~ ~: ~;
..~::::::.~:n:.v:::::::r: '.::'.::~:~.:::::::::::::::..~~::5:::::::.wns~::v.,:
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::.:y::::::::>::..'.~:::;;.:q~,._..:.y,;,;,.: :.:..:!:..:;.:.,:.,:::.::.:,-.c.:o::..:....: ~.:.,.,.:,.,..:~.,.,":>,. ::::.:..:.,......
y c) from about 4% to about 5% of pentacrylate;
d) about 4.5°/a of 2-hydroxy-1-(4-~hy~lroXy_ethoxy)phenyfj-z-meihy!-1-propane;
and e) about 5.5~° of a trlarylsuifonium hexafluorophosphate salt of the formula PFa A still more preferred radiation-cura5le transparentizing composition of tf~e present invention comprises:
a) about 34.5°l0 of a polyeroxide of the formula O O

b) about 54% of tripropyienegiycoi diacryiate;
1Q c~ about 4.5°l0 of pentacryiate;
d) about 4.5% of 2-hydroxy-7-[4-(hydroxy-ethoxy)phenyl]-2-methyl-1-propane;
and e) about 5.5% of a triarylsulfonium hexafluorophosphate salt of the formula PFg AiNENDED SHEET ,~ .,_,.
:::::::::':::::::::.~:._:~w~02334314':2000 ::.~:::.:a C~''~~air.:~:::::.=..:r.;::~..--..:T.:~.;; -12-07 /.'V!:.:~'fl~'~':xita.~.;:. I ,:.1.l.'..:'.F:I;.:a:<~.;:hr::a;~~..:;un:..:. ~
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.:.:.:.:.:::.,.ry..
:..:::::.~..::.:. ~:::::.:::.::.::,::: .:r. ::: -..::.~.:.::::.:..~...:;
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-r.:. . . .ra,:»:: ;::::.~,:.~,f::: :k~>F>::;.:.:
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sTD soa pa Yet a still more preferred radiation-curable transparentizing composfion of the present invention comprises:
a) about 31.5% of a polyepoxide of the formula O O
O

b) about 54% of tripropyleneglyco! diacrylate;
c) about 4.5% of pentacrylate;
d) about 4.5% of 2fiydroxy-1-[4-(hydroxy-ethoxy)phenylJ-2-methyl-9-propane;
and e) about 5.5% of a triarylsulfonium hexafluorophospha~te salt of the formula - s ~ ~ s PFs io Preferably, the polymerizable transparentizing composition is cured by exposure to one of radiation-eith~r electron beam, visible or ultraviolet radiation.
Curing causes the polymerizabie constituents of the transparentizing material to polymerize, fihus making a permanently transparentized portion. once the 9~ transparentizing composition is cured, it is a solid and will not migrate or volatilize.
Advantageously, the rapidity with which the present transparentizing material penetrates the substrate allows curing thereof almost immediately following its application to the substrate, thus providing substantially no opportunity for the material to migrate or volatilize beyond the area to which it has been applied. The 20 liquid polymerizable transparentizing compositions of the present invention are cured rapidly and completely. For example, transparentizing compositions of the present :::::::::::::::::_:::::::::::~..:;:~~.:::::::::....::...::: ED SHEET :::.
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_3g_ invention which contain both free radical and living cationic catalysts wilt typically demonstrate a 95% or greater completion of cross-(inking reactions. (n addition, compositions containing living cationic catalysts, either alone or in combination with free radical catalysts, will continue to cure to some extent even after exposure to radiation has ceased. And while the application of radiation alone activates both the free radical and living cationic catalysts components of the polymerizable transparentizing composition to initiate cross-linking, the crosslin(cing rate may be enhanced by the application of neat which may be convanien~y provided by infrared radiation. Heat is particularly effective in promoting the activity of the cationic catalyst.
The speed at which the transparentizing material of the present invention penetrates substrate '12 allows fransparentizing to occur in a continuous, in-line process. Such a process can include any conventional printing method such as flexographic, gravure, or screen. A continuous transparentization process can be set up in which the transparenti~ing material is first applied to area 24 in a fiexographic printing press and then cured immediately thereafter by electron beam, visible, or ultraviolet radiation.
In the case of a flexographic printing press in combination with ultraviolet curing, for example, an acceptable rate of transparentization {i.e., applying the 2t1 transparenfizing material to substrate 12 and curing it } is from about 75 to about 150 linear feet (i.e., about 22.9 meters to about 45.72 meters} of substrate per minute.
Obviously faster production speeds are usually preferred. One expedient for increasing production speed is to mildly heat the substrate andlor transparentiz(ng material (50°C-100°C) to effectively reduce viscosity and increase the penetration rate. The preferred viscosity of the coating at 25°C is from about 30 to about 100 cent(poise and more preferably from about 30 to about 70 centipoise. The preferred wavelength of the ultraviolet curing sight is from about 200 to about 400 nanometers, and the preferred ultraviolet curing light capacifiy is from about 300 to about 600 watts per inch of substrate width.
3o The transparentizing material can be applied to one or both sides of substrate 12 at area 24. it is preferred, however, that it be applied simultaneously to both sides AMENOEO ~N~EET
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of area 24. Such simultaneous application provides even faster penetration of the transparentizing material into the substrate.
Advantageously, the use of polymerizable transparentizing composition of the present invention, without oligomers or prepotymers, resuEts in a transparentizing material which not only penetrates substrate 12 quicf~ly, but also produces a transparentized portion 14 which meets all of the desired physical and chemical properties. Physically, transparentized portion 14 is strong, flexible and durable such that it will maintain its transparency when subjected to rough handling. !n addition, transparentized pardon 14 is highly receptive to inks andlor toners. An advantage of such good receptivity to inks andlor toners is that it allows a reverse image to be printed on the lower surface of the transparentized portion. This feature will be explained in greater detail below.
Chemically, the transparentized portion 14 has suftfcient resistance to ultraviolet radiation that it does not lose its transparency aver time. The transparentized portion meets U.S. Postal Service specifications for reflectance and PCR. This is believed possible due to the fact that the above-recited monomers achieve substantially complete penetration of substrate 12. Additionally, transparentized portion 14 has sufficient resistance to migration andfor volatilization of the radiation cured transparentizing material that it does not lose its transparency over time. Due to the rapid penetration of the transparendzing material into substrate 12, the transparentizing material can be cured almost immediately after it has be~n applied to area 24. Moreover, although compatible with polar organic solvents, the transparentizing material of the present invention does not require the use of organic solvents. Therefore, it is less volatile after curing than one containing an organic solvent, thus further reducing the tendency to migrate or volatilize.
!t is preferred that the transparentizing material, once cured, have a refractive index as close as possible to that of substrate 1Z. This wilt ensure that the transparentized portion 14 will be sufficiently transparent. Most ceilulosic substrates have a refractive index of around 1.5. Thus, the preferred refractive index of the cured coating is similarly around 1.5.
However, some ceilulosic substrates have a refractive index which is greater than 1.5. With such substrates, it may be desirable to include one or more ..:,~.~~.~::~:CA...02334314_.,2000 12 07 ~; ~ ~ _' ::::::::::::::::'..:::~:::::::::...<:::::::::::'.-:: ~v~IIE~ :::::: :.:

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prepolymers with the transparentizing material in order to increase the refractive index of the cured transparentizing material to substantially match that of the substrate. Typically, 9 .55 is the highest value that the refractive index of the cured transparentizing material will need to attain in this manner. The preferred s prepolymers for this function include styrene-malefic anhydride, styrene-acrylic acid and, styrene-methacryiic acid. The most preferred prepolymer of this group is styrene.maleic anhydride.
It may also be desirable in certain situations to have a transparentfized portion with extra flexibility. For this purpose, an oiigomer rnay be included with the ~!~ transparentizing material. The preferred oligamers in this instance are urethane acryiate oligomer and styrene-acrylic oligomer.
Referring now to FIGS. 5 and fi, the reverse image printing feature of the present invention will be discussed. FlG. 8 is a view of the lower surface 30 of substrate 12 and shows reverse image 80, which has been .printed an the lower 't5 surface 20 of fransparentized portion ~i4. Reverse image 8d can be printed with any conventional printing mea-rs, such as laser printing, ion deposition prinfing, ink jet printing, or thermal transfer techniques. FIG. 5 is a view from the upper surface 82 of substrate 12 and shows reverse image 80 as it appear; through the upper surtace Z8 oftransparentiz~ed portion 1~.-.i.e., as a normal image. When substrate 92 is used to 20 form a mailer, the normal image of reverse image 80 is the image that will be seen by the observer.
While representative embodiments and certain details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various cha;~ges in the methods and apparatus disclosed herein may be made 25 without departing from the scope of the invention, which is defined in the appended claims.
::...::::~:::::::::::::::::::::::::::::::::::::::: ENDED SHED :::::::::::.
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:::::'::::::~::::::::;~~.02334314'..2000 12 07 :..:,;.~, :...: - -

Claims (18)

1. A cellulosic substrate having at least one transparentized portion, said transparentized portion comprising an area of said substrate which has been impregnated with a polymerizable transparentizing material comprising:
i) a cationic catalyzable constituent selected from 1) a vinyl ether, 2) a polyepoxide, 3) a mixture of vinyl ethers, 4) a mixture of polyepoxides, or 5) a mixture of at least one vinyl ether and at least one polyepoxide;
ii) a free radical catalyzable constituent selected from at least one compound of the Formula I:
Wherein, R" is any mono- or polyfunctional organic radical which comprises at least one and no more than four functional groups which are reactive with ethylene or propylene oxide;
R is H or CH3;
R' is H or -C(O)C(R)=CH2, with the proviso that at least one R' is -C(O)C(R)=CH2;
z is an integer from 1-4;
n is an integer from 0-20 and is independent of z; and iii) a catalyst constituent comprising at least one free radical catalyst and at least one living cationic catalyst;
wherein said transparentizing material has been cured with radiation.
2. A cellulosic substrate as claimed in claim 1 wherein the polyepoxide is selected from wherein R is a straight or branched chain, saturated or unsaturated C1-C8 alkylene.
3. A cellulosic substrate as claimed in claim 1 wherein the vinyl ether is selected from vinyl pyrrolidone, hydroxybutyl vinyl ether, cyclohexandimethanol divinyl ether, polyester vinyl ether, fluoroalkyl vinyl ether, urethane divinyl ether, triethyleneglycol divinyl ether, vinyl/ether terminated urethane monomers and oligomers, or vinyl ether terminated ester monomers and oligomers.
4. A cellulosic substrate as claimed in claim 1 wherein the at least one free radical catalyst is selected from 2-hydroxy-1-[4-(hydroxy-ethoxy)phenyl]-2-methyl-1-propane, benzoin ether benzophenone, methyl diethanolaminedimethylquinoxiline 4,4'-bis(dimethylaminebenzophenone),2,2-diethoxyacetophenone, or t-butyltrichloroacetophenone.
5. A cellulosic substrate as claimed in claim 1 wherein the at least one living cationic catalyst is a triarylsulfonium salt or a diaryl iodonium salt of the formula III:
[Ar x Q+]y Z y- where III
Ar is an aromatic radical;
Q is a sulfur atom or iodine atom;
x is 3 when Q is a sulfur atom;
x is 2 when Q is an iodine atom;
y is 1 or 2; and Z is SbF6 or PF6.
6. A cellulosic substrate as claimed in claim 5 wherein the at least one living cationic catalyst is selected from:
7. A cellulosic substrate as claimed in claim 1 wherein the transparentizing material further includes an oligomer, a prepolymer, or mixtures thereof.
8. A cellulosic substrate as claimed in claim 7 wherein the prepolymer is selected from the group styrene-maleic anhydride prepolymer, styrene-acrylic acid prepolymer, or styrene-methacrylic acid prepolymer.
9. A cellulosic substrate as claimed in claim 7 wherein the oligomer is selected from styrene-acrylic acid oligomer or urethane acrylate oligomer.
10. A cellulosic substrate as claimed in claim 1 wherein the transparentizing material further includes 0.2% to 1% of an additive or a mixture of additives selected from the group consisting of fluorocarbons and silicon prepolymers.
11. A cellulosic substrate as claimed in claim 10 wherein the transparentizing material further includes an oligomer, prepolymer, of mixtures thereof.
12. A cellulosic substrate as claimed in claim 1 wherein the cationic catalyzable constituent comprises at least one polyepoxide.
13. A cellulosic substrate as claimed in claim 1 wherein the cationic catalyzable constituent comprises at least one vinyl ether in admixture with at least one polyepoxide.
14. A cellulosic substrate as claimed in claim 1 wherein the cationic catalyzable constituent comprises at least one vinyl ether.
15. A cellulosic substrate as claimed in claim 1 wherein the transparentizing material comprises:
a) from 30% to 40% of at the least one polyepoxide;
b) from 50% to 60% of the at least one compound of Formula I;
c) from 3% to 8% of the at least one free radical catalyst; and d) from 3% to 8% of the at least one living cationic catalyst.
16. A cellulosic substrate as claimed in claim 1 wherein the transparentizing material comprises:
a) from 30% to 40% of a polyepoxide of the formula b) from 50% to 60% of tripropyleneglycol diacrylate;
c) from 3% to 6% of pentacrylate;
d) 4.5% of 2-hydroxy-1-[4-(hydroxy-ethoxy)phenyl]-2-methyl-1-propane; and e) 5.5% of a triarylsulfonium hexafluorophosphate salt of the formula
17. A cellulosic substrate as claimed in claim 1 wherein the transparentizing material has a refractive index of 1.5 when cured.
18. A cellulosic substrate as claimed in claim 1 wherein the substrate is in the form of an envelope or mailer having at least a first ply and a second ply, with the at least one transparentized portion on the first ply.
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CA2334314A1 (en) 1999-12-29
WO1999067465A1 (en) 1999-12-29
AU752118B2 (en) 2002-09-05
JP2002519526A (en) 2002-07-02
BR9911501A (en) 2001-03-20
EP1088132A1 (en) 2001-04-04
AU4431699A (en) 2000-01-10
US6103355A (en) 2000-08-15
ZA200006538B (en) 2002-02-11

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