CA1184382A - Carbonless copy paper system - Google Patents
Carbonless copy paper systemInfo
- Publication number
- CA1184382A CA1184382A CA000402173A CA402173A CA1184382A CA 1184382 A CA1184382 A CA 1184382A CA 000402173 A CA000402173 A CA 000402173A CA 402173 A CA402173 A CA 402173A CA 1184382 A CA1184382 A CA 1184382A
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- Prior art keywords
- wax
- parts
- reacting
- pressure sensitive
- product obtained
- Prior art date
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Abstract
ABSTRACT
An improved chemical carbonless copy paper system including an improved hot melt type of coating for one surface of pressure sensitive carbonless copy paper having discrete liquid droplets of metallic salt solution electron accepting chromogenic reagent material contained therein in operative association with an image receptor coating for the other surface of said paper employing tri (p-phenylamino) phenyl methanol as a dye precursor type chromogenic reagent material therein.
An improved chemical carbonless copy paper system including an improved hot melt type of coating for one surface of pressure sensitive carbonless copy paper having discrete liquid droplets of metallic salt solution electron accepting chromogenic reagent material contained therein in operative association with an image receptor coating for the other surface of said paper employing tri (p-phenylamino) phenyl methanol as a dye precursor type chromogenic reagent material therein.
Description
SPECIFICATION
This invention rela-tes to pressure sensitive information transfer and duplicating systems and particularly to improved chemical type transfer and reproduction media for effecting duplicative image transfer on sheet ma-terial in response to selectively applied pressure and to processes for forming the same Pressure sensitive image transfer media of di`verse character are widely employed in the information recording and duplîcating arts. Chemical type or so-called "carbonless" pressure sensitive transfer and duplicating systems, wherein a visable image ls ~ormed by the selective chemical reaction of two essentially colorless reagents, have been long recognized as a viable expedient for the formation of duplicate copy material.
Such systems no.rmally broadly comprise a substrate supported coating that contains a first normally inactive chemical reage:nt material that is selec-tively transferable in response to applied pressure into a reaction provid~ng and color producing relationship with a second normally inactive chemical reagent material contained within or comprising a second coa-ting disposed on the surface of an interfacially contiguous second substrate. Conven-tionally illustrative of such chemical type reproduction systems `.~, '~
~[la~ ,~
,, , ,,~
are transfer and duplicating systems wherein the rear surface on one paper sheet substrate is provided ~ith a coating and which sheet is then termed a "CB" (i.e. coated bacl;) sheet and the front side of tbat same andlor a separate paper shee~ substrate is provided with a coating which is then termed a "CFB" (i.e.
coated front and back) or "CF" (i.e. coated fr~nt) sheet, respect-ively. When the coatings on a CB and a CF sheet are place~l in interfacially contiguous relation and s-ubjecred to selectively applied pressure, as by the pressure of a stylus or the impact of a typewriter key on the obverse sur~ace of the CB sheet, the operative and usually colorless chemical reagents i~ such coatings are brought in~o co-reactive relationship, as for example on the surface of the CF sheet, to produce a colored image conforming to the contour of the selectively applied pressure member.
Such chemical type pressure sensitive transfer and duplicating systems are in widespread and expanding use at the present time for the making of multiple copies of selectively recordable duplicative information on sheet material, such as paper and the like due, at least in part, to their basic clean-liness and to the fact that the color producing reagents are inaeti~e until placed into operative co-reactive relationship in response to selective application of pressure.
Although it was early recognized, as for example in the Gill U.S. Patent 1,781,902, that many colorless chemical reagents ~ere capable of producing a visable colored image upon interreaction therebetween, most of the systems in wide commercial usage at the present time employ a colorless organic dyestuff as a dye precursor in encapsulated liquid form distributed
This invention rela-tes to pressure sensitive information transfer and duplicating systems and particularly to improved chemical type transfer and reproduction media for effecting duplicative image transfer on sheet ma-terial in response to selectively applied pressure and to processes for forming the same Pressure sensitive image transfer media of di`verse character are widely employed in the information recording and duplîcating arts. Chemical type or so-called "carbonless" pressure sensitive transfer and duplicating systems, wherein a visable image ls ~ormed by the selective chemical reaction of two essentially colorless reagents, have been long recognized as a viable expedient for the formation of duplicate copy material.
Such systems no.rmally broadly comprise a substrate supported coating that contains a first normally inactive chemical reage:nt material that is selec-tively transferable in response to applied pressure into a reaction provid~ng and color producing relationship with a second normally inactive chemical reagent material contained within or comprising a second coa-ting disposed on the surface of an interfacially contiguous second substrate. Conven-tionally illustrative of such chemical type reproduction systems `.~, '~
~[la~ ,~
,, , ,,~
are transfer and duplicating systems wherein the rear surface on one paper sheet substrate is provided ~ith a coating and which sheet is then termed a "CB" (i.e. coated bacl;) sheet and the front side of tbat same andlor a separate paper shee~ substrate is provided with a coating which is then termed a "CFB" (i.e.
coated front and back) or "CF" (i.e. coated fr~nt) sheet, respect-ively. When the coatings on a CB and a CF sheet are place~l in interfacially contiguous relation and s-ubjecred to selectively applied pressure, as by the pressure of a stylus or the impact of a typewriter key on the obverse sur~ace of the CB sheet, the operative and usually colorless chemical reagents i~ such coatings are brought in~o co-reactive relationship, as for example on the surface of the CF sheet, to produce a colored image conforming to the contour of the selectively applied pressure member.
Such chemical type pressure sensitive transfer and duplicating systems are in widespread and expanding use at the present time for the making of multiple copies of selectively recordable duplicative information on sheet material, such as paper and the like due, at least in part, to their basic clean-liness and to the fact that the color producing reagents are inaeti~e until placed into operative co-reactive relationship in response to selective application of pressure.
Although it was early recognized, as for example in the Gill U.S. Patent 1,781,902, that many colorless chemical reagents ~ere capable of producing a visable colored image upon interreaction therebetween, most of the systems in wide commercial usage at the present time employ a colorless organic dyestuff as a dye precursor in encapsulated liquid form distributed
-2- .
.
within the CB sheet coating and an electron accepting material in the CF sheet coating. I~hen such CB and CF sheet coatings are placed in contiguous interfacial relation, the application of pressure effects a rupture of the liquid dyestuff confining capsular elements in the area of applied pressure to effect a release of the dye precursor material and selective transfer of at least a portion thereof into co-reac~ing and color producing relationship with the electron accepting material in the con-tiguous coating on ~he CF sheet wi~h the resulting formation of a duplicative ima~e thereon.
Some early and relatively recent patents that illus-tratively disclose chemical type or so-called "car~onless"
transfer media employing encapsulated dye precursor materials as the chromogen;c reagent in the CB coating and electron accepting materials as the chromogenic reagent in the CF coating are USP
2,712,507 (1955) to Green; USP 2,730,456 (1956) to Green et al.;
and USP 3,455,721 (1969) to Phillips et al.
Other more recent patents that illustratively disclose the dispositi~n of the dye precursor material in the CF coating and encapsulated electron accepting material in the CB coating include USP 3,787,325 (1974) to Hoover and USP 3,984,168 (1975) to Brockett et al.
Such "carbonless" transfer media as presently commer-cially employed and par~icularly those that conventionally e~ploy an encapsulated type vehicle for one of the reactive constitucnts, most usually an organic dyestuff, are not without disadvantage. Among the recognized disadvantages of such media are the fact that they are not only relatively expensive, re-quiring specialized fabrica~in~ techniques, but are also undulypressure sensitive. Such undue sensitivity often results in undesired premature transfer occasioned by inadvertent dye pre-ursor release and transfer resulting from pressures normally attendant packaging, handling and processing operations, spot coating delineation, printing operations and t~te like, particu-larly where multicopy manifoldlng operations are involved. In addition,-such media are inherently subject to a progressively increasing lack of copy definition as the number of desired copies increases as well as by a fading of the copied image with ~inte.
The recently issued Shackle and Young U.S. Patent No. 4,063,754 discloses the utilization of non-aqueous "hot melt" coating compositions for CF sheets in a carbonless transfer system incorporating acid reacting color developin~
reagent materials. Such patent describes, at considerable length, numerous dlsadvantages attendant employing solvent or water based compositions for effecting the deposition of such carbonless coatings on substrates. Among such entlmerated disadvantages are the health and fire hazards attendant the release of generally volatile solvent vapors and the expenditure of significant amounts of energy for the evaporation of the water from aqueous solvent systems. In addition, the practical necessities of solvent recovery and the drying of aqueous coating compositions requires relatively complex and expensive apparatus as well as the attendant pro~lem of solvent safety hazards and disposal of polluted water attendant preparation and clean-up of such aq~teous coating compositions.
, _4_ .
A further recently issued paten~ to Shackle and Young's assignee, i.e. U.S. Patent No. 4,I12,138, Davis and Shackle for Mani~old Carbonless Fo~n and Process for the Production Tnereof discloses the utilization of non-aqueOus, solvent free "hot melt" coating compositions for CB sheets.
The specification of this patent similarly describes, at consider-ablc length, the numerous disadvantages attendant employing solven~
or water based compositions for effecting the deposition of carbonless coatings on substrates.
The Shackle and Young patent and the Davis and Shackle patent stress the "non-aqueous" and "solvent free" character of the assertedly novel hot melt coating compositions, apparently based upon the asserted disadvantages flowing from the presence of water both in the fabrication process and in the finished product. The Davis and Shackle patent discloses the preferred use of microcapsular chromogenic reagent materials in ~he CB coating although the process claims are not expressly limited thereto.
Although the Shackle and Young patent is expressly directed to a hot melt CF coating, the vehicular form of the acidic electron accepting type of colGr developer, i.e. whether microencapsulated.
capsulated, dispersed or other form, is not particularly speci~ied.
It is relatively clear, however, that the described CF product is intended for use with CB sheets incorporating an organic dyestuff dye precursor in encapsulated form and, as such, repre-sents an asserted improvement for the capsular type systems presently in widespread commercial use.
The present day widespread commercial employ~ent o CB '`
sheets incorporating encapsulated or~anic dyestuff dye precursor .
.
within the CB sheet coating and an electron accepting material in the CF sheet coating. I~hen such CB and CF sheet coatings are placed in contiguous interfacial relation, the application of pressure effects a rupture of the liquid dyestuff confining capsular elements in the area of applied pressure to effect a release of the dye precursor material and selective transfer of at least a portion thereof into co-reac~ing and color producing relationship with the electron accepting material in the con-tiguous coating on ~he CF sheet wi~h the resulting formation of a duplicative ima~e thereon.
Some early and relatively recent patents that illus-tratively disclose chemical type or so-called "car~onless"
transfer media employing encapsulated dye precursor materials as the chromogen;c reagent in the CB coating and electron accepting materials as the chromogenic reagent in the CF coating are USP
2,712,507 (1955) to Green; USP 2,730,456 (1956) to Green et al.;
and USP 3,455,721 (1969) to Phillips et al.
Other more recent patents that illustratively disclose the dispositi~n of the dye precursor material in the CF coating and encapsulated electron accepting material in the CB coating include USP 3,787,325 (1974) to Hoover and USP 3,984,168 (1975) to Brockett et al.
Such "carbonless" transfer media as presently commer-cially employed and par~icularly those that conventionally e~ploy an encapsulated type vehicle for one of the reactive constitucnts, most usually an organic dyestuff, are not without disadvantage. Among the recognized disadvantages of such media are the fact that they are not only relatively expensive, re-quiring specialized fabrica~in~ techniques, but are also undulypressure sensitive. Such undue sensitivity often results in undesired premature transfer occasioned by inadvertent dye pre-ursor release and transfer resulting from pressures normally attendant packaging, handling and processing operations, spot coating delineation, printing operations and t~te like, particu-larly where multicopy manifoldlng operations are involved. In addition,-such media are inherently subject to a progressively increasing lack of copy definition as the number of desired copies increases as well as by a fading of the copied image with ~inte.
The recently issued Shackle and Young U.S. Patent No. 4,063,754 discloses the utilization of non-aqueous "hot melt" coating compositions for CF sheets in a carbonless transfer system incorporating acid reacting color developin~
reagent materials. Such patent describes, at considerable length, numerous dlsadvantages attendant employing solvent or water based compositions for effecting the deposition of such carbonless coatings on substrates. Among such entlmerated disadvantages are the health and fire hazards attendant the release of generally volatile solvent vapors and the expenditure of significant amounts of energy for the evaporation of the water from aqueous solvent systems. In addition, the practical necessities of solvent recovery and the drying of aqueous coating compositions requires relatively complex and expensive apparatus as well as the attendant pro~lem of solvent safety hazards and disposal of polluted water attendant preparation and clean-up of such aq~teous coating compositions.
, _4_ .
A further recently issued paten~ to Shackle and Young's assignee, i.e. U.S. Patent No. 4,I12,138, Davis and Shackle for Mani~old Carbonless Fo~n and Process for the Production Tnereof discloses the utilization of non-aqueOus, solvent free "hot melt" coating compositions for CB sheets.
The specification of this patent similarly describes, at consider-ablc length, the numerous disadvantages attendant employing solven~
or water based compositions for effecting the deposition of carbonless coatings on substrates.
The Shackle and Young patent and the Davis and Shackle patent stress the "non-aqueous" and "solvent free" character of the assertedly novel hot melt coating compositions, apparently based upon the asserted disadvantages flowing from the presence of water both in the fabrication process and in the finished product. The Davis and Shackle patent discloses the preferred use of microcapsular chromogenic reagent materials in ~he CB coating although the process claims are not expressly limited thereto.
Although the Shackle and Young patent is expressly directed to a hot melt CF coating, the vehicular form of the acidic electron accepting type of colGr developer, i.e. whether microencapsulated.
capsulated, dispersed or other form, is not particularly speci~ied.
It is relatively clear, however, that the described CF product is intended for use with CB sheets incorporating an organic dyestuff dye precursor in encapsulated form and, as such, repre-sents an asserted improvement for the capsular type systems presently in widespread commercial use.
The present day widespread commercial employ~ent o CB '`
sheets incorporating encapsulated or~anic dyestuff dye precursor .
3~
materials, is, as mentioned above, not without disadvantage, such as undue expense, premature activa~ion, limited reproduc-tion fidelity in multiple copies and detrimental fading of the reproduced images. Such disadvantages have been largely tolera-ted because of thc absence of a viable commercially acceptable alternative. As pointed out above, it was early recognized that many chemical reagents were capable of producing visable ~uplicative images in chemical transfer paper usage. The afore-mentioned Gill U.S. patent, for example, employed a member of the gallo-tannic acid series as the chromogenic reagen~ in the CB sheet coating in association ~ith a ferrous or ferric salt as the chromogenic reagent in the CF sheet coating. In contxa-distinctlon to the later Shackle and Young and Davis and Shackle's disclosures, this system requires the presence of solvent at or in the CF sheet coating for the color producing reaction to go fo~ard and hence Gill teaches the inclusion of "a small percent-age of glycerine or other non-drying substance, or a hygroscopic ingredient" in the CF sheet coating. The need for the presence of moisture ~nd the deleterious effects of such moisture on the paper substrate was early recognized in the Gookin et al.
U.S. Patent No. 1,950,982, who provided a water impervious film intermediate the substrate and the CB and C~ sheet coatings and included in the :latter both magnesium chloride as chromogenic reagent material and glua or gelatine as moîsture retaining material. A somewhat different approach was followed in Groak U.S. Patent No. 2,168,098, who disclosed a CB sheet coating composed of a hard waxy substance having dispersed therein an admixture of starch, a hydroscopic material, such as glycerine, ' and a color producing reac-tive subs-tance. In neither of these approaches, however, was water included as a necessary ingredient in -the coating composition and thus basically conformed in such disclosure and teaching to the later issued Shackle pa-~ents.
Some of -the aspects of the approach that was early suggested by the Gill, Gookin and Groak patents have recently reappeared in Austrian Patent No. 331,825 which issued March 25, 1976. In these disclosures, an organic dyestuff dye precursor is dispersed in a binder on the CF sheet and used in conjunction with an essentially fully transferable CB sheet coating which incorporates cla~ materials as the electron accepting chromogenic reagent material, either alone or in association with phenolic material and inorganic salts of multivalent metals. Sol~ent, water based and hot melt systems are specifically disclosed for the CB sheet coatings. Significantly, howe~er, the hot melt CB sheet coatings are all water free, again in conformity with the Shac~cle teachings.
A later issued West German published patent application 24 56 083.2 of September 2, 1976, as referenced in U.S. Patent No. 4,096,314, discloses the utilization of me-tal chlorides, preferably in combination with urea or urea derivatives, as CF sheet coatings in both solvent and aqueous systems. In association therewith, there is disclosed the u-tilization of mab/ ~ r 3 ~ f ~ 3~ ~
organic dyestuff dye precursors dispersed in a hot mel~ co~tir.g medium as the CB coatin~. The preferred CF sheet coatings are identified as those, for a water based coating, that contain zinc chloride and urea and further include a metal stearate.
- While considerable effort has also been directed over the past years to the improvement of encapsulation techniques and to the provision of improved CB type coatings, a further problem faced in this art is the ever increasi.ng expense of co~ventionally employed dye precursor materials such as crystal violet lactone and the like and the degradable sensi~ivi.ty there-of to both light and water. These latter pose con~inuing and as yet unsolved problems in the search for improved and lower cost chemical carbonless transfer systems.
This invention may be briefly described, in its broad aspects, as an improved chemical type transfer and duplicating system comprising a hot melt type o CB sheet coating containing and retaining discrete and selectively constituted liquid electron accepting chromogenic reagerlt material and to methods for forming the same. ~n its narrower aspects, the subject invention includes a novel hot melt CB coating constituted of an intermiY.tUre of natural and synthetic waxes containing and retaining discrete microscopic droplets of a selectively constituted solution of a metallic chloride, preferably zinc chloride in ~Jater suitably buffered to minimize, if not effectively neutraliæe, the avail-able acidic chloride content thereof uniformly distributed therewithin as a color producing reagent. In operative association therewith the invention includes a compatible and improved sol-ven~ sy-tem type CF sheec coat Dg employing ~i (p-ph~nyl~mino) ' .
r ~
phenyl methanol as a dye precursor ~ype chromogenic reagent material s~lcctively dispersed throughout an alkaline biased carrier film.
~ mong the manifold advantages attendant the practice of the subject invention is the provision of improved low cost carbonless transfer media that serve to provide markedly increased numbers of duplicative copies with sharper, more intense and highly smear resistant transferred images. Additional advantages include compatability wi~h "one time" carbon papers and standard printing inks; a permitted reduction in basis weights and the provision of an odorless CB sheet coating that can be reused one or more times, thus permitting retyping on the obverse surface there-of. Other advantages include the provision of a CB sheet coating that can be readily striped and spot coated and which is recyclable.
Still other advantages include the provision of a CB sheet coating that can be fabricated with minimal energy requirements on conventional coating equipment requiring minimal capital investment.
Additional advantages attendant the practice of the subject invention include the permitted use of a broadly acid responsive, inexpensive and readily available pigment type product as a dye precursor; the provision of an image receptor coating that is effectively water and light stable and, absent interreaction ~ith available acidic material, is highly resistant to premature actuation normally resulting from extreme climatic conditions.
Further advantages of the disclosed combination of coa~.ings include the provision of transferred images that are effectively stable in character and a system which is operable at tempera-turcs as lo~ as -30F. Still further advantages include the provision of transfer and image receptor coatings of extencled _g_ .
shel life that are markedly resistant ~e undesired premature aetivation under conditions of high temperature and/or high humid-;ty; that are characterized by reduced potential to irritate sensitive skins and to corrode iron rollers and other components of coating, printing and cullating apparatus; coatings that are essentiaLly uncritical as to substrate character and which are highly resi:stant to undesired transfer on printing presses, collators and other equipment normally inciden~ to manifolding, printing and packaging operations.
The principal object of this invention is the provision of impro~red chemical type pressure sensitive transfer and re-production system and to processes for abricating the same.
A furcher principal object of this invention is the provision of an impro~ed hot melt chromogenic reagent containinO
eoating composition for CB transfer sheets in association with an ine~pensive, light and water stable dye precursor containing image receptor coating for chemical carbonless copy systems.
Another object of this invention is the provision of an improved composite wa~ base hot melt type of CB sheet eoating containing discrete droplets of a selectively con-stituted water solution of a zinc chloride suitably buffered to minimize, if not effectively neutralize, the available acidic ehloride content thereof uniformly distributed therewithin as a color producing reagent in association with an image receptor eoating that employs tri (p-phenylamino) phenyl methanol as a dye precursor type chromogenic reagent material thcrein.
A further object oE this invencion i5 the provision of a water base zinc chloride solution for use as eleccron 3~
accepting chromogenic reagent material in carbonless transfer systems that is effectively non-corrosive and non-irritating and which is hig~ly resistive, when dispersed in a hot melt carrier vehicle, to undesired premature image actua~ion under conditions of high temperature and/or high h~midity in association with a light and water stable receptor coating that employs tri (p-phenylamino) phenyl methanol dispersed throughout an alkaline biased carrier film as the chromogenic reagent therein.
Other objects and advantages of the subject invention will become apparent from the following portions of this specifica-tion which describe, in accord with the mandate of the patent statutes, the principles of the invention and best mode presently contemplated by the inventors for carrying out said inventions.
Figure 1 is a schematic representation of chemical type pressure sensitive transfer and reproduction media incorporating the principles of this invention; and Figures 2a and 2b are photomicrographs (4200~ and 14000X) of an improved hot melt CB coating formed and constituted in accordance with the principles of this invention.
~ eferring to the drawings and initially to Figure 1, there is provided an illustrative set of chemical type or carbon-less transfer and reproduction media fabricated in accord with the principles of the invention. As there shown9 suc~ sct includes a CB sheet comprising a first planar substrate 10, suitably a paper sheet or ~Jeb, having a thin solidified hot melt CB coating 12, constituted as hereinafter described, disposed on the under-surface thereof. Atlapted to be positioncd in interfacially con-tiguous relation with the CB coating 12 on thc undersitle of substrate 10 is a CF sheet coating 16 dîsposed on the upper surface oE a second paper sheet substrate 14. Such subs~rate 14 may have its undersurface coated with a CB coating 12 and thus constitute a CFB sheet, or may have an uncoated under-surface and thus constitute a CF sheet. Alternatively, and illustratively adapted to be disposed in interfacially contiguous relation with either a CB coating 12 on the underside o~ the "CFB" sheet 14 or with a CB coating 12 on the underside of the "CB" sheet 10, is a separately illustrated "CF" sheet having a CF coating 16 disposed on the upper surface of a third substrate 18. As will be apparent ~o those skilled in the art, any number of intermediate CFB sheets or webs 14 rnay be interposed in stacked relation to form a multilamina transfer and reproduction system. Likewise, such multilamina se~ may include one time carbon transfer sheets interposed with uncoated or CB coated sheets or webs in a manifold arrangement in accord with the dictates of the user thereof.
The novel and improved hot melt CB sheet coating broa~ly comprises the resulting set or solidi,ied film from an j applied and subsequently cooled emulsified liquid intermi~ture of a melted low oil content wax carrier vehicle, preferably of composite character, a melted synthetic flow wax and dispersant and a chromogenic reagent solution oE zinc chloride dissolved in water and suitably buffered to minimize, if not effectively neutralize the available acidic chl.oride content thereof; said emulsified intermixture also desirably having uniformly dispersed therein small but critically limited amounts of a resinous film forming a~cnt to promote film hardness and toughness, an isolating 3~ -Agent to minimize, if not effectively preclude, undesired transfer of the coating or portions thereof in response to un-intentional pressure application and an opaciEier-filler to reduce the gloss of the finished copy and preserve t~le appearance of the substrate.
In its narrower aspects, the subject invention includes a hot melt~CB sheet coating composition formed o about 35 to 75 percent of a meltable low oil content synthetic or naturally derived hard wax vehicle; at least 1 to about 15 percent of a ehemically modified wax-like material having properties of a flow agent, dispersant and emulsifier; and at least 10 to about 35 percent of a chromogenic reagent component in the form of a Lewis aeid, desirably zinc chloride dissolved in an appropriate amount o water necessary to form a relatively concentrated solution thereof.
Optionally but desirably included in such CB sheet coating composition for provision of an enhanced commercially attractive product are one or more of the following additional constituents.
One sueh optional constituent comprises a film orming agent to encourage the formation of a harder and tougher surface film after setting and to thus minimize premature actuation of the color producing reaction. This film forming agent must be non-reactive with the chromogenic reagent and may vary in amount from a mini~1~m of about 2% up to an amount that deleteriously effects the flow eharaeteristics of the mix. Another sueh optional but yet desirable constituent comprises an isolating agent that is essentially inco~.patible with the wa~ vehicle when solidified and which serves to provide desirable surface characteristics to the -13~
~ 3~
resultan~ ~ilm, such as to minimize, if not effec~ively preclude, undesired transfer of the coating or portions thereof in response to unintentiona:l pressure application. The isola~ing agent may vary in amount from a desira~le minimu~ of about 2% up to a ma-~i mum of about 20%. A still fur~her optional but desirable con~
sti~uen~ is an opacifier-filler to enhance the appearance o~ ~he coated surface of t~e CB sheet, such as by reducing the-gloss thereof. As is well kno~n in this art, such opacifier-filler may vary in amount required to provide a desired appearance, typically about 5%, and may include titani~m dioxide, various non-acidic high brightness clays, lithopone or other recognized materi.als.
The mel~able wa~ vehicle may suitably comprise any of the low oil oontent paraffin wa~es, microcrys~alline waxes, carnauba, Montan or other conventionally emp]oyed low oil con-tent vegetable, synthetic or mineral derived hot melt ~ax type carrier vehicles. The presently preferred meltable wax vehicle is a composi~e made up of abou~ 3 to 4 p2rts of a 101J oil con~en~
paraffin wax, intermixed with about 1 part or less o~ carnauba wax. A prèsently preferred para~fin ~Jax is a low oil content, hig~ melting point, fully re~ined paraffin ~ax, sui~ably Pace-maker*53 as manufactured and sold by Cities Service Oil Co. of Tulsa, Oklahoma. Suc~ wax has the following properties:
~elting point, AST~I, F 143-150 Melting point, ~ 146-153 Oil Content, Wt. % ma~ 0.25 Odorless Viscosity, cs at 210F 5.5 *trade mark Y~i!JA,,,`
3~
~eedle penetration a~ 77~F 13 Flash point F 485 O~ller suitable low oil conten~ hot melt ~7ax carrier vehicles include alpha olefinic waxes, suitably ~6817 Synthetic l~ax as ~vailable from Moore & Munger Inc. of Fairfield, Conne~ti-cut; microcrystalline wax, suitably 195 Be Square ~ite*, available from Pe~roli~e Corporations Bareco ~ivision or c ~ auba wax, suitably Brazilian Refined available ~rom Baldini & Company of Milburn, New Jersey.
Moore ~ Munger's ~6817 Synthetic Wa~ has the foll.owing properties:
Congealing Point, F., AST~ D 938 162 Needle penetra~ion, mrn/10, AST~ D 1321 77F. 14 Viscosity, Saybolt (a) ~10~.
(SVS), ~SI~l D 2161 52 ~iscosity, Kinematic ~a) 210~F.
(Cs ). ASl~ D 445 8 Color, Saybolt, ASTM ~ 156 +~
Flash Poin~, F. (COC) 510 Bareco's 195 Be Square l~ite microcr~s~alline wax has the Eollowing propertîes:
Melting Poin~, F. ASTM D 127 193/198 Penetration (a) 77F. ASI~I 6/7 Color AST~I D 1500 0.5/0.5 A pre:Eerred carnauba wax is Baldini's Brazilian Reflned Carnauba wax that is possessed o the ollowlng properties:
Melting point, min., F. 180.5 ~cid Number minimurn 4~0 maY~imulrl 10 . O
*~rade mark ,~' ~ r Saponification Number minim~n 78.0 maximum 88. n The mel~able chemically modified ~ax-like material having the desired properties of a flow agent, dispersant and emulsifier most suitably comprises a material of the - .
type disclosed in U.S. Patent No. 3,941,608. Other sui~ably chemically modi~ied wax materials having the somewhat similar properties include modified synthetic waxes as disclosed in U.S. Patent Nos. 2,890,124, 2,890,125 and 39163,548. ~ preferred con~erciall.y available wax-lik~ ma~.erial ~ormulated in accord with U.S~ Patent No~ 3,941~608 is ~7315 wax as sold by Moore & ~lunger, Inc., o Fairfield, Connecticut. Such #7315 wax has the following general properties:
Penetration Hardness (FLP)I-22 5 Typical Melting Point (Fisher Johns) 144~ypical Acid N~ber (AST~I D 97~) 2 Typical ~ no~her suitable wa~-like material having somewhat si.mi.lar properties as the foregoing suitably comprises an amide of a fatty acid, such as Armid*HT as available from ~rmour Industrial Chemical Company. Such Armi~*HT is possessed of the following properties:
~mide % (min.~ 90 Iodine value minimum maximum 5 Free fatty acid ~/~
minimu~ -maximum 5 *trade mark g Poi~t, C.
minimu~ . 9~
~.a~imum 103 r~he resinous film forming agent serves to enhance the formati.on of a relatively hard and tough coating ~o minimize undesired transfer of reagent material across t~ CB/CF inter-face in the absence of intentional positive pressure application.
A suitable film for~ing agen~, which must be non~reactive with chromogenic reagent component, desirably comprises a relatively low ~elting point ethylene-vinyl acetate copolymer,.such as ~C-~0~*
as manufactured and sold by ALlied Chemical Corporat~on. Such resin.ous ~ilm forming agent has the following properties:
Softening Point (AS~I E-28~ 20~F.
Hardness dmm (ASTM D-5) 9.5 Density ~/cc (ASI~I D-1505) ~.92 Viscosity (284F - Brookfield~ 55~ ~
~ nother suitable filTl formi.ng agent comprises oxidized polyethylene, suitably AC-629 as manufactured and sold by Allied Chemical Company. Such ~ilm forming agent has ~h~ following prop-er~ies:
Softening Point 2~4F.
Hardness 5.5 Density g/cc 0.93 A~erage Viscosity CPS 284F lGO
Acid Number 15 The isolating agent cooperatively functions as b]ooming agent to provide a lubricating and barrier surface to ~he solidifi.ed coating. Such isolating agent, which should be essentially incompatible with the wa~ carrier veh~cle when solidi-~*tracle mark - J--fied, so as to be selec~ively effective at the exposed sur~ace, suitably comprises a small amount of stearic acid, desirably HYSYRE~E 9718 as manu~actured and sold by the H~m~o Chem;cal Company. Zinc stearate may also be employed.
The opacifier-filler, ~lich co.smetically serves bo~h to reduce the gloss of the ~inished coa~ing and to preserve the appearance of the substrate, suitably comprises inely divided titanil~n dioxide such as UNIT~N~ 0-110 as manufac~ured and sold by ~merican Cyanamid Company. This material has a speci~ic gravity of about 3.9 and is so finely divided 2S to leave only about a 0.10% residue on a 325 mesh screen.
The chromogenic reagent component comprises a con- -centrated water base solution of ~inc chloride, suita~ly buffered to minimize, if not e~Eectively neutralizeJ the a~ailab~e acidic chloride conten~ thereof. Such solution is preferably made up of about 2 to 4 parts of zinc chloride with about 1 part of -~.Jater and which appxoaches a saturated solu~ion.
~ hile unbu~fered solutions of zinc chloride as the chromogenic reagent have provided highly efEective image Lormation in transfer coatings as formulated in accord -.~it~ the foregoing disclosed ~ormulaLions, such have been subject, undèr extreme climatic conditions o~ high temperatures and/or high humidity, to the apparent genera~lon and emanation of hydrogen chloride.
~lthou~l the quantities of hydrogen chloride so generated, appear to be minimal~ even ~mder such e~treme climatic conditions, the apparent emanation thereo~ from the applied coating has resul~ed in varying degrees o:E premature actuation of dye precursors over the entire sur~ace oE an interfacially contiguous CF coating and, *trade mark "., ~
r 3~2 depending on the ambient climatic condicions, in varying degrees of actuation of such CF sheet. Such premature actuation is, of course, highly undesirable as is thc generation of hydro~en chloride with its potential to irritate sensitive skins and to corrode iron rollers and other components of the processing equip-ment under any set of climatic conditions.
In order eo neutralize, if not actually prevent, the generation and emanation of such hydrogen chloride, a small amount of a neutralizinO ammonium salt, suitably ammonium carbonate or am~onium bicarbonate, is dissolved in the zinc chloride solution.
For a concentrated solution of about 2 parts of zinc chloride to 1 part of water, about .1 part of such neutralizing ammonium salt is generally satisfactory. Experience to date has generally indicated that the addition of about 2 to 4% of ammonium carbonate to zinc chloride solutions of the type herein disclosed results in effective avoidance of the above problems in an improved product.
While the mechanics of the reaction process are not fully understood it is surmised that the ammonium salt operates to neutralize or otherwise reduce the available active or acid chloride ion content and to thus preclude its association with avail~ble hydrogen ions. Also the possible availability of ammonia in both the liquid and gaseous phase ~ay also contribute to the neutralization of hydrogen chloride in both such phases.
Apart from the fore~oing, the additions of such neutralizing ammoni~m salt has provided some totally unexpected and, as yet, unexplai~able advantages and results. Such unexpected results are a bleaching and a marked increase in the h~rdness of , -19- . , tbe solidified CB hot melt coating. Such increase in hardness not Gnly functions to minimize pick off on processing components, reduces the tendency to smear and provides sharper copy, but also permits of significant reduction in the quantity of carnauba wax that is otherwise desirably included therein. Carnauba wax is not only one of the more cost significant components of the coating but is also only obtainable from a foreign source of supply who controls the ever increasing price thereof.
The unexpected bleaching action also enhances the appear-ance of the product through an enhancement of the "whiteness" of the coating.
A presently preferred ho~ melt CB sheet coating broadly comprises the rPsulting set or solidified film from an applied and subsequently cooled emulsified liquid întermixture of about 50-60% of a melted low oil content composite wax carrier vehicle, made up of about 3 to 4 parts of a low oil content paraffin wax intermixed ~Jith about 1 part of carnauba wax; about 2 to 5% of a chemically modified synthetic flo~J wax and dispersant and about 25-35% of a chromogenic reagent solution of at least 2 parts of zinc chloride dissolved in about 1 part of water buffered by a small amount of ammonium carbonate as outlined above; said emulsified intermixture also desirably having uniformly dispersed therein abou~ 3 to 10% of a resinous film forming agent to promote fil~ hardness and toughness, about 3-10% of an isolating agent to minimize, if noe effectively yreclude, undesired transfer of the coating or portions thereof in response to unintentional pressure applica~ion and about 5% of an opacifier-filler to reduce the gloss of the finished copy and preserve the appearance of tlle substrate.
In the production of ~he above described preferred CB sheet coating composition in accord with the principles of this invention, the requisite amounts of ~inc chloride and water are intermixed in a reaction vessel, suitably a steam jacketed kettle having a 210F temperature setting, to form a hot con-centrated solution thereof. To such solution is then added the ~eutralizing ammonium salt, preferably a~onium carbonate. To such elevated temperature and now neu~ralized chromogenic reagent solution, the requisite amounts of melted low oil content paraffin wax and carnauba wax components of the composite ~ax carrier vehicle are added and thoroughly intermixed as by use of a high speed dispersing blade for about 10 minutes or longer. To the intermixture as so constituted, the flow wax and dispersant constituent and the polyethylene filming agent and stearic acid isolating a~en~ constituents are added in solid form with con-tinual mixing until such consti~uents arP completely melted and dissolved in the composite wax carrier vehicle. ~en 50 melted and dissolved the opacifier-filler, preferably titanium dio~ide is added and the entire mass thoroughly mixed at high speed for 30 to 40 minutes to form a selectivel~ constituted liquid hot melt emulsion.
~ he resulting liquid hot melt emulsion is readily and selectively applied in the form of a thin filml as for e~ample at a coating weight of as low as 2 grams/square meter, by conven-tional means to the surface of a substrate, such as a sheet or web of paper or resinous film. The conventional coating means may comprise a print type coater, a roll coatcr or the like. The so coated substrate is then passed over a chill roll or the like to rapidly solidi~y or set the applied emulsified coating composi-tion.
I~ contradistinction to the systems of the prior art which were operatively dependent upon an Pxternal water source (often humid air) to provide the necessary ionized zinc chloride to react with the dye precursor, the system of the present in-vention contains and retains water as an operative element in discrete droplet liquid form within the solidified CB film and -thus effects the selective transfer of ionized zinc chloride as the operative entity.
Photomicrographs of coatings formulated in accord with the principles of this invention are shown in Figures 2a and 2b at magnifications of 4200X and 14000X respectively. These photomicrographs clearly depict the presence of discrete, micro-scopically sized zinc chloride am~onium salt solution globules distributed throughout the coating. Most of such globules are less than l micron in diameter with the great majority tnereof falling between .25 and .75 microns. Such photomicrographs further show that such zinc chloride solution globules peripherally incorporate an interface layer or the like that differs, at least in some ph~sical respects from bo.h the zinc chloride solution globules and from t~e surrounding solidified wa~ material as evidenced by the clearly different refractive indices involved.
The the ~bove ends, the foregoing described method of formulation provides a selectively constituted emulsion in whlch zinc chloride solution entities are thoroughly dispersed within the film. The basic hygroscopic, if not actual deliquescent, properties of zinc chloride and the nature of the resul~ant film -~2- ~
~erv~ to min:imize, i~ not e~ectively prevent, w~iter loss in storage with enhanced operating life for the product.
Anothe-r factor which contribu~es to the ~etention of the dispersed zinc chloride solution in discre~e liquid c~lobular :~orm within the CB film is the enhanced emulsific~i~n obtained through the use o~ an essentially alkaline and a~ino containing dispersa~ - flow wax consti~uen~ in association r~ith t~e relatively high acid number wax and film forming components.
jBy way of further examples the Eollo~7inv ~ormula~ions have provided CB sheet coating having in varying ~egree, the mani-~old advantages earlier set forth.
, EX~MPLE I
Paraffin Wax 7315 Wax ~.~
- ~C-400 Polyethylene 5 0 Stearic Acid 3 O
Titanium Dioxide 5 Zinc Chloride 30.
Water 10 EX~MPLE II
Paraffin Wax 4~.
7315 Wax 2.~
AC-629*Polyethylene 7.0 Titaniu~ Dio~ide 5 ~
Zinc Stearate lO.O
~inc Chloride 30.0 I~Jater 5-0 *trade mark t EX~IPLE II~ %
Paraffin Wax - 35.0 AC-400*Polyethylene lO.0 Zinc Chloride 20.0 Water - lO.0 ~315 Wax lO.0 Stearic Acid lO 0 Ti~anium Di~xide 5 0 E ~IPLE IV %
Paraffin Wax 55.0 Carnauba Wax 20~0 Zinc Chloride 15.0 Water 5i~0 7315 Wax 2~0 Stearic Acid 3 0 EX~MPLE V
%
Par~fin l~ax lO 0 Microcrystalline ~Jax 3G 0 Stannous Chloride 3~ 0 Water lQ 0 7315 Wa~ ~ o Stearic Acid 7 0 Titanium Dioxide lQ 0 -2~-*trade mark EX~`~LE VI
Carnauba ~ax 10 0 Alpha Olefin Wax 4~ ~
~C-629*Polyethylene 7 0 Ferric Chloride 20 ~
Water .lO~O
. 7315 Wax 3.0 Stearic Acid 5 Titanium Dioxide 5 i~
. ~y way of further preferen~ial example, ~.;he above formu-lations, when buffered to minimizej if not effect~vely neutralize~ ~
the available acidic chloride content thereof, are modified as j~:ol low5:
EX~IPLE IA
~/
Para~fin Wax ~2.
. 7315 Wax 2.
~C-400*Polyethylene 5.
Stearic Acid 2.
Titanium Dioxide 5.
Zinc Chloride 30.
Ammonium Carbonate 3.
Water lO.
EXA*.PLE II~ %
Paraffin Wax 38 7315 l~a~ 2.
*trade mark - -AC 62~ Polyethylene ~ 0 Titanium Dioxide ~.0 Zinc Stearate l~ 0 Zinc Chloride . 3~ 0 Ammonium Bicarbonate ~ 0 Water ~ 0 .
EX~IPLE IIIA
Para~fin Wax ~3~0 AC-40G~ Polyethylene l~ 0 Z;nc Chloride 2~ 0 Am~lonium Carbonate 2 0 Water 1~ 0 7315 Wax ~QI 0 Stearic ~cid lO i~0 Titanium Dioxide 5 ,0 EX~LE IVA
%
PararXin Wax 51 0 Carnauba Wax 20` 0 Zinc Chloride 15 0 Ammonium Carbonate 4 0 Water 5 0 7315 Wax ~ 0 Stearic Acid 3 0 *trade mark `t~ r~
EX~r~PL E ~A %
Paraffin Wax ~-Microcrystalline Wax ~ 0 Stannous Chloride 30~0 Ammonium ~icarbonate - 3 ~
Water . 10 Q
7315 Wax 3-0 Stearic Acid 7 0 Tii-anium Dioxide 1~.0 EX~LE V-.[A
Carnauba Wax 8 0 Alpha Ole~in Wax 38 0 AC-629 Polyethylene 7 ~
Ferric Chloride 2~ O
Ammonium Carbona~e 4 0 l~ater lO 0 -7315 Wcl~; 3 Stearic Acid 5 T.i-~anium Dioxide 5 ~
The Eollowin~ Eormulations have provided highly preEerred CB sheet coatings:
EYA~LE VII
/c~
Para~Ein Wax 39.0 Carnauba Wax 14.0 Zinc Chl.oride ~0.0 Water 10 *trade mark f' 3L~3B~
731S l~a~ 2 0 ~C-400 Polyethylene 5 0 ~tearic Acid 5.0 Titanium Dioxide 5 0 E ~MPLE VIIA
%
Paraffin l~ax 36 0 Carnauba Wa~ 0 Zinc Chloride 20 0 Water IO O
Ammonium Carbonate 3 0 7315 Wax 2 0 AC-400*Polyethylene 5 0 Stearic Acid 5 ~
Titanium Dioxide S O
The impro~ed CF or image receptor coating comprises the soli.d residue of an applied alkaline biased homogeneous mixture o~ an evaporable non-polar hydrocarbon solvent, a chemically neutral or alkaline resinous binder, an opaci~ier--filler and tri (p-phen~lamirlo) phenyl methanol as a dye precursor type of chromogenic reagent material. Such solidified CF coating i5 further characterized by the presence of such dye precursor in solid form and which dye precursor is insoluble in water or other polar solvents. Optionally but desirably included therein is a dis-persant to assist in the uniform dispersion of su~h dye precursor throughollt the mix and a thickener to provide the requisite ~is-cosity properties to facilitate the coatin~ of the mi~ in accord with the particular requirements of the co~ing equip~ent employed.
*trade maL^k The evaporable liquid vehicle mus~ be of non-polar character and a solvent for the tri (p-phenyla.tino) phenyl methanol dye precursor component. Suitable non--po]ar organic solvents include acetone, toluene, hep,ane ~nd naph~ha, with ~oluene being presently preferred for use.
A presently preferred CF coating comprises the solid residue of an applied intermi~ of an evaporable non-polar sol-ven~, suitably 50 to 80 parts of toluene, having disso:Lved therein at least about 7 to 20 parts of a chemically ne-ut~al or alkaline resinous binder, suitably polyvinylacetate. Added thereto is about .1 to .5 parts of a dispersant and about .1 to 4 parts of dry potassium hydroxide to provide an alkaline bias to the mi~ and to minimize inadvertent color reactions in the CF coated sheets. Also included in the mix is about up to 45 parts of opacifier-~illers~
sui~ably up to abou~ 20 parts finely divided ~;itanium dioxide and the remainder of calcium carhonate; and about .5 to 5 parts of tri (p-phenylamino) phenyl methanol as the chromogenic reagent.
The nature of the binder is not attended ~7ith any particular degree o~ criticality as long as it is of chemically neutral or of alkaline character and func-tions as a binding agent for the opacifier-filler and the color precursor, with both of the latter being in solid form. A pre~erred binder material hich is readily soluble in the above described evaporable non-polar solvent carrier comprises polyvinylacetate, suitably Vinac*
B-15, as manufactured by Air Products & Chemicals Company.
A presently preEerred dispersant com?rises sodium salt of polymeric carboxylic acid such as Tamol*731 as manuEactured by Rohm & Haas Company of Philadelphia, Penns,lvania.
*trade mark '3 ~i The opacifier-~iller, which serves both ~o enchance the appearance of the coating and to cooperate in the uniform dis~
tribution and spaced separation of the solid co~or precursor in the CF c02ting must also be of neutral or alkaline character.
Such ~iller may suitably comprise calclum carbo~a.te such ~s Alba-glos as manufactured byr Chas. Pfizer ~ Co. This material has a pH o~ g.4, a specific gravity o~ 2.7 and an aver~ge par~icle size of about .75 microns. Another suitable opacifier-~iller employed in conjunction with the above is Unitane 0-1110 ~itanium dioxide as manufactuxed by the American Cyanamid Compan~. This ma~erial has a mini.mum TiO2 content of 99%, a pH ~ about 7.7 and a speciflc gravity o~ about 3.9. - .
As noted ahove, the chromogenic reagent .~mployed is tri (p~phenyla~ino) phenyl methanol. Such chromogenic reagent, as disclosed in the Pig~ent Handbook (Vol I) pu~lished by John Wiley & Sons (Ed. Temple C. ~atton; 1973~, purportedl~ has the following chemical structure:
o ~3 .
~3 The depicted incorporation of the hydro~rl group inter-mediate the methane carbon atom and ~he phenyl gr~up, however, is incorrcct and the correct structural formula thereof is *trade mark .
T
~ N ~ - c ~ ~
~.
.;~
~ ' Such text further indicates however that in any commer-cially available supply ~hereof, that some lower phenylated product having the follo~ing chemical composition is probably also presen~:
0~
~N ~ I ~ H ~3 ~,, ' i ~H2 Such material may be described as biphenyl triamino triphenyl methanol.
The dlscls)sed tri (p-phenylamino) phenyl methanol as identified above is obtainable from The Sher~7in-WilLiams Company and from BASF albei.t in an apparently somewhat impure or contaminated form. As indicated in Sher~in-Williams technical bulletin AB-47, the tri (p-phenylamino) phenyl methanol ~therein called "Spirit Blue Carbinol Form") in the presence of an acld pH and a chloride forms an intensely colored dye stuf~ Icnown as Solvent Blue 23 (CI No. 42760).
Transposition into or from its colorless for~ is solely pH responsive, with intense color being produced in an acid pll environment. Alkaline biasing of the coating is main~ained by the selective utilization of .~lkaline biased constituent~ as set .
forth above and by the inclusion of small amounts of potassiu~
hydroxide when necessary or desirable.
In the production of the above described receptor coating for CF sheets, a liquid mixture is first formed by inter-mixing the non-polar toluene solvent ~7ith the polyvinylacetate binder material, the dispersant, the potassium hydroxide (to cast the pk of the solution to the all~aline side) with continuous agitation until all solids are completely dissolved after l~7hich the organic dyestuff dye precursor material is added with continued stirring until it is dissolved. To the above liquid mixture is then added the requisite amounts of calcium carbonate and the titanium dioxide opacifier-filler. Such addition should be accompanied by continuous stirring of such constituents in the liq~id vehicle to obtain a uniform dispersion thereof.
The specified dye precursor can be added as a powder, or it can be added in its acidified colored form. If the latter colored form is so utiliæed, the requisite alkaline cast of the other constituents, including any necessary amounts of potassium hydroxide, will cause the dye to revert to its colorless form in the mixture.
By ~ay of specific example the following formulation has provided an improved but yet inexpensive CF sheet coating.
E ~LE I
Toluene ~3.0 Potassium }Iydroxide 1.0 Calcium Carbonate 31.8 Tri (p-phenylamino) phenyl methanol 1.0 Polyvinylacetate 13.0 Dispersant 0.2' -3~-EXAMPLE Il Toluene ~3.0 Potassium l~ydroxide 1.9 Calcium Carbonate 27.0 Titanium Dioxide 4.8 Tri (p-phenylamino) phenyl methanol 1.0 Polyvinylacetate 13.0 Dispersant 0.2 The foregoing CF coating formulation results in a CF
c~ating layer of neutral or alkaline character, of acceptable appearance and having the color precursor chromogenic reagent homogeneously distributed there throughout. Such coatings are singularly inexpensive, abrasion and odor free and have been formed of coating weights as low as .2 grams/square meter.
Used with the CB coatings herein disclosed the image forming reaction proceeds without the color precursor chromogenic reagent material in the CF coating being solubilized and ionized by the liquid electron accepting chromogenic reagent material emitted rom the CB coating and in a markedly improved chemical carbon-less copy paper system.
Having thus described our invention, .
.
materials, is, as mentioned above, not without disadvantage, such as undue expense, premature activa~ion, limited reproduc-tion fidelity in multiple copies and detrimental fading of the reproduced images. Such disadvantages have been largely tolera-ted because of thc absence of a viable commercially acceptable alternative. As pointed out above, it was early recognized that many chemical reagents were capable of producing visable ~uplicative images in chemical transfer paper usage. The afore-mentioned Gill U.S. patent, for example, employed a member of the gallo-tannic acid series as the chromogenic reagen~ in the CB sheet coating in association ~ith a ferrous or ferric salt as the chromogenic reagent in the CF sheet coating. In contxa-distinctlon to the later Shackle and Young and Davis and Shackle's disclosures, this system requires the presence of solvent at or in the CF sheet coating for the color producing reaction to go fo~ard and hence Gill teaches the inclusion of "a small percent-age of glycerine or other non-drying substance, or a hygroscopic ingredient" in the CF sheet coating. The need for the presence of moisture ~nd the deleterious effects of such moisture on the paper substrate was early recognized in the Gookin et al.
U.S. Patent No. 1,950,982, who provided a water impervious film intermediate the substrate and the CB and C~ sheet coatings and included in the :latter both magnesium chloride as chromogenic reagent material and glua or gelatine as moîsture retaining material. A somewhat different approach was followed in Groak U.S. Patent No. 2,168,098, who disclosed a CB sheet coating composed of a hard waxy substance having dispersed therein an admixture of starch, a hydroscopic material, such as glycerine, ' and a color producing reac-tive subs-tance. In neither of these approaches, however, was water included as a necessary ingredient in -the coating composition and thus basically conformed in such disclosure and teaching to the later issued Shackle pa-~ents.
Some of -the aspects of the approach that was early suggested by the Gill, Gookin and Groak patents have recently reappeared in Austrian Patent No. 331,825 which issued March 25, 1976. In these disclosures, an organic dyestuff dye precursor is dispersed in a binder on the CF sheet and used in conjunction with an essentially fully transferable CB sheet coating which incorporates cla~ materials as the electron accepting chromogenic reagent material, either alone or in association with phenolic material and inorganic salts of multivalent metals. Sol~ent, water based and hot melt systems are specifically disclosed for the CB sheet coatings. Significantly, howe~er, the hot melt CB sheet coatings are all water free, again in conformity with the Shac~cle teachings.
A later issued West German published patent application 24 56 083.2 of September 2, 1976, as referenced in U.S. Patent No. 4,096,314, discloses the utilization of me-tal chlorides, preferably in combination with urea or urea derivatives, as CF sheet coatings in both solvent and aqueous systems. In association therewith, there is disclosed the u-tilization of mab/ ~ r 3 ~ f ~ 3~ ~
organic dyestuff dye precursors dispersed in a hot mel~ co~tir.g medium as the CB coatin~. The preferred CF sheet coatings are identified as those, for a water based coating, that contain zinc chloride and urea and further include a metal stearate.
- While considerable effort has also been directed over the past years to the improvement of encapsulation techniques and to the provision of improved CB type coatings, a further problem faced in this art is the ever increasi.ng expense of co~ventionally employed dye precursor materials such as crystal violet lactone and the like and the degradable sensi~ivi.ty there-of to both light and water. These latter pose con~inuing and as yet unsolved problems in the search for improved and lower cost chemical carbonless transfer systems.
This invention may be briefly described, in its broad aspects, as an improved chemical type transfer and duplicating system comprising a hot melt type o CB sheet coating containing and retaining discrete and selectively constituted liquid electron accepting chromogenic reagerlt material and to methods for forming the same. ~n its narrower aspects, the subject invention includes a novel hot melt CB coating constituted of an intermiY.tUre of natural and synthetic waxes containing and retaining discrete microscopic droplets of a selectively constituted solution of a metallic chloride, preferably zinc chloride in ~Jater suitably buffered to minimize, if not effectively neutraliæe, the avail-able acidic chloride content thereof uniformly distributed therewithin as a color producing reagent. In operative association therewith the invention includes a compatible and improved sol-ven~ sy-tem type CF sheec coat Dg employing ~i (p-ph~nyl~mino) ' .
r ~
phenyl methanol as a dye precursor ~ype chromogenic reagent material s~lcctively dispersed throughout an alkaline biased carrier film.
~ mong the manifold advantages attendant the practice of the subject invention is the provision of improved low cost carbonless transfer media that serve to provide markedly increased numbers of duplicative copies with sharper, more intense and highly smear resistant transferred images. Additional advantages include compatability wi~h "one time" carbon papers and standard printing inks; a permitted reduction in basis weights and the provision of an odorless CB sheet coating that can be reused one or more times, thus permitting retyping on the obverse surface there-of. Other advantages include the provision of a CB sheet coating that can be readily striped and spot coated and which is recyclable.
Still other advantages include the provision of a CB sheet coating that can be fabricated with minimal energy requirements on conventional coating equipment requiring minimal capital investment.
Additional advantages attendant the practice of the subject invention include the permitted use of a broadly acid responsive, inexpensive and readily available pigment type product as a dye precursor; the provision of an image receptor coating that is effectively water and light stable and, absent interreaction ~ith available acidic material, is highly resistant to premature actuation normally resulting from extreme climatic conditions.
Further advantages of the disclosed combination of coa~.ings include the provision of transferred images that are effectively stable in character and a system which is operable at tempera-turcs as lo~ as -30F. Still further advantages include the provision of transfer and image receptor coatings of extencled _g_ .
shel life that are markedly resistant ~e undesired premature aetivation under conditions of high temperature and/or high humid-;ty; that are characterized by reduced potential to irritate sensitive skins and to corrode iron rollers and other components of coating, printing and cullating apparatus; coatings that are essentiaLly uncritical as to substrate character and which are highly resi:stant to undesired transfer on printing presses, collators and other equipment normally inciden~ to manifolding, printing and packaging operations.
The principal object of this invention is the provision of impro~red chemical type pressure sensitive transfer and re-production system and to processes for abricating the same.
A furcher principal object of this invention is the provision of an impro~ed hot melt chromogenic reagent containinO
eoating composition for CB transfer sheets in association with an ine~pensive, light and water stable dye precursor containing image receptor coating for chemical carbonless copy systems.
Another object of this invention is the provision of an improved composite wa~ base hot melt type of CB sheet eoating containing discrete droplets of a selectively con-stituted water solution of a zinc chloride suitably buffered to minimize, if not effectively neutralize, the available acidic ehloride content thereof uniformly distributed therewithin as a color producing reagent in association with an image receptor eoating that employs tri (p-phenylamino) phenyl methanol as a dye precursor type chromogenic reagent material thcrein.
A further object oE this invencion i5 the provision of a water base zinc chloride solution for use as eleccron 3~
accepting chromogenic reagent material in carbonless transfer systems that is effectively non-corrosive and non-irritating and which is hig~ly resistive, when dispersed in a hot melt carrier vehicle, to undesired premature image actua~ion under conditions of high temperature and/or high h~midity in association with a light and water stable receptor coating that employs tri (p-phenylamino) phenyl methanol dispersed throughout an alkaline biased carrier film as the chromogenic reagent therein.
Other objects and advantages of the subject invention will become apparent from the following portions of this specifica-tion which describe, in accord with the mandate of the patent statutes, the principles of the invention and best mode presently contemplated by the inventors for carrying out said inventions.
Figure 1 is a schematic representation of chemical type pressure sensitive transfer and reproduction media incorporating the principles of this invention; and Figures 2a and 2b are photomicrographs (4200~ and 14000X) of an improved hot melt CB coating formed and constituted in accordance with the principles of this invention.
~ eferring to the drawings and initially to Figure 1, there is provided an illustrative set of chemical type or carbon-less transfer and reproduction media fabricated in accord with the principles of the invention. As there shown9 suc~ sct includes a CB sheet comprising a first planar substrate 10, suitably a paper sheet or ~Jeb, having a thin solidified hot melt CB coating 12, constituted as hereinafter described, disposed on the under-surface thereof. Atlapted to be positioncd in interfacially con-tiguous relation with the CB coating 12 on thc undersitle of substrate 10 is a CF sheet coating 16 dîsposed on the upper surface oE a second paper sheet substrate 14. Such subs~rate 14 may have its undersurface coated with a CB coating 12 and thus constitute a CFB sheet, or may have an uncoated under-surface and thus constitute a CF sheet. Alternatively, and illustratively adapted to be disposed in interfacially contiguous relation with either a CB coating 12 on the underside o~ the "CFB" sheet 14 or with a CB coating 12 on the underside of the "CB" sheet 10, is a separately illustrated "CF" sheet having a CF coating 16 disposed on the upper surface of a third substrate 18. As will be apparent ~o those skilled in the art, any number of intermediate CFB sheets or webs 14 rnay be interposed in stacked relation to form a multilamina transfer and reproduction system. Likewise, such multilamina se~ may include one time carbon transfer sheets interposed with uncoated or CB coated sheets or webs in a manifold arrangement in accord with the dictates of the user thereof.
The novel and improved hot melt CB sheet coating broa~ly comprises the resulting set or solidi,ied film from an j applied and subsequently cooled emulsified liquid intermi~ture of a melted low oil content wax carrier vehicle, preferably of composite character, a melted synthetic flow wax and dispersant and a chromogenic reagent solution oE zinc chloride dissolved in water and suitably buffered to minimize, if not effectively neutralize the available acidic chl.oride content thereof; said emulsified intermixture also desirably having uniformly dispersed therein small but critically limited amounts of a resinous film forming a~cnt to promote film hardness and toughness, an isolating 3~ -Agent to minimize, if not effectively preclude, undesired transfer of the coating or portions thereof in response to un-intentional pressure application and an opaciEier-filler to reduce the gloss of the finished copy and preserve t~le appearance of the substrate.
In its narrower aspects, the subject invention includes a hot melt~CB sheet coating composition formed o about 35 to 75 percent of a meltable low oil content synthetic or naturally derived hard wax vehicle; at least 1 to about 15 percent of a ehemically modified wax-like material having properties of a flow agent, dispersant and emulsifier; and at least 10 to about 35 percent of a chromogenic reagent component in the form of a Lewis aeid, desirably zinc chloride dissolved in an appropriate amount o water necessary to form a relatively concentrated solution thereof.
Optionally but desirably included in such CB sheet coating composition for provision of an enhanced commercially attractive product are one or more of the following additional constituents.
One sueh optional constituent comprises a film orming agent to encourage the formation of a harder and tougher surface film after setting and to thus minimize premature actuation of the color producing reaction. This film forming agent must be non-reactive with the chromogenic reagent and may vary in amount from a mini~1~m of about 2% up to an amount that deleteriously effects the flow eharaeteristics of the mix. Another sueh optional but yet desirable constituent comprises an isolating agent that is essentially inco~.patible with the wa~ vehicle when solidified and which serves to provide desirable surface characteristics to the -13~
~ 3~
resultan~ ~ilm, such as to minimize, if not effec~ively preclude, undesired transfer of the coating or portions thereof in response to unintentiona:l pressure application. The isola~ing agent may vary in amount from a desira~le minimu~ of about 2% up to a ma-~i mum of about 20%. A still fur~her optional but desirable con~
sti~uen~ is an opacifier-filler to enhance the appearance o~ ~he coated surface of t~e CB sheet, such as by reducing the-gloss thereof. As is well kno~n in this art, such opacifier-filler may vary in amount required to provide a desired appearance, typically about 5%, and may include titani~m dioxide, various non-acidic high brightness clays, lithopone or other recognized materi.als.
The mel~able wa~ vehicle may suitably comprise any of the low oil oontent paraffin wa~es, microcrys~alline waxes, carnauba, Montan or other conventionally emp]oyed low oil con-tent vegetable, synthetic or mineral derived hot melt ~ax type carrier vehicles. The presently preferred meltable wax vehicle is a composi~e made up of abou~ 3 to 4 p2rts of a 101J oil con~en~
paraffin wax, intermixed with about 1 part or less o~ carnauba wax. A prèsently preferred para~fin ~Jax is a low oil content, hig~ melting point, fully re~ined paraffin ~ax, sui~ably Pace-maker*53 as manufactured and sold by Cities Service Oil Co. of Tulsa, Oklahoma. Suc~ wax has the following properties:
~elting point, AST~I, F 143-150 Melting point, ~ 146-153 Oil Content, Wt. % ma~ 0.25 Odorless Viscosity, cs at 210F 5.5 *trade mark Y~i!JA,,,`
3~
~eedle penetration a~ 77~F 13 Flash point F 485 O~ller suitable low oil conten~ hot melt ~7ax carrier vehicles include alpha olefinic waxes, suitably ~6817 Synthetic l~ax as ~vailable from Moore & Munger Inc. of Fairfield, Conne~ti-cut; microcrystalline wax, suitably 195 Be Square ~ite*, available from Pe~roli~e Corporations Bareco ~ivision or c ~ auba wax, suitably Brazilian Refined available ~rom Baldini & Company of Milburn, New Jersey.
Moore ~ Munger's ~6817 Synthetic Wa~ has the foll.owing properties:
Congealing Point, F., AST~ D 938 162 Needle penetra~ion, mrn/10, AST~ D 1321 77F. 14 Viscosity, Saybolt (a) ~10~.
(SVS), ~SI~l D 2161 52 ~iscosity, Kinematic ~a) 210~F.
(Cs ). ASl~ D 445 8 Color, Saybolt, ASTM ~ 156 +~
Flash Poin~, F. (COC) 510 Bareco's 195 Be Square l~ite microcr~s~alline wax has the Eollowing propertîes:
Melting Poin~, F. ASTM D 127 193/198 Penetration (a) 77F. ASI~I 6/7 Color AST~I D 1500 0.5/0.5 A pre:Eerred carnauba wax is Baldini's Brazilian Reflned Carnauba wax that is possessed o the ollowlng properties:
Melting point, min., F. 180.5 ~cid Number minimurn 4~0 maY~imulrl 10 . O
*~rade mark ,~' ~ r Saponification Number minim~n 78.0 maximum 88. n The mel~able chemically modified ~ax-like material having the desired properties of a flow agent, dispersant and emulsifier most suitably comprises a material of the - .
type disclosed in U.S. Patent No. 3,941,608. Other sui~ably chemically modi~ied wax materials having the somewhat similar properties include modified synthetic waxes as disclosed in U.S. Patent Nos. 2,890,124, 2,890,125 and 39163,548. ~ preferred con~erciall.y available wax-lik~ ma~.erial ~ormulated in accord with U.S~ Patent No~ 3,941~608 is ~7315 wax as sold by Moore & ~lunger, Inc., o Fairfield, Connecticut. Such #7315 wax has the following general properties:
Penetration Hardness (FLP)I-22 5 Typical Melting Point (Fisher Johns) 144~ypical Acid N~ber (AST~I D 97~) 2 Typical ~ no~her suitable wa~-like material having somewhat si.mi.lar properties as the foregoing suitably comprises an amide of a fatty acid, such as Armid*HT as available from ~rmour Industrial Chemical Company. Such Armi~*HT is possessed of the following properties:
~mide % (min.~ 90 Iodine value minimum maximum 5 Free fatty acid ~/~
minimu~ -maximum 5 *trade mark g Poi~t, C.
minimu~ . 9~
~.a~imum 103 r~he resinous film forming agent serves to enhance the formati.on of a relatively hard and tough coating ~o minimize undesired transfer of reagent material across t~ CB/CF inter-face in the absence of intentional positive pressure application.
A suitable film for~ing agen~, which must be non~reactive with chromogenic reagent component, desirably comprises a relatively low ~elting point ethylene-vinyl acetate copolymer,.such as ~C-~0~*
as manufactured and sold by ALlied Chemical Corporat~on. Such resin.ous ~ilm forming agent has the following properties:
Softening Point (AS~I E-28~ 20~F.
Hardness dmm (ASTM D-5) 9.5 Density ~/cc (ASI~I D-1505) ~.92 Viscosity (284F - Brookfield~ 55~ ~
~ nother suitable filTl formi.ng agent comprises oxidized polyethylene, suitably AC-629 as manufactured and sold by Allied Chemical Company. Such ~ilm forming agent has ~h~ following prop-er~ies:
Softening Point 2~4F.
Hardness 5.5 Density g/cc 0.93 A~erage Viscosity CPS 284F lGO
Acid Number 15 The isolating agent cooperatively functions as b]ooming agent to provide a lubricating and barrier surface to ~he solidifi.ed coating. Such isolating agent, which should be essentially incompatible with the wa~ carrier veh~cle when solidi-~*tracle mark - J--fied, so as to be selec~ively effective at the exposed sur~ace, suitably comprises a small amount of stearic acid, desirably HYSYRE~E 9718 as manu~actured and sold by the H~m~o Chem;cal Company. Zinc stearate may also be employed.
The opacifier-filler, ~lich co.smetically serves bo~h to reduce the gloss of the ~inished coa~ing and to preserve the appearance of the substrate, suitably comprises inely divided titanil~n dioxide such as UNIT~N~ 0-110 as manufac~ured and sold by ~merican Cyanamid Company. This material has a speci~ic gravity of about 3.9 and is so finely divided 2S to leave only about a 0.10% residue on a 325 mesh screen.
The chromogenic reagent component comprises a con- -centrated water base solution of ~inc chloride, suita~ly buffered to minimize, if not e~Eectively neutralizeJ the a~ailab~e acidic chloride conten~ thereof. Such solution is preferably made up of about 2 to 4 parts of zinc chloride with about 1 part of -~.Jater and which appxoaches a saturated solu~ion.
~ hile unbu~fered solutions of zinc chloride as the chromogenic reagent have provided highly efEective image Lormation in transfer coatings as formulated in accord -.~it~ the foregoing disclosed ~ormulaLions, such have been subject, undèr extreme climatic conditions o~ high temperatures and/or high humidity, to the apparent genera~lon and emanation of hydrogen chloride.
~lthou~l the quantities of hydrogen chloride so generated, appear to be minimal~ even ~mder such e~treme climatic conditions, the apparent emanation thereo~ from the applied coating has resul~ed in varying degrees o:E premature actuation of dye precursors over the entire sur~ace oE an interfacially contiguous CF coating and, *trade mark "., ~
r 3~2 depending on the ambient climatic condicions, in varying degrees of actuation of such CF sheet. Such premature actuation is, of course, highly undesirable as is thc generation of hydro~en chloride with its potential to irritate sensitive skins and to corrode iron rollers and other components of the processing equip-ment under any set of climatic conditions.
In order eo neutralize, if not actually prevent, the generation and emanation of such hydrogen chloride, a small amount of a neutralizinO ammonium salt, suitably ammonium carbonate or am~onium bicarbonate, is dissolved in the zinc chloride solution.
For a concentrated solution of about 2 parts of zinc chloride to 1 part of water, about .1 part of such neutralizing ammonium salt is generally satisfactory. Experience to date has generally indicated that the addition of about 2 to 4% of ammonium carbonate to zinc chloride solutions of the type herein disclosed results in effective avoidance of the above problems in an improved product.
While the mechanics of the reaction process are not fully understood it is surmised that the ammonium salt operates to neutralize or otherwise reduce the available active or acid chloride ion content and to thus preclude its association with avail~ble hydrogen ions. Also the possible availability of ammonia in both the liquid and gaseous phase ~ay also contribute to the neutralization of hydrogen chloride in both such phases.
Apart from the fore~oing, the additions of such neutralizing ammoni~m salt has provided some totally unexpected and, as yet, unexplai~able advantages and results. Such unexpected results are a bleaching and a marked increase in the h~rdness of , -19- . , tbe solidified CB hot melt coating. Such increase in hardness not Gnly functions to minimize pick off on processing components, reduces the tendency to smear and provides sharper copy, but also permits of significant reduction in the quantity of carnauba wax that is otherwise desirably included therein. Carnauba wax is not only one of the more cost significant components of the coating but is also only obtainable from a foreign source of supply who controls the ever increasing price thereof.
The unexpected bleaching action also enhances the appear-ance of the product through an enhancement of the "whiteness" of the coating.
A presently preferred ho~ melt CB sheet coating broadly comprises the rPsulting set or solidified film from an applied and subsequently cooled emulsified liquid întermixture of about 50-60% of a melted low oil content composite wax carrier vehicle, made up of about 3 to 4 parts of a low oil content paraffin wax intermixed ~Jith about 1 part of carnauba wax; about 2 to 5% of a chemically modified synthetic flo~J wax and dispersant and about 25-35% of a chromogenic reagent solution of at least 2 parts of zinc chloride dissolved in about 1 part of water buffered by a small amount of ammonium carbonate as outlined above; said emulsified intermixture also desirably having uniformly dispersed therein abou~ 3 to 10% of a resinous film forming agent to promote fil~ hardness and toughness, about 3-10% of an isolating agent to minimize, if noe effectively yreclude, undesired transfer of the coating or portions thereof in response to unintentional pressure applica~ion and about 5% of an opacifier-filler to reduce the gloss of the finished copy and preserve the appearance of tlle substrate.
In the production of ~he above described preferred CB sheet coating composition in accord with the principles of this invention, the requisite amounts of ~inc chloride and water are intermixed in a reaction vessel, suitably a steam jacketed kettle having a 210F temperature setting, to form a hot con-centrated solution thereof. To such solution is then added the ~eutralizing ammonium salt, preferably a~onium carbonate. To such elevated temperature and now neu~ralized chromogenic reagent solution, the requisite amounts of melted low oil content paraffin wax and carnauba wax components of the composite ~ax carrier vehicle are added and thoroughly intermixed as by use of a high speed dispersing blade for about 10 minutes or longer. To the intermixture as so constituted, the flow wax and dispersant constituent and the polyethylene filming agent and stearic acid isolating a~en~ constituents are added in solid form with con-tinual mixing until such consti~uents arP completely melted and dissolved in the composite wax carrier vehicle. ~en 50 melted and dissolved the opacifier-filler, preferably titanium dio~ide is added and the entire mass thoroughly mixed at high speed for 30 to 40 minutes to form a selectivel~ constituted liquid hot melt emulsion.
~ he resulting liquid hot melt emulsion is readily and selectively applied in the form of a thin filml as for e~ample at a coating weight of as low as 2 grams/square meter, by conven-tional means to the surface of a substrate, such as a sheet or web of paper or resinous film. The conventional coating means may comprise a print type coater, a roll coatcr or the like. The so coated substrate is then passed over a chill roll or the like to rapidly solidi~y or set the applied emulsified coating composi-tion.
I~ contradistinction to the systems of the prior art which were operatively dependent upon an Pxternal water source (often humid air) to provide the necessary ionized zinc chloride to react with the dye precursor, the system of the present in-vention contains and retains water as an operative element in discrete droplet liquid form within the solidified CB film and -thus effects the selective transfer of ionized zinc chloride as the operative entity.
Photomicrographs of coatings formulated in accord with the principles of this invention are shown in Figures 2a and 2b at magnifications of 4200X and 14000X respectively. These photomicrographs clearly depict the presence of discrete, micro-scopically sized zinc chloride am~onium salt solution globules distributed throughout the coating. Most of such globules are less than l micron in diameter with the great majority tnereof falling between .25 and .75 microns. Such photomicrographs further show that such zinc chloride solution globules peripherally incorporate an interface layer or the like that differs, at least in some ph~sical respects from bo.h the zinc chloride solution globules and from t~e surrounding solidified wa~ material as evidenced by the clearly different refractive indices involved.
The the ~bove ends, the foregoing described method of formulation provides a selectively constituted emulsion in whlch zinc chloride solution entities are thoroughly dispersed within the film. The basic hygroscopic, if not actual deliquescent, properties of zinc chloride and the nature of the resul~ant film -~2- ~
~erv~ to min:imize, i~ not e~ectively prevent, w~iter loss in storage with enhanced operating life for the product.
Anothe-r factor which contribu~es to the ~etention of the dispersed zinc chloride solution in discre~e liquid c~lobular :~orm within the CB film is the enhanced emulsific~i~n obtained through the use o~ an essentially alkaline and a~ino containing dispersa~ - flow wax consti~uen~ in association r~ith t~e relatively high acid number wax and film forming components.
jBy way of further examples the Eollo~7inv ~ormula~ions have provided CB sheet coating having in varying ~egree, the mani-~old advantages earlier set forth.
, EX~MPLE I
Paraffin Wax 7315 Wax ~.~
- ~C-400 Polyethylene 5 0 Stearic Acid 3 O
Titanium Dioxide 5 Zinc Chloride 30.
Water 10 EX~MPLE II
Paraffin Wax 4~.
7315 Wax 2.~
AC-629*Polyethylene 7.0 Titaniu~ Dio~ide 5 ~
Zinc Stearate lO.O
~inc Chloride 30.0 I~Jater 5-0 *trade mark t EX~IPLE II~ %
Paraffin Wax - 35.0 AC-400*Polyethylene lO.0 Zinc Chloride 20.0 Water - lO.0 ~315 Wax lO.0 Stearic Acid lO 0 Ti~anium Di~xide 5 0 E ~IPLE IV %
Paraffin Wax 55.0 Carnauba Wax 20~0 Zinc Chloride 15.0 Water 5i~0 7315 Wax 2~0 Stearic Acid 3 0 EX~MPLE V
%
Par~fin l~ax lO 0 Microcrystalline ~Jax 3G 0 Stannous Chloride 3~ 0 Water lQ 0 7315 Wa~ ~ o Stearic Acid 7 0 Titanium Dioxide lQ 0 -2~-*trade mark EX~`~LE VI
Carnauba ~ax 10 0 Alpha Olefin Wax 4~ ~
~C-629*Polyethylene 7 0 Ferric Chloride 20 ~
Water .lO~O
. 7315 Wax 3.0 Stearic Acid 5 Titanium Dioxide 5 i~
. ~y way of further preferen~ial example, ~.;he above formu-lations, when buffered to minimizej if not effect~vely neutralize~ ~
the available acidic chloride content thereof, are modified as j~:ol low5:
EX~IPLE IA
~/
Para~fin Wax ~2.
. 7315 Wax 2.
~C-400*Polyethylene 5.
Stearic Acid 2.
Titanium Dioxide 5.
Zinc Chloride 30.
Ammonium Carbonate 3.
Water lO.
EXA*.PLE II~ %
Paraffin Wax 38 7315 l~a~ 2.
*trade mark - -AC 62~ Polyethylene ~ 0 Titanium Dioxide ~.0 Zinc Stearate l~ 0 Zinc Chloride . 3~ 0 Ammonium Bicarbonate ~ 0 Water ~ 0 .
EX~IPLE IIIA
Para~fin Wax ~3~0 AC-40G~ Polyethylene l~ 0 Z;nc Chloride 2~ 0 Am~lonium Carbonate 2 0 Water 1~ 0 7315 Wax ~QI 0 Stearic ~cid lO i~0 Titanium Dioxide 5 ,0 EX~LE IVA
%
PararXin Wax 51 0 Carnauba Wax 20` 0 Zinc Chloride 15 0 Ammonium Carbonate 4 0 Water 5 0 7315 Wax ~ 0 Stearic Acid 3 0 *trade mark `t~ r~
EX~r~PL E ~A %
Paraffin Wax ~-Microcrystalline Wax ~ 0 Stannous Chloride 30~0 Ammonium ~icarbonate - 3 ~
Water . 10 Q
7315 Wax 3-0 Stearic Acid 7 0 Tii-anium Dioxide 1~.0 EX~LE V-.[A
Carnauba Wax 8 0 Alpha Ole~in Wax 38 0 AC-629 Polyethylene 7 ~
Ferric Chloride 2~ O
Ammonium Carbona~e 4 0 l~ater lO 0 -7315 Wcl~; 3 Stearic Acid 5 T.i-~anium Dioxide 5 ~
The Eollowin~ Eormulations have provided highly preEerred CB sheet coatings:
EYA~LE VII
/c~
Para~Ein Wax 39.0 Carnauba Wax 14.0 Zinc Chl.oride ~0.0 Water 10 *trade mark f' 3L~3B~
731S l~a~ 2 0 ~C-400 Polyethylene 5 0 ~tearic Acid 5.0 Titanium Dioxide 5 0 E ~MPLE VIIA
%
Paraffin l~ax 36 0 Carnauba Wa~ 0 Zinc Chloride 20 0 Water IO O
Ammonium Carbonate 3 0 7315 Wax 2 0 AC-400*Polyethylene 5 0 Stearic Acid 5 ~
Titanium Dioxide S O
The impro~ed CF or image receptor coating comprises the soli.d residue of an applied alkaline biased homogeneous mixture o~ an evaporable non-polar hydrocarbon solvent, a chemically neutral or alkaline resinous binder, an opaci~ier--filler and tri (p-phen~lamirlo) phenyl methanol as a dye precursor type of chromogenic reagent material. Such solidified CF coating i5 further characterized by the presence of such dye precursor in solid form and which dye precursor is insoluble in water or other polar solvents. Optionally but desirably included therein is a dis-persant to assist in the uniform dispersion of su~h dye precursor throughollt the mix and a thickener to provide the requisite ~is-cosity properties to facilitate the coatin~ of the mi~ in accord with the particular requirements of the co~ing equip~ent employed.
*trade maL^k The evaporable liquid vehicle mus~ be of non-polar character and a solvent for the tri (p-phenyla.tino) phenyl methanol dye precursor component. Suitable non--po]ar organic solvents include acetone, toluene, hep,ane ~nd naph~ha, with ~oluene being presently preferred for use.
A presently preferred CF coating comprises the solid residue of an applied intermi~ of an evaporable non-polar sol-ven~, suitably 50 to 80 parts of toluene, having disso:Lved therein at least about 7 to 20 parts of a chemically ne-ut~al or alkaline resinous binder, suitably polyvinylacetate. Added thereto is about .1 to .5 parts of a dispersant and about .1 to 4 parts of dry potassium hydroxide to provide an alkaline bias to the mi~ and to minimize inadvertent color reactions in the CF coated sheets. Also included in the mix is about up to 45 parts of opacifier-~illers~
sui~ably up to abou~ 20 parts finely divided ~;itanium dioxide and the remainder of calcium carhonate; and about .5 to 5 parts of tri (p-phenylamino) phenyl methanol as the chromogenic reagent.
The nature of the binder is not attended ~7ith any particular degree o~ criticality as long as it is of chemically neutral or of alkaline character and func-tions as a binding agent for the opacifier-filler and the color precursor, with both of the latter being in solid form. A pre~erred binder material hich is readily soluble in the above described evaporable non-polar solvent carrier comprises polyvinylacetate, suitably Vinac*
B-15, as manufactured by Air Products & Chemicals Company.
A presently preEerred dispersant com?rises sodium salt of polymeric carboxylic acid such as Tamol*731 as manuEactured by Rohm & Haas Company of Philadelphia, Penns,lvania.
*trade mark '3 ~i The opacifier-~iller, which serves both ~o enchance the appearance of the coating and to cooperate in the uniform dis~
tribution and spaced separation of the solid co~or precursor in the CF c02ting must also be of neutral or alkaline character.
Such ~iller may suitably comprise calclum carbo~a.te such ~s Alba-glos as manufactured byr Chas. Pfizer ~ Co. This material has a pH o~ g.4, a specific gravity o~ 2.7 and an aver~ge par~icle size of about .75 microns. Another suitable opacifier-~iller employed in conjunction with the above is Unitane 0-1110 ~itanium dioxide as manufactuxed by the American Cyanamid Compan~. This ma~erial has a mini.mum TiO2 content of 99%, a pH ~ about 7.7 and a speciflc gravity o~ about 3.9. - .
As noted ahove, the chromogenic reagent .~mployed is tri (p~phenyla~ino) phenyl methanol. Such chromogenic reagent, as disclosed in the Pig~ent Handbook (Vol I) pu~lished by John Wiley & Sons (Ed. Temple C. ~atton; 1973~, purportedl~ has the following chemical structure:
o ~3 .
~3 The depicted incorporation of the hydro~rl group inter-mediate the methane carbon atom and ~he phenyl gr~up, however, is incorrcct and the correct structural formula thereof is *trade mark .
T
~ N ~ - c ~ ~
~.
.;~
~ ' Such text further indicates however that in any commer-cially available supply ~hereof, that some lower phenylated product having the follo~ing chemical composition is probably also presen~:
0~
~N ~ I ~ H ~3 ~,, ' i ~H2 Such material may be described as biphenyl triamino triphenyl methanol.
The dlscls)sed tri (p-phenylamino) phenyl methanol as identified above is obtainable from The Sher~7in-WilLiams Company and from BASF albei.t in an apparently somewhat impure or contaminated form. As indicated in Sher~in-Williams technical bulletin AB-47, the tri (p-phenylamino) phenyl methanol ~therein called "Spirit Blue Carbinol Form") in the presence of an acld pH and a chloride forms an intensely colored dye stuf~ Icnown as Solvent Blue 23 (CI No. 42760).
Transposition into or from its colorless for~ is solely pH responsive, with intense color being produced in an acid pll environment. Alkaline biasing of the coating is main~ained by the selective utilization of .~lkaline biased constituent~ as set .
forth above and by the inclusion of small amounts of potassiu~
hydroxide when necessary or desirable.
In the production of the above described receptor coating for CF sheets, a liquid mixture is first formed by inter-mixing the non-polar toluene solvent ~7ith the polyvinylacetate binder material, the dispersant, the potassium hydroxide (to cast the pk of the solution to the all~aline side) with continuous agitation until all solids are completely dissolved after l~7hich the organic dyestuff dye precursor material is added with continued stirring until it is dissolved. To the above liquid mixture is then added the requisite amounts of calcium carbonate and the titanium dioxide opacifier-filler. Such addition should be accompanied by continuous stirring of such constituents in the liq~id vehicle to obtain a uniform dispersion thereof.
The specified dye precursor can be added as a powder, or it can be added in its acidified colored form. If the latter colored form is so utiliæed, the requisite alkaline cast of the other constituents, including any necessary amounts of potassium hydroxide, will cause the dye to revert to its colorless form in the mixture.
By ~ay of specific example the following formulation has provided an improved but yet inexpensive CF sheet coating.
E ~LE I
Toluene ~3.0 Potassium }Iydroxide 1.0 Calcium Carbonate 31.8 Tri (p-phenylamino) phenyl methanol 1.0 Polyvinylacetate 13.0 Dispersant 0.2' -3~-EXAMPLE Il Toluene ~3.0 Potassium l~ydroxide 1.9 Calcium Carbonate 27.0 Titanium Dioxide 4.8 Tri (p-phenylamino) phenyl methanol 1.0 Polyvinylacetate 13.0 Dispersant 0.2 The foregoing CF coating formulation results in a CF
c~ating layer of neutral or alkaline character, of acceptable appearance and having the color precursor chromogenic reagent homogeneously distributed there throughout. Such coatings are singularly inexpensive, abrasion and odor free and have been formed of coating weights as low as .2 grams/square meter.
Used with the CB coatings herein disclosed the image forming reaction proceeds without the color precursor chromogenic reagent material in the CF coating being solubilized and ionized by the liquid electron accepting chromogenic reagent material emitted rom the CB coating and in a markedly improved chemical carbon-less copy paper system.
Having thus described our invention, .
.
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A pressure sensitive chemical type transfer medium comprising:
planar sheet material having an at least partially transferable coating layer disposed on one surface thereof con-stituted by the solidified residue of an applied hot melt low oil content wax base emulsified liquid film including a chemically modified wax-like material having flow agent, dispersant and emulsifying properties and having discrete liquid droplets of a concentrated water base solution of ionized zinc chloride and an acidic halogen neutralizing agent dispersed therein and a non-transferable image producing receptor layer dis-posed on the other surface thereof;
said image receptor layer comprising the solid residue of an applied alkaline biased liquid intermixture of an evaporable non-polar liquid hydrocarbon solvent vehicle, a non-acidic resinous binder, opacifier-filler materials and a chromogenic reagent selected from the group consisting of tri (p-phenylamino) phenyl methanol and biphenyl triamino triphenyl methanol dispersed there-within and being selectively convertable into a color producing condition upon interreaction with said zinc chloride chromogenic reagent material.
planar sheet material having an at least partially transferable coating layer disposed on one surface thereof con-stituted by the solidified residue of an applied hot melt low oil content wax base emulsified liquid film including a chemically modified wax-like material having flow agent, dispersant and emulsifying properties and having discrete liquid droplets of a concentrated water base solution of ionized zinc chloride and an acidic halogen neutralizing agent dispersed therein and a non-transferable image producing receptor layer dis-posed on the other surface thereof;
said image receptor layer comprising the solid residue of an applied alkaline biased liquid intermixture of an evaporable non-polar liquid hydrocarbon solvent vehicle, a non-acidic resinous binder, opacifier-filler materials and a chromogenic reagent selected from the group consisting of tri (p-phenylamino) phenyl methanol and biphenyl triamino triphenyl methanol dispersed there-within and being selectively convertable into a color producing condition upon interreaction with said zinc chloride chromogenic reagent material.
2. A pressure sensitive chemical type transfer medium as set forth in Claim 1 wherein:
said applied hot melt low oil content wax base emulsified liquid film includes an amine modified synthetic wax flow agent and dispersant as an emulsifying agent therewithin.
said applied hot melt low oil content wax base emulsified liquid film includes an amine modified synthetic wax flow agent and dispersant as an emulsifying agent therewithin.
3. A pressure sensitive chemical type transfer medium as set forth in Claim 1 wherein:
said acidic chloride neutralizing agent is selected from a group consisting of ammonium carbonate and ammonium bicarbonate.
said acidic chloride neutralizing agent is selected from a group consisting of ammonium carbonate and ammonium bicarbonate.
4. A pressure sensitive chemical type transfer medium as set forth in Claim 2 wherein:
the majority of said discrete droplets of the concen-trated water base solution of zinc chloride are homogeneously distributed within the solid coating layer and the majority of which are less than 1 micron in diameter.
the majority of said discrete droplets of the concen-trated water base solution of zinc chloride are homogeneously distributed within the solid coating layer and the majority of which are less than 1 micron in diameter.
5. A pressure sensitive chemical type transfer medium as set forth in Claim 1 wherein said image receptor coating further includes a dispersant and sufficient dry potassium hydroxide to assure an alkaline bias to said receptor layer.
6. A pressure sensitive chemical type transfer medium as set forth in Claim 1 wherein:
said image receptor layer comprises the solid residue of an applied alkaline biased liquid intermixture of 50 to 80 parts of an evaporable non-polar liquid hydrocarbon solvent vehicle selected from the group consisting of toluene, acetone, heptane and naphtha; about 7 to 20 parts of said non-acidic resinous binder; opacifier-filler material selected from the group consisting of titanium dioxide and calcium carbonate and about 1/2 to 5 parts of said chromogenic reagent dispersed therewithin.
said image receptor layer comprises the solid residue of an applied alkaline biased liquid intermixture of 50 to 80 parts of an evaporable non-polar liquid hydrocarbon solvent vehicle selected from the group consisting of toluene, acetone, heptane and naphtha; about 7 to 20 parts of said non-acidic resinous binder; opacifier-filler material selected from the group consisting of titanium dioxide and calcium carbonate and about 1/2 to 5 parts of said chromogenic reagent dispersed therewithin.
7. A pressure sensitive chemical type transfer medium as set forth in Claim 1 wherein:
said image receptor layer comprises the solid residue of an applied alkaline biased liquid intermixture of about 53 parts of toluene as a non-polar hydrocarbon solvent, about 13 parts of polyvinylacetate binder material, about 32 parts of opacifier-filler material, about 1 part of potassium hydroxide, about 0.2 parts of a dispersant and about 1 part of chromogenic reagent material dispersed therewithin.
said image receptor layer comprises the solid residue of an applied alkaline biased liquid intermixture of about 53 parts of toluene as a non-polar hydrocarbon solvent, about 13 parts of polyvinylacetate binder material, about 32 parts of opacifier-filler material, about 1 part of potassium hydroxide, about 0.2 parts of a dispersant and about 1 part of chromogenic reagent material dispersed therewithin.
8. A pressure sensitive chemical type transfer medium as set forth in Claim 2 wherein said amine modified wax-like flow agent is selected from the group consisting of the product obtained by reacting a selectively oxidized linear unsaturated hydro-carbon having a terminal carbon double bond with ammonia or a primary organic amine and further reacting the resulting modified hydrocarbon with an isocyanate; the product obtained by reacting an oxidized microcrystalline wax with an isocyanate, the product obtained by reacting an oxidized non-benzenoid wax with an isocyanate; the product obtained by reacting an oxidized microcrystalline wax with ammonia or an amine and further reacting the resulting modified hydrocarbon with an isocyanate and the product obtained by reacting an oxidized non-benzenoid wax with ammonia or an amine and further reacting the resulting modified hydrocarbon with an isocyanate.
9. A pressure sensitive chemical type transfer medium comprising:
a planar sheet material having at least partially trans-ferable coating layer disposed on one surface thereof;
said transferable coating layer constituted by the solid-ified residue of an applied hot melt emulsified film con-sisting of about 35 to 75% of a meltable low oil content hard wax compositely constituted of a major portion of a wax selected from the group consisting of paraffin wax, microcrystalline wax and alpha olefin wax;
at least 1% to about 15% of an amine modified synthetic wax flow agent and dispersant as an emulsifying agent therein;
about 10 to 35% of a concentrated water solution of zinc chloride containing a relatively small amount of an acidic chloride neutralizing agent selected from the group consisting of ammonium carbonate and ammonium bicarbonate and a nontransferable image producing receptor layer disposed on the other surface thereof, said image receptor layer comprising the solid residue of an applied alkaline biased liquid intermixture of 50 to 80 parts of an evaporable non-polar liquid hydrocarbon solvent vehicle selected from the group consisting of toluene, acetone, heptane and naphtha; about 7 to 20 parts of a non-acidic resinous binder; opacifier-filler material selected from the group consisting of titanium dioxide and calcium carbonate and about 1/2 to 5 parts of a chromogenic reagent selected from the group consisting of tri (p-phenyl-amino) phenyl methanol and biphenyl triamino triphenyl methanol.
a planar sheet material having at least partially trans-ferable coating layer disposed on one surface thereof;
said transferable coating layer constituted by the solid-ified residue of an applied hot melt emulsified film con-sisting of about 35 to 75% of a meltable low oil content hard wax compositely constituted of a major portion of a wax selected from the group consisting of paraffin wax, microcrystalline wax and alpha olefin wax;
at least 1% to about 15% of an amine modified synthetic wax flow agent and dispersant as an emulsifying agent therein;
about 10 to 35% of a concentrated water solution of zinc chloride containing a relatively small amount of an acidic chloride neutralizing agent selected from the group consisting of ammonium carbonate and ammonium bicarbonate and a nontransferable image producing receptor layer disposed on the other surface thereof, said image receptor layer comprising the solid residue of an applied alkaline biased liquid intermixture of 50 to 80 parts of an evaporable non-polar liquid hydrocarbon solvent vehicle selected from the group consisting of toluene, acetone, heptane and naphtha; about 7 to 20 parts of a non-acidic resinous binder; opacifier-filler material selected from the group consisting of titanium dioxide and calcium carbonate and about 1/2 to 5 parts of a chromogenic reagent selected from the group consisting of tri (p-phenyl-amino) phenyl methanol and biphenyl triamino triphenyl methanol.
10. A pressure sensitive chemical type transfer medium as set forth in Claim 9 wherein said image receptor layer comprises the solid res-idue of an applied alkaline biased liquid intermixture of about 53 parts of toluene as a non-polar hydrocarbon solvent, about 13 parts of polyvinylacetate binder material, about 32 parts of opacifier-filler material, about 1 part of potassium hydroxide, about 0.2 parts of a dispersant and about 1 part of chromogenic reagent material dispersed there-within.
11. A pressure sensitive chemical type transfer medium as set forth in Claim 10 wherein said amine modified wax-like flow agent is selected from the group consisting of the product obtained by reacting a selectively oxidized linear unsaturated hydrocarbon having a terminal carbon double bond with ammonia or a primary organic amine and further reacting the resulting modified hydrocarbon with an isocyanate; the product obtained by reacting an oxidized microcrystalline wax with an iso-cyanate, the product obtained by reacting an oxidized non-benzenoid wax with an isocyanate; the product obtained by reacting an oxidized microcrystalline wax with ammonia or an amine and further reacting the resulting modified hydrocarbon with an isocyanate and the product obtained by reacting an oxidized non-benzenoid wax with ammonia or an amine and further reacting the resulting modified hydro-carbon with an isocyanate.
12. A pressure sensitive chemical type transfer medium comprising:
planar sheet material having an at least partially transferable coating layer disposed on one surface thereof, said transferable coating layer constituted by the solidified residue of an applied hot melt emulsified liquid film consisting of about 50 to 60% of a composite meltable low oil content wax carrier vehicle made up from 3 to 4 parts of paraffin wax to 1 part of carnauba wax;
about 2 to 5% of a synthetic chemically modified wax-like material having the properties of a flow agent and dispersant;
about 3 to 10% of a polyethylenic film forming agent;
about 5% of an opacifier-filler;
about 3 to 10% of stearic acid and about 25 to 35% of a concentrated solution of zinc chloride made up of at least 2 parts of zinc chloride to 1 part of water as an electron accepting chromogenic reagent in emulsified discrete liquid droplet form in said layer together with a relatively small amount of an acid chloride neutralizing agent selected from the group consisting of ammonium carbonate and ammonium bicarbonate non-transferable image producing receptor layer disposed on the other surface thereof;
said image receptor layer comprising the solid residue of an applied alkaline biased liquid intermixture of an evaporable non-polar liquid hydrocarbon solvent vehicle, a non-acidic resinous binder, opacifier-filler material and a chromogenic reagent selected from the group consisting of tri (p-phenylamino) phenyl methanol and biphenyl triamino triphenyl methanol dispersed therewithin and being selectively convertable into a color producing condition upon inter-reaction with said zinc chloride chromogenic reagent material.
planar sheet material having an at least partially transferable coating layer disposed on one surface thereof, said transferable coating layer constituted by the solidified residue of an applied hot melt emulsified liquid film consisting of about 50 to 60% of a composite meltable low oil content wax carrier vehicle made up from 3 to 4 parts of paraffin wax to 1 part of carnauba wax;
about 2 to 5% of a synthetic chemically modified wax-like material having the properties of a flow agent and dispersant;
about 3 to 10% of a polyethylenic film forming agent;
about 5% of an opacifier-filler;
about 3 to 10% of stearic acid and about 25 to 35% of a concentrated solution of zinc chloride made up of at least 2 parts of zinc chloride to 1 part of water as an electron accepting chromogenic reagent in emulsified discrete liquid droplet form in said layer together with a relatively small amount of an acid chloride neutralizing agent selected from the group consisting of ammonium carbonate and ammonium bicarbonate non-transferable image producing receptor layer disposed on the other surface thereof;
said image receptor layer comprising the solid residue of an applied alkaline biased liquid intermixture of an evaporable non-polar liquid hydrocarbon solvent vehicle, a non-acidic resinous binder, opacifier-filler material and a chromogenic reagent selected from the group consisting of tri (p-phenylamino) phenyl methanol and biphenyl triamino triphenyl methanol dispersed therewithin and being selectively convertable into a color producing condition upon inter-reaction with said zinc chloride chromogenic reagent material.
13. A pressure sensitive chemical type transfer medium as set forth in Claim 12 wherein said image receptor layer comprises the solid residue of an applied alkaline biased liquid intermixture of 50 to 80 parts of an evaporable non-polar liquid hydrocarbon solvent vehicle selected from the group consisting of toluene, acetone, heptane and naphtha; about 7 to 20 parts of said non-acidic resinous binder; opacifier-filler material selected from the group consisting of titanium dioxide and calcium carbonate and about 1/2 to 5 parts of said chromogenic reagent dispersed therewithin.
14. A pressure sensitive chemical type transfer medium as set forth in Claim 12 wherein said image receptor layer comprises the solid res-idue of an applied alkaline biased liquid intermixture of about 53 parts of toluene as a non-polar hydrocarbon solvent, about 13 parts of polyvinylacetate binder material, about 32 parts of opacifier-filler material about 1 part of potassium hydroxide, about 0.2 parts of a dispersant and about l part of chromogenic reagent material dispersed therewithin.
15. A pressure sensitive chemical type transfer medium as set forth in Claim 12 wherein said chemically modified wax-like material is selected from the group consisting of the product obtained by reacting a selectively oxidized linear unsaturated hydrocarbon having a terminal carbon double bond with ammonia or a primary organic amine and further reacting the resulting modified hydrocarbon with an isocyanate; the product obtained by reacting an oxidized microcrystalline wax with an iso-cyanate, the product obtained by reacting an oxidized non-benzenoid wax with an isocyanate; the product obtained by reacting an oxidized microcrystalline wax with ammonia or an amine and further reacting the resulting modified hydro-carbon with an isocyanate and the product obtained by reacting an oxidized non-benzenoid wax with ammonia or an amine and further reacting the resulting modified hydrocarbon with an isocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000402173A CA1184382A (en) | 1982-05-03 | 1982-05-03 | Carbonless copy paper system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000402173A CA1184382A (en) | 1982-05-03 | 1982-05-03 | Carbonless copy paper system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1184382A true CA1184382A (en) | 1985-03-26 |
Family
ID=4122699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000402173A Expired CA1184382A (en) | 1982-05-03 | 1982-05-03 | Carbonless copy paper system |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1184382A (en) |
-
1982
- 1982-05-03 CA CA000402173A patent/CA1184382A/en not_active Expired
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