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United States Patent Office 3,455,721

Patented July 15, 1969
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3,455,721 and better performance. Color-reactant recording systems
COLOR SENSITIZED RECORD MATERIAL COM are so called because the reactant chromogenic material
PRISING PHENOLIC RESIN AND ACID TYPE content of the ink used in such systems is substantially
MINERAL colorless and assumes a color when applied to a specially
Paul S. Phillips, Jr., and Gerald M. Hein, Dayton, Ohio, sensitized recording surface, some of the chromogenic ma
assignors to The National Cash Register Company, terial coloring at once and some coloring on prolonged
Dayton, Ohio, a corporation of Maryland contact with the associated particulate material. This in
No Drawing. Filed Dec. 21, 1964, Ser. No. 420,193 vention, when the composition is applied as a coating to
Int. CI. B41m 5/12; D21h 1/28 paper or incorporated therein as a filler, provides a record
U.S. CI. 117–36.2 13 Claims member with such specially-sensitized recording surface
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which also is distinguished in use for regular colored oily
ink reception because it utilizes a paper-coating or paper
ABSTRACT OF THE DISCLOSURE loading material which is well recognized as improving
The invention provides a record material sensitized with the printing quality of paper and at the same time acts
interspersed microfine solid particles of acid-reacting oil 15 as one of the reactants. Thus the sensitized sheet can be
soluble polymeric material, preferably a phenolic poly printed on at one time with regular printing inks and at
mer, and microfine solid particles of an acid-reacting another time at another place with the colorless ink.
mineral, preferably kaolin clay; the polymeric material As distinguished from pigment inks, the chromogenic
forming a distinctive mark upon application of a basic material in the colorless ink of these systems is in the
chromogenic material, usually dissolved in an oil, and the 20 nature of a colorless dye or combination of dyes that as
mineral providing a site for reaction of a second chromo sume, through chemical reaction, a visually distinctive
genic material which produces its distinctive mark over a color when undergoing reaction with the particulate par
ticles on the sheet. In one form of use of the sheet which
period of time. is the subject of the invention, the chromogenic reactant
25 in colored form is blended in the applied ink with an
This invention relates to a record member sensitized already colored dye component, so that the ink makes one
with microfine color-reactant particles of different kinds color, the color of the colored dye component, on an
that are distinguished in one way by their chemical reac unsensitized record sheet and a blend of colors of the
tion characteristics and in another way by their solubility colored dye and the reacted colorless component on a sen
characteristics. The invention also relates to a composi 30 sitized record sheet. This kind of ink is disclosed in
tion for sensitizing the record member. United States Patent No. 2,714,074, which issued July
The record member consists of a base sheet or web 26, 1955, on the application of Barrett K. Green.
member either of fibrous construction, such as paper, For most recording purposes, it is essential from a
or of continuous structure, such as films, of organic poly commercial standpoint that a distinctively colored mark
meric material, carrying the color-reactant particles in an 35 make prompt appearance on the application of the color
exposed state with respect to applied ink. The particles are less ink to the recording surface, to produce a visible
arranged in intimate juxtaposition to form an apparently representation of whatever is meant to be recorded; that
unbroken ink-receptive surface, yet substantially each par the color be of distinctive hue but also of high intensity;
ticle individually is available for contact with applied ink. and that the mark remain colored for a long period of
While the record member is adapted to receive any kind 40 time consistent with the objective of permanent recording.
of ink, whether colored or colorable, its special utility is The well-known infirmities of colored dyes as regards
its use with an oily ink which is normally colorless and permanence relate to light-fading, thermal fading, and
carries in liquid solution a colorless chromogenic reactant molecular rearrangements and disintegrations of various
for each of at least two of the particle kinds, each kind kinds in which part or all of the visually perceptible color
of chromogenic material having the property of becom 45 is lost. It is an object of the invention to overcome, as far
ing colored upon contact of its solution state with its as possible, the loss of color in the color-reactant marks
associated kind of particle. All of the particles are in which are occasioned by passage of time, by exposure
soluble in water; however, at least one kind of particle to environment, or by intentional chemical or physical
is soluble in the oily ink, and at least one other kind of attrition or obliteration.
particle is insoluble in the oily ink. At least one of the 50 During the last decade, one of the most prominent
kinds of chromogenic reactant material of the special ink of such colorless recording systems utilized a multiple
undergoes an acid-base reaction with its paired kind of coloring principle in which an oily ink having two types
particle when and where applied to the novel record of chromogenic reactants, normally colorless, was used on
member to produce a distinctively colored mark, and at an ink-receiving sheet sensitized with substantially insol
least another of the kinds of chromogenic reactant ma 55 uble acid-like materials of high surface activity, such as
terial, when and where applied, undergoes hydrolysis fol attapulgite and zeolite material. As the normally color
lowed by an oxidation-reduction reaction to produce its less chromogenic material content of inks used therewith,
distinctive color. As the two chromogenic materials are the most outstanding are Crystal Violet Lactone and
both applied to the same areas, their color will be a blend Benzoyl Leuco Methylene Blue, both of which in the col
of their individual hues. While in its simplest form the 60 ored form have intense hues in the blue end of the visual
invention can be carried out by using just two kinds of spectrum band. Such a system is disclosed in United
particle reactants, typified by acid-reacting oil soluble States Letters Patent No. 2,712,507, which issued July 5,
phenolic polymeric material and kaolin, in some cases, 1955, on the application of Barrett K. Green, and per
for which examples will be given, supplementary kinds of tains to a construction in which the ink is applied from an
oversheet by pressure-release from microscopic capsules.
reactants may be added for additional properties which This system is now in world-wide use and commands a
it is desired to have present in the record member, and predominant position in the field of colorless recording
these added properties may be physical or chemical. systems, and its continued use is expected. It employs
The whole utilitarian purpose of providing the novel only insoluble particulate material to cause coloration in
sensitized record member has many facets, all contribut 70 applied inks, the coloration of Crystal Violet Lactone
ing to the fuller commercial acceptance of color-reactant being developed by an electron donor-acceptor solid
recording systems by reason of lower cost, wider utility, surface reaction with acid clay-like material, and the

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The latter absorp mine. It has been No. dissolving an excess of the polymeric material. 2. Janu In the base-acid color system. In general. acid properties are deemed equivalents of kaolin. because of its pages 530 to 531 (ethylene-maleic anhydride copolymer). basic mono azo dyes: p-dimethyl available for reaction with the chromogenic materials to aminoazobenzene-o-carboxylic acid (Methyl Red). applied as a dispersion coating to a continuous film-like A further criterion of the solvent is that it must not web such as synthetic organic polymeric material made interfere with the mark-forming reaction. so as to be economical.455.828.5-dichloro hydroxyl groups) and not having an absorption in the phenyl) leucauramine. a larger amount of polymeric material—up to. 15 or more percent—to form an efficient reaction. but following azo dyes. bands. and hydroxyl groups and consequently makes such groups un anisylidene acetone. and the preparation of the phenol 20 8'-methoxybenzoindolinospiropyran.093. g. and methylene blue. there are many useful with the basic chromogen-acidic polymer mark other materials of a mineral nature which can be used forming components are toluene. may be used. preferably in excess of 2%. all coming within certain limits the mark-forming reaction or diminish the intensity of merely set as practical and not set for any chemical or the mark. so as to to be applied to a wet sheet of paper in the formative state provide every opportunity for utilization of the chromo 50 in any desired manner. so 60 relates to criteria of the factors of intensity. and the remainder from 60% down to group are diaryl phthalides: 3. definition. on a weight basis. meric mark-forming component(s) chosen must be The preparation of the maleic anhydride copolymers acidic relative to the basic chromogenic compound and re is described in the literature. Other types of particulate and substantially vents are high-boiling-point petroleum fractions and colorless water.” volume 41. January 1951. basic mono to be of inventive or operative significance. 1958. A white kaolin is used. and this mark-forming components into intimate admixture. 3. and xylene. that the mark-forming contact proceeds. but not yl) Rhodamine B Lactams. and 6'-chloro. 2. and a single 35 or multiple component solvent may be used which is the paper-making and paper-converting industries. 1958. particularly N-(2. States Patent No. if they are still soluble. or on the other hand tion at a reaction site. in which case the solvent chosen should be physical reason. color. an aqueous dispersion of the methoxy benzoindolinospiropyrans. whiteness. issued to Clyde S. dibenzylidene acetone. Rhodamine B Lactams such as N-(p-nitrophen and empolying the inventive concept. the publication “Vinyl and Related Polymers. through solution. or made a part of the paper furnish genic material and thus to assure the maximum colora from which a paper sheet is made. leucauramines: the N-halo ponent. and a great many other factors with regard to the Colorable by the specified polymeric materials are a characteristics of the base web material. or to any record sup stances. Of course.052. and Mary Lou Frazier on A laboratory method useful in the selection of suitable Mar.3-bis(4-dimethylaminophenyl) phthalide ponent to one part. brought the make useful records for the purpose in view. 25. as a rule of thumb but not as a limitation. such as. of the oil-insoluble com tone). the presence of the solvent may interfere with 55 port material surface. all above-mentioned Miller and Phillips United States patent of which come within the paper manufacturers' and application. 2.-1 region (which is indicative of the free rated by reference herein.8'-trimethoxybenzoindolinospiropyran. volume 43. and Malachite Green Carbinol. polyaryl carbinols: bis(p-di described in “Industrial and Engineering Chemistry. pages 628 to 630 30 of acid characteristics necessary to color benzoyl leuco (vinyl methyl ether-maleic anhydride copolymer).” by Calvin Kaolin is generally known and used in the paper-making E. acyl auramines: N-benzoyl aura 1600–1700 cm. and 45 different specific compositions on a dry basis may be made. Generally. Examples of non-volatile sol 40 of perfection. versal abundance in supply. Rhodamine B Lactams: N-(p-nitrophen meric materials suitable for practicing this invention is 15 yl) Rhodamine B Lactam. and the compound acetylene polymers is described in “Industrial and En p-dimethylaminostyryl quinoline. the sufficiently vaporizable to assure its removal from the re materials should be used in just sufficient quantities to action site after having. and 4-phenylazo-1 The preparation of the phenolic-formaldehyde poly naphthylamine. although not so good as kaolin from a rheological standpoint. as stated above.341. petroleum distillate. Examples of volatile solvents low cost. of the basic From the foregoing choice of materials. issued to Herbert Hönel on 4. and N-acetyl auramine..and oil-insoluble minerals of the necessary chlorinated diphenyls. issued to Clyde S. 65 printers' skill and general knowledge and are not deemed acyl auramines.721 5 6 Resoles. such being diaryl phthalides. and these may then be used as desired. Adams and Marjorie J. a number of chromogenic material. by weight. said patents being incorpo 3200–3500 cm. and. of the oil-soluble com (Malachite Green Lactone). its plate-like particle form. leucauramines.828. a particular Crystal Violet Carbinol. and the environment of use. by weight. c. In some in into record sheets. for example. and the N-alkylhalophenyl derivatives of phenolic resins is a determination of the infra-red ab leucauramine disclosed in United States Letters Patent sorption pattern of a candidate material. the characteristics large number of basic dyes which also are disclosed in the of the ink to be applied. 25. phenyl derivatives of leucauramine disclosed in United Amounts of paper-coating adhesives are added as is neces . subject to change in properties upon aging. per instead of and matched against kaolin clays as the standard chloroethylene. found that phenolic resins showing an absorption in the Cormack on Mar. Cormack. second printing.3-bis(p-dimethylamino 25% of the particulate reactants divided generally on a phenyl)-6-dimethylaminophthalide (Crystal Violet Lac basis of four parts. one 25 active with the chromogenic material to effect distinctive of the maleic anhydride-vinyl copolymers. Marjorie J. 4– be specified. Aug. Incorporated. as being made into in the preferred system. Illustrative compounds of each 70 water. and its wholly or partially volatile. polyaryl carbinols. which gives it un The liquid solvent of the ink used must be capable of paralleled coating properties in aqueous slurries. as disclosed in color formation or color change. some Generally. the solvent should be capable of an aqueous slurry to be coated on a finished paper sheet.342. though States Letters Patent No. Adams. its uni dissolving the mark-forming chromogenic components. However. called Michler's Hydrol. published April 1959 industry as “China clay” and is outstandingly preferable as by John Wiley & Sons. 25. which may be identi particulate materials could well be from 40% to 75% fied as (8'-methoxy BIPS).–1 region are suitable.” methylaminophenyl) methanol. the poly ary 1949. solving at least 1%. aminoazobenzene (Oil Yellow AAB). the solvent chosen should be capable of dis being bentonites. its historical general usage in The solvent may be volatile or non-volatile. pages 134 to 141. polymer thereof is described in Example 1 of United 8'-methoxy BIPS: 8'-methoxy benzoindolinospiropyran. Schildknecht. or strips. by weight. and 3. 1936.7. gineering Chemistry. 8-unsaturated aryl ketones. it is an ideal material. say. pages 73 to 77. and 8' as a limitation in any sense. See pages 65 to 68 the particulate oil-insoluble and water-insoluble material (styrene-maleic anhydride copolymer).8-unsaturated aryl ke tion region is indicative of the desensitization of the 10 tones: dianisylidene acetone.

~ * * ~ * * 3 position may vary greatly. all of such factors tending to de . 60%. if not on a cost and kaolin in water containing sodium silicate. 1 lic resin -----------------------------. or zeolite material may be used with the polymeric ma Sufficient water to make a solids content of 25% to terial. At least 10. attapulgite. of course. to paper-coating practices. Example IV crease the efficient use of the associated active particles be Paper-coating kaolin (white) ------------------. 1 again. and. Here. for oil-base ink. Solids. parts/weight (e) Polyvinyl alcohol ---------------------. 0 I because of their physical situation or condition in the sup port sheet.0 Such a coating composition contains binder material and 50 (g) Water to make 25% to 60% solids content. In this area of permissible sub stitutes or addition materials. parts/weight The particle size of the reactants preferably should be (a) Kaolin (as specified) ------------------. Example III It will be apparent that the ratio of the solids content of acid mineral to polymeric material content to the com Paper-coating kaolin (white) -------. 1 (c) Binder ----------------------------. - Oil-soluble acid-reactant organic polymeric material – 1 Binder as required. and that other materials of reactant nature can be 60%.75–100 tion in regard to either choice or necessity. may one to three microns. Silica gel is oil-insoluble but adsorbent thereof. 33–300 Oil-soluble acid-reactant organic polymeric material .. mask the particles physically should not be used. finally. although 35 (b) Silica gel ----------------------------. of actual requirements.0 terials to the most effective size is too expensive. 1.30. 0 i: effect in the characteristics stated.2 cause of a limitation of the exposed surface area.9–3. and as of now the best (c) Sodium silicate -----------------------.0 economy is tolerable.10 60 (g) Water to make 20% to 35% solids content. 30. ' One of the chief considerations in selecting a preferred (a) Attapulgite (attapulgus clay) -----------. employed to supplement the main pair of particulate reac EXAMPLE: V tants. may contain defoamers and dispersing agents common 1. basis. up to ----------------------. 75–100 from one to three microns in largest dimension. United States of America. (f) Minimum binder up to ----------------. 0.*-* * * * :. The polymeric-material-produced color of 30 Crystal Violet Lactone is significantly more persistent Example VI than that produced by silica gel. up to ---------------. and Ger polymeric material are slightly delayed in responsiveness 20 I?lany-------------------------------.15–40 Solids. used singly or in combination ---. the paper makers’ and printers’ skill and judgment Silica gel -----------------------------------.9–3. 300. 40 (g) Water to make 25% to 60% total solids con On the other hand.0 Paper-coating kaolin (white) -------------------.0. 0–25 considerable latitude at the expense of efficiency and (c) Sodium silicate ----------------------. (a) Clay—one or more selected from the Example II group consisting of kaolin. nor Sufficient water to make a solids content of 25% to should any material be used as an adhesive in great excess 60%. Example VIII way is to mean a limitation of the practice of the inven (a) Attapulgite (attapulgus clay) -----------. Where the particles of kaolin and acid the Cornwall district of Great Britain.0.1 0–100 manufacture of the record sheet.1. but such use is not (c) preferentially are ground together necessary to the practice of the invention in its simplest 25 until the phenolic material has reached a particle size in the range of form. for specific purposes. kaolin and water.0–4. The examples pertain especially . some attapulgite 10 Minimum necessary binder. then the ground mixture is blended into a slurry of the be finely ground. 15–40 larger particle sizes are tolerable as long as sufficient color (f) Minimum binder up to ----------------. 7 3. disperses readily in water.1 applied.721 8 sary to adhere the particles to the base web to which it is Oil-soluble acid-reactant polymeric material ------. and a lighter weight finished sheet may thereby Example VII be produced. if the grinding of ma (d) Polyvinyl alcohol --------------------. U.1 Example IX Sufficient water to make a solids content of 25% to 60%. Czechoslovakia. 1. their (e) Phenolic resin (as specified) ------------.15–40 the novel composition to a finished web of paper as it (e) Polyvinyl alcohol ---------------------. as from 10 to 1 in Example I Silica gel -----------------------------------.5 Binder as required. and this must be con sidered in the use of the latter material.S. but. adhesives that have a tendency to Binder as required up to -----------------------. () 30. Attapulgite ----------------------------------. 1 It has been mentioned that. Oil-soluble acid-reactant polymeric materials -----. 55 (b) Silica gel ----------------------------. silica gel has considerable 15 Permissible Preferred range amount standing because it is capable of instantaneously strongly coloring oil solutions of Crystal Violet Lactone (although (a) White kaolin of high kaolinite con tent as mined in Georgia and South the color is not persistent) and is an efficient oil receptor Carolina.1 0–100 embodiment of the invention must be concerned with the 45 (b) Kaolin (as specified) -----------------. but their specification in no • . if desired. 100 Paper-coating kaolin (white) -------------------.20–112. 3 (b) Polymeric material—acid-reacting pheno Attapulgite ----------------------------------.0 reaction per unit area of the record material is provided. 1 (d) Water to yield a total solids content of 4% Sufficient water to make a solids content of 25% to 70 to 31%. finer grinding may result in more effi tent like Example V except disperse silica gel cient use of materials on a weight basis.30. and bentonite. is colorless. the and may be treated to increase its porosity and effective latex and starch binders in the chosen amount are added.9–3.455.--------------------------------------------------- ness as an acid.0 (f) Minimum binder up to ----------------. 1 play a part.S.R.0–25 COATING COMPOSITIONS (c) Sodium silicate -----------------------.9–3. For instance. Items (b) and 15–40 0.0 passes the coating station in a paper-making machine. .2–5 Example I (d) Oil-soluble acid-reacting phenolic resin ---. an amount of silica gel up to equal the amount of acid polymeric material may be used for its beneficent (b) Phenolic resin----- (c) Polyvinyl alcohol----- (d) Minimum binder up to------------- (e) Sufficient water to make a solids content of 25% to 60%.1 to 1 to 3 in Example IX. up to ----------------------. 0–4 way to sensitize a sheet is to apply an aqueous slurry of (d) Oil-soluble acid-reacting phenolic resin ---.

The record member of claim 5 in which the web multitude of microfine solid particles of both an oil is paper. arranged on a auramine is easily sensed by a “Xerox” type of copy Supporting web. the is white13. one kind being reactant materials.S. from 1 to 10–4 to 1 on a weight basis. at least one kind being colored by acid-base 55 12. yield a liquid-solution color that will penetrate a porous : 4. the proportion of the polymeric material to the of permanence by an oxidation-reduction reaction. Primary Examiner kaolin clay in intimate juxtaposition in distribution and U. On the other hand. the end purpose may be to pro 25 ingfiber. The record member of claim 5 in which the web a continuous film of polymeric material. only such quantitative amounts should colored by acid-base reaction with the polymeric material be used that will insure reaction with the ink and integrity and the other kind being colored by oxidation-reduction of the paper web. fiber. the application from 1 to 10–4 to 1 on a weight basis.is The record member of claim 5 in which the min paper-coating clay.455. The reaction with the polymeric material and the other kind is kaolin. bentonite clay. 2. one kind being colored by an a non-adsorbent polymeric material of oil-soluble char acid-base reaction with the polymeric material. 3. a multitude of microfine particles of machine as well as visually. such being determined empirically by reaction brought about after contact with the clay. No references cited.A torecord 1 to 10. to one to three of the mixture to weight of the In any of the Systems. amount to form a visually continuous recording area. member sensitized to receive and to con Sensed by a “Xerox” type of copy machine. inwater-insoluble material of two kinds arranged on a web with a coating of two pounds dry solids per ream of 35 close intermingled juxtaposition to provide a visually paper 25 by 38 inches. 1. by weight. better results than have been ob continuous record surface area. distribution and amount to form a visually continuous is 10. and the inks containing the proper chromogenic the other kind being non-oil-soluble acid clay-like mineral. ticles of sensitizing material distributed therein to form The term “acid” used herein in any sense includes a recording area. a material selected from the group consisting of kaolin 10 some use of them is tolerable and even desirable.R. should be less wet. and the acteristics. A paper sheet having a mixture of microfine par support web such as paper. the the paper maker. to supply minerals relatively low in surface other kind being colored by an oxidation-reduction re activity to assist in developing color in the component action. 1. The present invention has made it possible to produce. - coated on One surface may be coated on the rear surface 6. of the mixture to to any specialized definition. N-benzoyl vert to a colored state oily solutions of colorless chro mogenic material applied to it. as there ordinarily will be no drying 3. In filling paper furnish with these least two kinds of chromogenic materials. multitude of microfine solid particles of both an oil Although the best practice of the invention has been Soluble acid-reactant organic polymeric material and pointed out in the use of non-surface-active minerals. and attapulgite clay in intimate main point of achievement being to reduce the solid juxtaposition in distribution and amount to form a visual mineral requirements of the system to save coating weight. soluble acid-reactant organic polymeric material and a 9. sheet. one kind be duce visually-Sensed marks or electro-optically-sensed of acid-reacting oil-soluble polymeric material and marks. 45 7. A record member carrying on a recording surface a 60 multitude of microfine solid particles of both an oil soluble acid-reactant organic polymeric material and MURRAY KATZ. one kind of particles be tained by coatings of five pounds of dry solids when sur ing of oil-soluble polymeric material having free acid face-active minerals such as attapulgite were used in groups for taking part in acid-base reactions. ly continuous recording area. consisting of two kinds of particles. for developing color in to supplant the adsorptive surface-active minerals of normally colorless oil solutions of chromogenic mate known colorless recording systems in substantial part by 15 rials of at least two kinds. materials. A record member carrying on a recording surface a of the coating by absorption. A record member carrying in a recording area a 8. including. whereas it is 30 Strongly sensed visually. X. This outstanding improvement is of enor other kind of particles being of a mineral structure having mous economic savings and is only one of the benefits 40 Lewis acid properties the proportion of the polymeric material to the mineral being from 1 to 10–4 to 1 on a provided by the invention. materials must be used for the end in view. The record member of claim 6 in which the web What is claimed is: is paper. for 65 117–155 developing color in normally colorless oil solutions of at . The record member of claim 5 in which the par with pressure-transfer material for use against an under ticles on the web extend interiorly thereof. The record member of claim 12 in which the clay proportion of the polymeric material to the mineral being kaolin. and being provided in an amount of Lewis acids in general and is not restricted in any sense from one to forty parts. Cl. and to clay being from 1 to 10–4 to 1 on a weight basis. proportion of the polymeric material to the clay being For coating non-fibrous web material. For instance. recording area. record member of claim 11 in which the clay being colored by oxidation-reduction reaction brought about after contact with the colorless acid mineral. the ratio of polymeric material to mineral ranging from the colored form of Crystal Violet Lactone is not easily 4 to5. The novel record material in that species which is weight basis. the clay. for developing color in normally color less oil solutions of at least two kinds of chromogenic eral11. and the predominance.721 10 9 to coatings for paper. The record member of claim 5 in which the web colorless acid type of mineral in intimate juxtaposition in is porous to oily inks.

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