US2646367A - Transfer paper - Google Patents

Description

inn

vided state.

I Patented July 21,1953

assignors to h m lI'Cash-Register Com- Dayton, Ohio, a corporation of Maryland j No Drawing. Application'June 28, 1951',

. Serial No. 234,161

This invention relates to a manifold sheet, and more particularly pertains to one having a transfer coating that is hydrophobic and which contains a colorless recording oil which carries a colorless color-reactant material. The oil is carried in a low polar wax binder. The sheet is for use on specially sensitized paper usedas an under sheet and the recording oil is transferred to the under sheet in printing-and writing operations in a manner similar to the way in which'transfer of coloring material is made from a carbon transfer sheet, the only color producing material being the color reactant carried in the oil. In making carbon transfer sheets which have'a wax coating containing a colored dye or pigment, oil is sometimes used with the wax to-plasticize it so that it will transfer better, but the oil plays no part in causing the colored mark, such being made by the colored Wax. The fact that the wax, oil, and

color-reactant carried by the oil, are all hydrol phobic, renders the transfer sheet immune to the effects of humidity. The color reactants are so chosen as to need no moisture for the creation of color on the underlying sheet.

2 Claims. (o1.117 ss) sheet onto 'an'under sheet, except that in the sheet of this invention the wax is colorless and plays no part in causing a mark on the under .actant. ;the oil are aromatic double-bond organic comment acts as an electron'acceptor with reference to the color reactant material carried by the oil, and is an adsorbent with respect to such color re- 1 The color reactant materials carried by pounds, normally colorless, which upon adsorption on the pigment are converted to a more highly polarized conjugated form, accompanied by the appearance of color. This color reaction phe- I ;nomenon is also fully set forth in the patent to which reference has been made. Examples of the l organic color reactant will be given in the description to follow. 'Several of the most. important features of the novel transfer sheet are that itmay be handled Without discoloring the hands. It may be rubbed ontoan unsensitized surface without leaving a mark. It is immune to humidity and it has a clean colorless appearance which is strikingly different from ordinary carbonmanifold transfer sheets heretofore known. The marks made on the sensitized under sheet requiring the presence,..

' in adsorption contact, of theacid-like pigment;

The sensitized under sheet with which the 7 novel manifold sheet is intended to be used is sensitized by particles of acid-like, inorganic ma- 1 terial, also colorless or nearly so in the finely di- Typical of such sensitizing pigments are ,attapulgite; sodium ,zeolitematerial; sodium zeolite material in which the natural sodium. exchange ions have been replaced by the ions of hydrogen, nickel, copper, iron, zinc, iner- V cury, barium, lead; cadmium, and potasfsiumf halloysitej and magnesium trisilicate'. These 7 pigments in finely divided form, either singly or mixed, may be applied to the paper in a suitable paper coating binder material, such as paper coating starch, casein, or latex, the proportion of pigment to binder material being such that a large proportion of the surface area-of the. pig; .ment particles'is exposed for contact byvthe re cording oiltransferred thereto by the novel mania fold sheet. The pigment materials mentioned are practically colorless and'give the same effect and adhere to the paper as does ordinary paper coating clay; Thesensitized receivingsheet is more fully described in United States Patent 2,548,364, which issuedf on the application of 7 Green and'Sandberg. The color reactioninwhichthefoilecarried color-reactant takes part is a socalled adsorption color: reactionin whichtheypigk for the appearance of color, will not come off onto the. hands of a person who makes contact with the colored marks, any oil thatis unused when rubbed off from the under sheet being colorless, andany of the reactant color-reactant material which may be desorbed from the receiving sheet losing its color and reverting to the original cola orlessstate. It willbe seen, therefore, that there are'uses for the novel manifold sheet in which these characteristics are of great value a's, for instance, inthe fieldof sales books, in which a duplicate copy of 'asales entry is made on the underlying sheet by means of amanifold transfer coating. The manifold sheet which constitutes the original entrywill have on its back the transfer coating, but it is colorless, will not be rubbed off by wet hands and may be safely placed with white merchandise without smudging such, Moreover, the copy on which the, marks were made by the transfer coating may be safely placed with such white merchandise without discoloring it because, as has been said, the wax which may he accidentally rubbed off is colorless, or nearly so, and contains no colored material, all the color in the mark being in the color reactant which is absorbed and attache'dto the'pigment particles I which are found upon the receiving sheet. Again,

inthisrespect, this manifold sheet differs from carbon paper in that the marks made by-carbon paper may rub off the receiving sheet with the wax, carrying with it the coloring material,

- mud in w at rem mes in .wni q e ewith...

hydrophyllic colloid film in which were dispersed discrete fluid inclusions of an oil which. contained either a coloring material in the colored form or a color-reactant. of the useful color-reactant materials, the compound tetra-methyl-diaminodiphenyl-phthalide,

which is commonly known as malachite green lactone, having the molecular formula 3,3 bis (p-dimethylaminophenyl) phthalide. That com.- pound is also useful in the transfer coating of this invention, but it is carried in a Wax binder and not in the form of liquid droplets in a hydrophyllic binder, the wax being hydrophobic. Neither should the transfer coating or film. of this invention be confused with the transfer coating set out in United States Patents 2,550, l66 to 2,550,473 inclusive, which disclose a rupturable film containing droplets, the film being of a hydrophyllic nature. In the patents to which reference was made, and which disclose a transfer coating consisting of a rupturable hydropliyllic film containing droplets, the transfer coating was made by deposition on paper of an emulsion having an external phase which is dryable to form the rupturable film and an oil internal phase, carrying the color, which remains in the dry film as droplets. The external phase is a solution of hydrophyllic colloid material in water and the coating dries to a film by evaporation of the water. In the manifold sheet of this invention the transfer film is applied as a hot melt coating which solidifies by cooling, and the oil is not contained in droplets but is combined with the wax as an intimate mixture of two hydrophobic materials.

The hydrophobic wax must be chosen so as not to have a tendency to coat over the active surfaces of the pigment particles, and the wax must hold a high content of the recording oil. Moreover, the wax must be of low polarity so as not to interfere with the color reactant, and it must be resistant to smudging action when resting on an underlying receiving sheet under moderate pressure. It will be appreciated that in marking and printing operations, the pressure per unit area is many times that which is obtained by mere stacking of the papers together. Another obstacle to be overcome is that the sensitizing materials on the underlying sheets are selected because of their adsorbent nature and hence they tend to draw out the oil from the transfer film in contact therewith and such film must be highly resistant to such adsorbent effect.

Therefore, it is an object of this invention to provide a manifold sheet having a transfer film including oil intimately mixed with a wax binder, said oil containing a colorless adsorbate colorreactant, for use on record material with a highly adsorbent" pigment which causes the ab'sorbate to assume adistinctive color when in adsorption contact therewith.

Another object of the invention is to provide such a manifold sheet'in which the film mate- That patent indicated as one:

rials, including the wax, oil and color-reactant, are all hydrophobic materials.

A still further object of the invention is to provide such a system in which, by the addition of inert particle material thereto, the resistance of the transfer film to smudging is increased.

With these and incidental objects in view, the invention includes certain novel features and combinations of ingredients, a preferred form or embodiment of which is hereinafter described in detail.

General description In the preferred embodiment of the invention,

about 55%, by weight, of colorless oil containing the hydrophobic color-reactant is mixed with 45%, by weight, of wax. The percentage of oil with respect to the wax may vary from 25%, by weight, to by weight. The colorless oil with reactant is made up of 94%, by weight, of petroleum lubricating oil of a 200 seconds Saybolt viscosity, and 6%, by weight, of the color reactant which is made up of one-half crystal violet lactone and. one-half benzoyl leuco methylene blue. The crystal violet lactone is 3,3 bis (p-dimethylaminophenyl fi-dimethyl-amino phthalide, and

may be made by the method disclosed in United States Patent Re. 23,024, which issued on the application of Clyde S. Adams. tone has the following structure:

N(CH3):

The benzoyl leuco methylene blue has the following structure:

cane wax, another 4/9 being fully refined parainn wax, and 1/9 being lvlontan wax. The wax is heated until it is melted to a consistency where it can be readily stirred and the oil, with the color reactant therein, is added and the mixture thoroughly stirred until the ingredients are homogeneously integrated. This mixture, While still in the melted condition, is applied as a coating on paper in the same manner as wax-base carbon paper coatings are applied, and to a comparable Crystal Violet Lac- 36 x48" being sufficient; although'm'ore or'less" I may be applied, ;This;-coating ;is discernible on the paper, not b'y its color; but by the textureof the surface and its light reflecting qualities.

In a second embodiment- 0f thein'vention "58%, by weight, ofthe colorless recording )il,-i's ;used

with 22%, by weight, of Ouricurywax'and20%1 'of fully refinedparaifih wax, and this is used in the same manner as the mixture of the preferred embodiment. I

In the third embodiment of the invention 55 by weight, of the colorless recording oil -ism'ixed with 45%, by weight, ofgCarnauba wax;

In a fourth embodiment of the invention. 60%, by weight, of the colorless recording oil isused with25%, by weight, of Ouricury-wax and 15.%', by Weight, of montan wax. 'In this embodiment, the colorless oil is 75%,"b3i'vi7e'ight, of thesiamje kind of petroleum lubricating oil mentioned in the preferred embodiment, and 25%, by weight,

I 6 I I and which turns from a normally colorless 'state': to dark blue on the sensitized record material.

"(0') "Malachite green lactone, which is 3,3 bis- (p-dimethylam'inophenyl) 'pnth'alide', having thestructure of chlorinated diphenyl of a chlorine content of 65%. The color reactants maybe .used in the same amount as described for the preferred embodiment. The resinous character of the chlorinated diphenyl helps prevent smudge. I

The wax may be modified by use of other resinous material than chlorinated diphenyl to increase smudge resistance, coumarone indene being suitable.

In a fifth embodiment, 50%, by weight, of the colorless recording oil of the preferred embodiment is mixed with by weight of montan wax, and 25%, by weight, of fully refined parafiin wax.

In all of the above embodiments, inert fillers to the extent of 5% to 15%, by weight, of the coating may be incorporated into the mixture to decrease the possibility of smudge when in stor agecontact with the sensitized paper with which it is to be used. Mineral fillers, such as titanium dioxide, calcium carbonate, and barium sulphate,

are satisfactory, but hydrophobic carbethoxylated starch derivatives such as sold by the National Starch Company, under the'name of Dryfio, have been found to be of exceptional merit. I

Following are some hydrophobic color-reactants, among the many available, which may be used alone or substituted for the crystal violet lactone with the benzoyl leuco methylene blue, which have been previously specified: g (a) Xanthene-Qp-benzoic acid, 3,6-bis-diethylamino 9 p-nitroanilino lactam, having the structure I f \ITTONO:

and which turns from a normallycolorless. state to red on the sensitized record material.

(b) Michlers hydrol, which is, bis(p-dimethylaminophenyl) methanol, having the structure Fahrenheit, and fatty-acid amides.

I I having the structure I which 'chang'es from its normally colorless state to green-onsensitimd paper. p I

(103,3 bis(p diethylaminophenyl) phthalide;

(mnemmoire which changes from its normally colorless state to blue-green on'sensitized paper.

(e) 3,3 bis(p-di-n propylaminophenyl) phthalide,v having the structure which changes from its normally colorless state to deep green on sensitized paper.

As substitutes for the petroleum oil mentioned are the'chlorinated or alkylated diphenyls havsistance required.

It will be evident from the foregoing that the novel manifold sheet may be made from many substances, and that the invention does not reside with the particular oils, waxes, and color reactants used,except for their characteristics of miscibility, hydrophobic nature, lack of color, and consistency for' use as transfer materials useful in printing and Writing.

While the embodiments of the'invention herein described are admirably adapted to fulfill the objects primarily stated, it is to be understood that it is not intended to confine the invention to the particular ingredients or embodiments herein disclosed, for the invention is susceptible of embodiment in various other forms.

What is claimed is:

1. A manifold sheet for use in conjunction with a copy-receiving sheet sensitized on the copy-receiving surface thereof with particles of inorganic clay-like material, said particles having acid-like adsorbent surfaces, including a base web; and a film on said web of a substantially colorless hydrophobic low polarity wax having mixed therein a substantially colorless atmospherically stable hydrophobic oil containing a substantially colorless hydrophobic double bond aromatic atmospherically stable adsorbate compound, which organic compound is converted to a more highly polar conjugated form accompanied by the appearance of a distinctive color therein when adsorbed on particles of inorganic clay-like ma- 8 terial which acts as an electron acceptor with respect to .said organic compound on adsorption contact therewith, and the oil and adsorbate compound being to of the total weight of the film.

2. The sheet of claim 1 in which there is incorporated, with-the wax, oil and color reactant, a hydrophobic finely divided filler material.

CHESTER DAVIS.

NED A. THACKER.

References Cited in the file of this patent UNITED STATES PATENTS Number Name 0 Date 2,040,075 Brower May 12,1936 2,503,680 Newman Apr. 11, 1950 2,548,366 Green Apr. 10, 1951 2,554,909 Holik May 29, 1951

Claims (1)

1. A MANIFOLD SHEET FOR USE IN CONJUNCTION WITH A COPY-RECEIVING SHEET SENSITIZED ON THE COPY-RECEIVING SURFACE THEREOF WITH PARTICLES OF INORGANIC CLAY-LIKE MATERIAL, SAID PARTICLES HAVING ACID-LIKE ADSORBENT SURFACES, INCLUDING A BASE WEB; AND A FILM ON SAID WEB OF A SUBSTANTIALLY COLORLESS HYDROPHOBIC LOW POLARITY WAX HAVING MIXED THEREIN A SUBSTANTIALLY COLORLESS ATMOSPHERICALLY STABLE HYDROPHOBIC OIL CONTAINING SUBSTANTIALLY COLORLESS HYDROPHOBIC DOUBLE BOND AROMATIC AT-LY MOSPHERICALLY STABLE ADSORBATE COMPOUND, WHICH ORGANIC COMPOUND IS CONVERTED TO A MORE HIGHLY POLAR CONJUGATED FORM ACCOMPANIED BY THE APPEARANCE OF A DISTINCTIVE COLOR THEREIN WHEN ADSORBED ON PARTICLES OF INORGANIC CLAY-LIKE MATERIAL WHICH ACTS AS AN ELECTRON ACCEPTOR WITH RESPECT TO SAID ORGANIC COMPOUND ON ADSORPTION CONTACT THEREWITH, AND THE OIL AND ADSORBATE COMPOUND BEING 25% TO 75% OF THE TOTAL WEIGHT OF THE FILM.