CA1219444A - Carbonless paper copying system - Google Patents

Abstract

ABSTRACT

A color developing CF sheet for pressure-sensitive recording systems comprising an admixture of an alkylide-nediphenol and calcium carbonate having a weight ratio of about 4 parts to about 12 parts phenol per 100 parts cal-cium carbonate. The admixture is formulated in high solids content coating colors having excellent rheolog-ical property and stability, which are used to produce CF
sheets having a coating weight of about 4 to about 10 g/m2. Preferably, the CF sheet comprises Bisphenol A in an amount of 4 to 10 parts per 100 parts calcium carbo-nate and the calcium carbonate weight % in the CF coating is greater than 50%. Other embodiments comprise an aqueous dispersion of the admixture and a pressure-sensi-tive recording manifold.

Description

CARBONLESS PAPER COPYING SYSTEM

FIELD OF THE INVENTION
The invention relates to color developers used to develop images in pressure-sensitive carbonless paper recording systems. More specifically, the invention relates to a color developer sheet for carbonless paper comprising an admixture of calcium carbonate and a bis-phenol and a carbonless paper manifold comprising such a color developer sheet.

BACKGROUND OF THE INVENTION
Pressure-sensitive carbonless paper recording sys-tems have evolved into a very large market, chiefly due to their convenience compared with carbon paper copying.
A review of the state of the carbonless paper art is Petitpierre, " DYES AND CHEMICALS FOR CARBONLESS COPYING
PAPER: HISTORY, PRESENT SITUATION, PROBLEMS AND TRENDS 11, 1983 Coating Conference, TAPPI PROCEEDINGS, p. 157-165.
As described therein, carbonless paper involves a manifold comprising a matched pair of paper sheets termed a donating paper and a receiving paper. When written upon, the donor paper is pressed into contact with the receiver paper, and an image substantially identical to the writing develops on the receiver paper.
This image development is brought about by the con-tact of a colorless dye precursor or color former con-tained on the donor paper with a color developer con-tained on the receiver paper. Generally, a solution of the color former in a solvent is encapsulated in micro-capsules and coated on the back side (CB) of the donor paper, which has an uncoated front or top side. The 94~
z color formers, often termed "leuco dyes", are, for example, triphenyl methanes (such as Crystal Violet Lac-tone), xanthenes (such as N-102 flouran), and thiazines (such as Benzoyl Leuco Methylene Blue). The color devel-oper is generally coated on the front side (CF) of thereceiving paper. When the CB and CF sheets are placed in contiguous relationship and pressure, such as from a writing instrument or typewriter, is applied, the microcapsules are crushed. The released color former solution is then adsorbed onto the CF sheet, where it contacts the color developer. The image on the CF sheet develops from a chemical transformation of the color former to a colored form caused by the color developer.
In general, this chemical transformation entails an acid-base type reaction wherein the color former changes from an uncharged, colorless state to a positive charqed, colored state.
Alternatively, the color former/microcapsules and color developer can be coated onto the same paper sheet or the developer can be on the CB sheet and the color former/microcapsules can be on the CF sheet. For conve-nience hereafter, "CB sheet" refers to a paper sheet coated with the color former solution in microcapsules, and "CF sheet" refers to a paper sheet coated with a color developer. In addition, the manifold assembly of paired CB and CF sheets can include more than one pair of sheets.
Currently, two types of color developers are in wide use. Phenolic resins are polymeric long-chain compounds, which are generally of high molecular weight resulting from the polymerization of formaldehyde and a biphenol compound. Their use has several drawbacks, however. For examplep they must be subjected to a long and complicated milling process to produce a resin of a specific particle size suitable for use in carbonless paper. In addition, the resins can decompose, releasing toxic formaldehyde.
Next, the resins give a yellowish background to the CF

~ 2 ~ ~3~ ~ ~

sheet resulting in a higher image background for the writing image, which is accordingly of lower quality.
Finally, the phenolic resins do not develop high image densities because the resins are of limited solubility in the color former solution again resulting in low image quality.
A second type of color developer is an acid-treated clay which has its own drawbacks. First, preparation of the clay requires careful treatment with a strony mineral acid because the color developing activity of an acid clay depends on the extent of hydrogen ion exchange into the clay to form color developing sites on the clay sur-face. In addition, a highly porous clay surface is necessary to ensure a good quality image which requires sufficient contact between the color former solution and the color developing sites on the clay surface. This problem of contact between the color former and acid clay is similar to the limited solubility of phenolic resins in the color former solution. Hence, image quality is highly sensitive to the chemistry and morphology of an acid clay, yet these parameters are very difficult to control.
In addition, CF sheets are prepared by coatin~ a slurry of the color developer and an adhesive onto paper and letting the coating dry. The coating slurry is known in the art as a coating color. High solids concentra-tions, which includes solids content of the developer and the adhesive, in the coating color are desirable for yood image quality, but concentrations above 45-50 weight %
are generally unattainable with phenolic resins or acid clays due to the poor rheology, caused by high viscosity, of coating colors containing them.
Biphenolic compounds, which have not been polymer-ized like the phenolic resins, have been disclosed as color developers for certain lactone-type color formers in U.S. 3,244,550, "Manifold Sheets Coated with Lactone and Related Chromogenous Compounds and Reactive Phenolics and Method of Making", Farnham et al., issued April 5, 1966. ~arnham also discloses that "neutral or inert"
pigments serve to make the coating containing the color developer whiter and more opaque. The pigments disclosed are titanium dioxide, zinc oxide, zinc sulfide or zirco-nium dioxide, which are all known as "hiding pigments" in the coating art~ and have high refractive indexes of 2.0 to 2.7. Farnham does not disclose a non-hiding pigment such as calcium carbonate which has a refractive index of about 1.5. Next, Farnham uses an amount of pigment of about 1/10 of the coatlng weight on a dry basis. Farnham states the pigment has "no noticeable effect" on image development. Farnham also uses a large amount, at least 10 weight %, of the biphenol in the CF coating, and in the only operative example, the amount of phenol is 35 parts and the amount of pigment is 4 parts in a 100 part coating color.
U.S. 3,450,553, "Pressure Sensitive Record Material", Billet et al., issued June 17, 1969, discloses lignin as the color former in carbonless paper, and two specific phenols, phloroglucinol and 3-hydroxy phenyl urea, as color developers for lignin.
U.S. 4,349,21~, "Copying Material Employing Flouran Color Formers", Garner, issued September 14, 1982, also discloses phenolic color developers for flourans, such as 4-t-butylphenol, 4-phenylphenol, 2,2'-dihydroxydiphenyl, 4,4'-isopropylidenediphenol (Bisphenol A), and 4,4'-isopropyliden-bis-(2-methyl-phenol). Garner does not disclose a phenol admixed with a pigment such as cal-cium carbonate.
Gr. Britain Patent No. 1,356,402, "Colour Develop~rSheet for Pressure Sensitive Recording", issued June 12, 1974 discloses a color developer of "one or more clays capable of acting as color developers" and at least one monomeric phenolic compound. The amount of phenolic com-pound is about 1 to 10 parts by weight per 100 parts o clay. The clays listed are "attapulgite, acid clay, ~5--active clay, zeolite and bentonite." These clays are either the acid treated clays discussed above or certain smectite clays which are known as active color developers without acid treatment.
U. S. 4,046,941, "Support Sheet with Sensitized Coating of Organic Acid Substance and Organic High Molec-ular Compound Particulate Mixture", Saito, issued Sep-tember 6, 1977, discloses a two component color developer mixture of an aromatic carboxylic acid or its metal salt with an organic high molecular compound. The aromatic carboxylic acids disclosed include certain hydroxy car-boxylic acids such as salicylic acid. The organic high molecular compound has a molecular weight above 400, such as polybutadiene, and must be compatible, i.e., miscible, with the aromatic acid. The amount of high molecular compound must also be enough to give the composition the desired resistance to heat, light and moisture~ In one aspect, the mixture is adsorbed around an inorganic powder such as clay or calcium carbonate. Although Saito does disclose an admixture of CaC03 and color developer, Saito's color developer must contain both the carboxylic acid compound and the high molecular compound. Moreover, the high molecular compound in the color developer pre-sents the same drawbacks as phenolic resins.
U. S. Patent 4,416,471, "Color-Developing Sheet for Pressure Sensitive Recording Sheet," Yamato, issued November 22, 1983, discloses a color developing sheet with a layer of an organic color developer, calcium car-bonate and a specific binder, an acrylamide modified polyvinyl alcohol, in an amount of 5-25 weight % to glue the developer and pigment on the sheet. This specific polyvinyl alcohol is critical to Yamato since he dis-closes that fine particle size calcium carbonate in a coating creates numerous gaps between particles which act as capillaries to adsorb the color former solution, and that this binder does not mask the gaps. Yamato dis-closes the organic color developer are phenolic resins or their metal salts, or organic acid substances such as a "metal salt of 2,2-bisphenol sulfone." Yamato does not disclose that his color developing sheet can be produced using a coating color of hi~h solids content.
U.S. 4,480,260, "Color-Developing Sheet for Pres-sure-Sensitive Recording Sheets", Yamato, issued October 30, 1984, discloses a color developing layer for a CF
sheet consisting of zinc carbonate, thiourea, a bisphenol compound and an acid clay. ~amato also discloses that an inorganic pigment such as calcium carbonate can be added to the CF sheet~ Yamato discloses, however, that the CF
sheet is specifically formulated to permit activation of a single black forming flouran color former by an acid clay, so the bisphenol is not the primary color devel-oper. Yamato also does not disclose the specific combi-nation of calcium carbonate with bisphenol, nor a weight ratio of bisphenol to calcium carbonate.
Although not directed to color developers, U.S. 3,894,168, "Paper Coating Pigment Material, Brockett, issued July 8, 1975, discloses a treated pig-ment color former. Brockett adsorbs a color former such as Crystal Violet Lactone on a pigment such as calcium carbonate to produce a coated pigment particle. However, the Brockett color former is unprotected from being con-verted to a colored form by, for example, air, the oil from human skin, or the other components in a paper coating.
What is needed is a low-cost, carbonless paper mani-fold which is capable of developing high quality images.
It is an object of Applicants' invention to provide such a manifold comprising a CF sheet coated with calcium car-bonate. Another object is to use a CF sheet wherein the primary color developer comprises a bisphenol instead of a phenolic resin or acid clay~ Another object is to pro-vide a manifold having a CB sheet comprising a solventsuitable for use with a bisphenol color developer. Other objects appear below.

~2~
-7~

SUMMARY OF THE_INVENTION
The invention comprises a CF sheet useful in pres-sure sensitive recording systems wherein the components substantially responsible for color development activity comprise an admixture of calcium carbonate with a monom-eric bisphenol color developer having the general for-mula: R
(HO)~ C~(OH) Rz wherein N is 1, 2, 3, 4, or 5, Rl and R~ are the same or different and are H, alkyl, substituted alkyl, amino, or substituted amino. Preferably the ratio of bisphenol to calcium carbonate i5 about 4 to about 14 parts per 100 parts by weight calcium carbonate. The CF sheet is an - effective color developer for any CB sheet color former converted to a colored form by an acid-base type reac-tion. The invention further comprises a carbonl~ss paper manifold consistin~ of the CF sheet paired with a CB
sheet containing a solvent specifically suited for use with the bisphenol CaCO3 CF sheet.
Manifolds of the invention comprising ~he composi-tion develop high quality images with good image density.
In addition, the color developing admixture can be formu-lated in a high solids content coating color which results in faster coating and drying, thereby enhancing the paper quality and throughput~
DETAILED DESCRIPTION OF THE INVENTION
The invention comprises a color developing composi-tion comprising a monomeric phenol color developer com-pound adsorbed onto or admixed with an alkaline earth carbonate such as calcium carbonate. The monomeric phenol has the general formula sho~n a~ove and is herein termed a bisphenol. The r~lative amounts by weight of bisphenol and CaCO3 used are about 4 to about 14 parts ~8--bisphenol per 100 parts of CaCO3. The composition of the invention can be made by adsorbing the phenol onto CaCO3 or admixing the phenol and CaCO3. As used herein, the term "admixed with" or "admixture" refers to either an adsorbed composition or an admixed composition of bis-phenol and CaCO3~
A color developer dispersion comprising an aqueous dispersion of the pigment and bisphenol admixture which is used to make the CF coating color comprises one embod-iment of the invention. In another embodiment, the ` invention comprises a coating color comprising the phenol/CaCO3 admixture. In another embodiment, the invention comprises a CF sheet coated with the color developing composition. Another embodiment comprises a carbonless paper manifold assembly using a CF sheetcoated with the composition. The CB sheet used in such a manifold preferably comprises a leuco dye color former dissolved in a solvent comprising an organic material in which a bisphenol of the invention has a solubility of at least about 1 gram/cubic centimeter. Other embodiments comprise methods for making the color developing composi-tion, all of which employ a separate admixture step of mixing the monomeric bisphenol and calcium carbonate before formulating the coating color.
As seen in the Examples, the bisphenol/calcium car-bonate admixture of the invention when used in a CF sheet surprisingly and synergistically improves the quality of the image developed. Without wishing to be bound by theory, Applicants consider that the synergistic increase from admixtures of CaCO3 and a bisphenol of Formula I is due to enhanced polarization of the bisphenol caused by the CaCO3 when the color former solution contacts the CF
sheet, thereby rendering the bisphenol more acidic and thus the CF sheet more active.
~n important advantage of the invention is that the phenol and calcium carbonate admixture can be used in a CF coating color having good rheological properties and a _9_ solids content of about 50 to about 75 weight %, and preferably about 55 to about 65 weight %. This solids content includes the phenol, the CaCO3, and the binder solids. Such high solids content has not been used in carbonless paper coating colors, improves paper quality, and speeds up coating, drying and production at lower cost, since equipment utilization is increased~ Another advantage of the invention is that the phenol is evenly admixed with the pigment so that an even distribution of the color developer on the CF paper results. Yet another advantage is that the monomeric bisphenol can be a low cost phenol such as Bisphenol A. A further advantage is that calcium carbonate is readily-available at low cost - and is an established paper filler. CaCO3 also prevents yellowing of the CF sheets. Another significant advan-tage is that the color developer composition can be for-mulated as a stable aqueous dispersion which can thus be transported easily from a pigment mine site to a paper mill.
The calcium carbonate used in the invention in gen-eral is finely milled and is preferably white or color-less to enhance the contras~ of the image developed on the receiving paper. Colored or dyed CaCO3 can be used, but since their use can reduce image contrast due to dis-play against a colored pigment background, the color former used with dyed CaCO3 must be carefully chosen.
Any form of calcium carbonate, such as precipitated cal-cium carbonate or aragonite, can be used. The advantages of calcium carbonate in the invention comprise making the coated paper basic, thereby prolonging khe paper's shelf life. In addition, calcium carbonate has a bright white color and hence increases image contrast. ~inally and most important, as seen in the examples, CaCO3 has a syn-ergistic improvement on image density when used with a bisphenol of the above formula.
The particle size of the CaCO3 can be of any distri-bution, but preferably corresponds to the particle sizes ~Z~4~

of piyments conventionally used in paper coating colors.
For the CF sheets the CaC03 is preferably substantially all smaller than 4~m because the CF coating should be less than S~m thick. Thi~ 4~m top size is preferred because coarser sizes can cause an uneven coating surface on the CF sheet or cause "blue streaks" after paired with CB sheets by premature rupture of the CB microcapsules.
The amounts of the CaC03 used in the composition are dis-cussed below in conjunction with the method of making the composition. Finally, the CaC03 does not re~uire any special pretreatment such as, for example, to improve porosity, other than size reduction of the raw pigment.
The monomeric bisphenols admixed with CaC03 are Lewis acids which function by accepting/extracting an electron from the color former thereby chemically con-verting the color former into a highly-colored ionic form. As is developed below, bisphenols of the following Formula I admixed with CaC03 have good reactivity with color formers and show synergistic improvement in image density.
The monomeric bisphenols used have the general for-mula: R
( H ) ~ C ~ ~( H) Formula I
Formul~ I indicates that the phenolic OH groups can be located at any of the free positions, 2-6 and 2'-6' counting from the shared carbon atom (C in Formula I) between the benzene rings. N i ls 2, 3, 4, or 5 and indicates at least one OH group is on each benzene ring.
Bisphenols containing a total of at least two OH groups are used because phenols containing a single OH groups are not sufficiently reactive to develop good density when used with CaC03 in CF sheets. Particularly pre-ferred are bisphenols with only one OH moiety on eachbenzene ring located at the 4 and 4' (para or para') positions to the shared carbon atom, because this type of bisphenol develops high optical densities. Rl and R2 in Formula I can be the same or different and can be hydrogen; alkyl, such as -CH2-, -CH2CH3, isopropyl, or longer chain alkyl groups; substituted alkyls; amino; or substituted amino. Hydrogen or alkyl up to C3 are pre-ferred for R1 and R2 because of cost. Although not shown in Formula I, the aromatic rin~s can be substituted by substituents, preferably other than carboxylic acids, such as alkyl, phenyl, halo, nitro, amino, sulfate, sul-fonate, and sulfite, which do not make ineffective the color developing capability of the phenol when mixed with CaCO3. In this regard, some constituents, such as alkyl groups, or those located immediately next to the OH group can reduce the OH's acidity. Halogen substituted bisphe-nols are not preferred because of toxicity and cost prob-lems. Particularly preferred bisphenols are alkylidene-diphenols wherein Rl and R2 are hydrogen or alkyl, suchas 4,4'-methylidenediphenol, 2,4'-methylidenediphenol, 4,4'-secbutylidenediphenol and 4,4'-isopropylidenediphenol (Bisphenol A) The most pre-ferred bisphenol is Bisphenol A ~Rl and R2 ~ methyl, and single OH groups at the para positions in Formula I), because of the high quality carbonless paper image pro-duced by Bisphenol A and CaCO3 and because of its ready availability and lower cost. Bisphenol A is also known as 2,2-bis(p-hydroxyphenyl) propane~
A CF sheet coated on one side with the color devel-oping composition comprises another embodiment of the invention and a copying manifold employing this CF sheet comprises another embodiment. Before describing the CF
sheet in greater detail, the other components of the manifold are discussed.
The manifold preferably comprises at least one CB
sheet uncoated on its front and coated on its back with the microencapsulated color former and at least one CF
sheet coated on its front with the color developing com-position, wherein the CF and CB sheets are always in con-tiguous relationship. Other arrangements of the encapsu-lated color formers and the color developing compositionof the invention, noted above, can be used if desired.
For example, the color developing composition and the microcapsules containing the color former can each be coated onto the same paper sheet. The claims are intended to cover all possible arrangements of the mani-fold. More than a two sheet manifold can also be pro-duced. In this embodiment of the invention, the CF sheet comprising the color developiny composition is coated on its back (CB) with the color former/microcapsules.
Another CF sheet is placed below the CF/CB sheet. The manifold ~hus can be made to contain as many sheets as desirable, but at some point the manifold is too thick to transmit writing pressure to the bottom sheets.
The color formers which are activated ~y the color-developing composition genexally comprise any colorless chromogenic leuco dye which can be used in a carbonless paper manifold, but do not comprise chelating agents which function as color formers by chelation of a metal atom. The color former must be capable of transformation by the color developer of the invention from a colorless form into a colored form. For example, Petitpierre, dis-cussed above, lists several color formers, such as~
Crystal Violet Lactone, described in U.S. Patent No.

2,417,8S7, and flouran N-102, described in U.S. Patent No. 3,681,390. Suitable color formers comprise/ for example, Pyridyl Blue, which is an isomeric mixture of 7-(1-ethyl-2-methylindol-3-yl)-7~(4-diethylamino-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one;
and 5-(l~ethyl-2-methylindol-3-yl)-5-(4-diethylamino-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-7-one;
Benzoyl Leuco Methylene Blue (BLMB), which is 3,7-bis (dimethylamino)-10-benzoyl-phenothiazine; Crystal Violet 4~4 Lactone (CVL), which is 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide; flouran N-102, which is 2'-anilino-6'-diethylamino~3'-methylfluoran Indolyl Red, which is 3,3-bis(l-ethyl-2~methylindol-3-yl)phthalide;

3,3-bis(l-butyl-2-methylindol-3-yl)phthalide; spiro-7-chloro-2,6-dimethyl-3-e~hylaminoxanthene-9,2-(2H)napththol [1,8-bc]furan; 7 chloro-6-methyl-3-diethylaminofluoran; 3-diethylamino-benzo[b]fluoran;
3-(4-diethylamino-2-ethoxy)-3-(2-methyl-1-ethylindol-3-y-1) phthalide; 3-(4-diethylamino-2-butoxy)-3-(2-methyl-l-ethylindol-3-yl)phthalide; and 3,7-bis(diethylamino)-10-ben~oylbenzocazine. Mixtures of color formers can also be used if desirable. A more extensive listing of useful color formers is not believed necessary because useful ones are well known to those skilled in the art.
The color former determines the color of the devel-oped image. For example, Crystal Violet Lactone, Benzoyl Leuco Methylene Blue, and Carbazoyl Blue develop blue images; Bisindoylphthaladide, monoaminoflouran and diami-noflouran develop red images; and flouran 1N-102) develops a green-gray image. A black image develops from a mixture of flouran (N-102), Crystal Violet Lactone, Benzoyl Leuco Methylene Blue, and monoaminoflouran, and this mixture is a preferred color former.
2S As is known in the art, the color former is dis-solved in a solvent system. The weight % of the color former in the solvent solution varies with the particular color former and the fluids making up the solvent system but is generally within about 0.5% to about 10% by weight, preferably about 1% to about 5~.
The solvent system for the color former is an impor-tant factor of the invention and comprises a transfer fluid and optionally a diluent and/or a dye solvent to improve color former solubility in the solvent. To permit microencapsulation, the solvent system is water immiscible and inert towards the encapsulation catalysts and must dissolve a sufficient amount of the color ~z~

former. The solvent is preferably substantially odorless for use in an office environment. The solvent also pre~
ferably has a boiling point within about 160 to about 325 C to produce faster evaporation after breaking of the microcapsules while lessening evaporation through the uncrushed capsules.
Since the image-forming reaction occurs through con-tact between the color former and the developer, the sol-vent must also dissolve the bisphenols of the invention.
Thus the solvent system comprises any organic material in which sufficient amounts of the bisphenol of Formula I
dissolve to react with the color former to produce an image having an image density of above about 0.40 and preferably 0.50 as measured at 500 nm. Applicants there-fore prefer that the solvent has a solubility for thebisphenol of greater than about l.0 gr/lO cc of solvent.
U. S. Patent 4,275,905 lists conventional organic transfer fluids and diluents which can be used. However, Applicants believe the present commercial transfer fluids do not achieve sufficient image density when used with the bisphenol CaCO3 developer.
Transfer fluids believed to have sufficient solu bility for the bisphenols comprise ketones having at least 6 carbon atoms, including alkyl, aromatic and cycloketones, such as 4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone, methyl isoamyl ketone, cyclo-hexanone, di isobutyl ketone, acetophenone, 2-octanone, isophorone, 2-heptanone, 3,3~dimethyl-2 butanone, and 1,3-diphenyl-2-propanone; ethers having at least 4 carbon atoms, including alkyl and aromatic ethers, such as benzyl ether, 2-ethoxy ethyl ether, phenyl ether, 1,2-dimethoxyethane, 2-methoxy ethyl ether; esters having at least 7 carbon atoms such as amyl acetate, benzyl ace-tate, butyl benzyl phthalate, pentyl acetate, 2-ethylhexylacetate, ethyl benzyl acetate~ oxynonyl ace-tate, ethylacetoacetate, propyleneglycolmono-methyl ethe-racetate, butyl octyl phthalate, butyl oleate, dibutyl ~21~
~15-phthalate~ 2-ethyl-hexylacetate, butyl stearate, diisobutyl phthalate, di-isodecyl phthalate, dibutyl maleate, diethyl succinate alkyl benzoates such as methyl benzoate, ethyl benzoate, n-butyl benzoate, 2,2,4-trimethylpentanediol-1,3-monisobutyrate and 2-ethoxy ethyl butyrate; diethyladipate, propylene carbo-nate; alcohols having 4 to 12 carbon atoms, such as n-bu-tanol, n-pentanol, n-hexanol, n-octanol, n-decanol, and benzyl alcohol; and aldehydes such as salicyladehyde.
Applicants prefer esters as the transfer fluid.
Of these solvents, the one selected, when incorpo-rated in a CB sheet and paired with the CF sheet con-taining the CaCO3/bisphenol admixture, at minimum should achieve development of a writing ima~e having an image density of at least about 0.40 and preferably 0.50 mea-sured at 500 nm. on a scale of from 0.0 (white) to 1.0 (jet black). Two preferred solvents meet this criteria and are n-butyl benzoate and 2,2,4-trimethyl pentane-diol-1,3-monoisobutyrate (available as TEXANOL from Mon-santo). Of these two, n-butyl benzoate is more preferred because of faster development speed and because of better color former solubility. A preferred solvent mixture thus comprises 25 to 75 wt.% n-butylbenzoate mixed with odorless mineral spirits.
It is also possible, however, that some transfer fluids can interfere with the polymerization catalyst used in the microcapsule formation. For example, some alcohols can interfere with di-isocyanate derivative catalysts. Thus, the transfer fluid and the type of microcapsules used must be compatible.
The transfer fluids can be used alone or in various mixtures, in mixtures with dye solvent materials having hiyh color former solubility such as isopropyl biphenyl, sec-butylbiphenyl or isopropylnapthylene, and/or in mix-tures with diluents. Diluents include high-boiling straight and branched-chain hydrocarbons. The diluents are used to decrease the cost of the solvent system. A

4~

preferred diluent is a mixture of saturated aliphatic hydrocarbon oils having a distillation temperature of 160C to 260C. Other diluents which can be employed include internal phase solvents known in the art, pro-vided that they are not halogenated, are at least par-tially miscible with the transfer fluid so as to give a single phase in the proportions used, and are not chemi-cally reactive with the transfer fluid, the other compo-nents of the color former solution, or the microcapsule components. The weight ratio of diluent to transfer fluid can be of any value, but in all solvent systems the amount of transfer fluid must be sufficient to dissolve the amount of color former used. To minimize cost the amount of transfer fluid is minimized, and a typical sol-vent system comprises, for example, 4 parts by weightdiluent and one part transfer fluid. The solvent system can also comprise additives to alter or control the final properties of the system such as viscosity control agents, vapor pressure control agents, freezing point depressants, odor masking agents, antioxidants, or colored dyes.
The color former solution is contained in microcap-sules. The microcapsules can be prepared by any method known in the art such as from gelatin as disclosed in U.S. Pat. Nos. 2,800,457 and 3,041,289, from a urea-for-maldehyde resin as disclosed in U.S. Pat. Nos. 3,516,~46, 4,001,14~, 4,087,376 and 4,089,802 or from various mela-mine-formaldehyde resins as disclosed in UOS. Pat.
No. 4,100,103. As known in the art, the microcapsule formulation used depends on the solvent for the color former because certain solvents can diffuse through some types of microcapsule shells. Urea-ormaldehyde polymers are preferred for use with solvents comprising the pre-ferred transfer fluids o the invention.
Any binder or pigment adhesive for the microcapsule coating on the CB sheet and the color dcveloping composi-tion coating on the on the CF sheet can be used. Sui-~z~

table binders comprise water soluble binders such as starch, carboxymethyl cellulose, polyvinyl alcohol, gelatin, gum arabic, or dextrine; latexes such as poly-vinyl acetate, butadiene-styrene copolymer, or polya-crylic, or any mixtures thereof. A preferred binder forthe CF sheet is butadiene-styrene copolymer latex because CF sheets using it as the binder develop higher optical density than sheets with other binders. The amounts of binder are discussed below.
Formulations and techniques for the preparation of the carbonless copy sheets per se are well known in the art, for example, as disclosed in U.S. Pat. Nos.
3,627,581, 3,775,424 and 3,853,869.
The methods of preparing the color developing compo-sition, a CF coating color comprising the composition,and the CF sheet comprising the composition are now described in more detail. It should be noted that the color developing composition is formulated in a liquid slurry or suspension, which can be dried to produce a powdered composition. For purposes herein, the term "color developer dispersion" refers to the liquid slurry or suspension of the color developing composition. The powdered color developing composition can be redispersed to produce the color developer dispersion. The color developer dispersion is used to produce the CF coating color which is eventually coated onto paper and dried to produce the CF sheets comprising the color developer com-position of the invention. The color developer disper-sion is an important aspect of the invention because it can be formulated at a CaC03 mine or production site and then shipped to a paper mill.
Next, as noted above, the color developer composi-tion can be the bisphenol adsorbed onto CaC03 or an admixture of the bisphenol and CaC03. It is preferred to formulate the composition as an admixture because this is an easier formulation than an adsorption process. The methods of making the color developer dispersion con-taining an admixture of bisphenol and CaCO3 are therefore discussed first.
As noted previously, preparation of the color devel-oper dispersion involves mixing the bisphenol and CaCO3, preferably prior to formulation of the coating colorO It is preferred to first formulate the dispersion, instead of direct production of a coating color, since this faci-litates even mixing of the bisphenol and CaCO3.
A first method of making the color developing compo-sition comprises forming an aqueous feed slurry or sus-pension comprising the bisphenol, CaCO3, a dispersant, and a protective colloid, and wet grinding the feed slurry to produce the color developer dispersion com-prising the color developing admixture. A second and preferred method of making the color developer dispersion is to formulate separately an aqueous bisphenol emulsion and a calcium carbonate slurry, and then blending the emulsion and carbonate slurry.
In the first method, the CaCO3 content in the feed slurry is preferably as high as possible to cut grinding cost. Thus, although lesser amounts can be used, CaCO3 preferably comprises within about 50~ to about 85% by weight of the feed slurry, since lesser amounts cause undue wear on the grinding mill and greater amounts agglomerate and prevent grinding A more preferred range is about 70 to 75 weight % CaCO3 since such feed slurries can be processed in one pass through a mill. The disper-sants are conventional solid grinding dispersants, can be any suitable type such as an anionic ammonium polyacry-late, a nonionic polyethylene oxide condensate, or polycarboxylic acid salts, and are added in an amount sufficient to disperse, i. e.; avoid agglomerating, the CaCO3. Such an amount preferably comprises about 5 to about 25 lbs. per ton of pigment.
The amount of bisphenol in the feed slurry comprises any amount sufficient to develop acceptable optical den-sities above about 0.40, and preferably above about 0.50, 4~

and is generally about 2.0 to about 20 weight ~ of the CaCO3. A preferred range is about 4.0 to about 14.0 weight % of the amount of CaCO3 because above this range the minimal increases in image optical density do not offset the increased cost. A more preferred range is about 4.0 to about 8.0 weight % of the CaCO3 since these amounts develop high optical density. These preferred weight ran~es of bisphenol are an advantage of the inven-tion because of decreased cost. For instance, the Farnham patent discussed above shows use of 35 weight percent of a biphenol compound in the coating color.
A protective colloid is added to the feed slurry in an amount effective to prevent flocculation of the bis-phenol, which is about 0.1 to about 1.0 wt. ~ of the CaCO3, more preferably about 0.2 to about 0.~ weight % of the CaCO3. The protective colloid comprises, for example, polyvinyl alcohol or carboxymethylcellulose, prevents poor rheology due to agglomeration of the phenol and pigment, and thus stabilizes the produced dispersion leading to a more uniform CF sheet and better optical density. The colloid does not convert the color former to a colored form in a carbonless paper system. The pro-tective colloid can also be added-to the color developer dispersion after the grinding but is preferably added to the grinding feed slurry because its presence can increase grinding rate.
Polyvinyl alcohol is typically ~repared by hydro-lysis of polyvinyl acetate. Any polyvinyl alcohol polymer can be used, and suitable polyvinyl alcohol polymers are hydrolyzed to an extent from about 85 to about 91 percent, and have molecular weights such that a 4 % solids solutions of the polyvinyl alcohol in water has a viscosity of from about 4 to about 25 centipoises at 25C. Suitable polyvinyl alcohols are available from Air Products and Chemicals, Inc. under the tradename VINOL~, and these are not acrylamide-modified as in the Yamato patent. It should be noted that the polyvinyl alcohol is often used as a coating binder, but in much larger amounts than above.
The aqueous feed slurry comprising the phenol, CaCO3, dispersant and protective colloid can be predis-S persed by mixing for a short period if desired, and atambient temperature is passed through any suitable grinding mill, such as a Netzsch or media mill, or other suitable particle comminution apparatus. In the grinding mill, the color developer compound is admixed with the CaCO3 and all solids are reduced in size to the preferred 4~m top size. Some heating occurs during grinding, gen-erally to less than about 85C, and this heating can cause a portion of the solid phenol to be adsorbed onto CaCO3. The grinding time period varies with the milling device but is generally a time sufficient to reach 4~ top size. Multiple passes can be necessary depending on the mill and the initial size of the CaCO3 and solid bis-phenol used~ To aid the grinding ra~e, the bisphenol can be milled before addition to the feed slurry. The resulting color developer dispersion comprises the color developing composition and is ready for making the CF
coating color.
The second method of making the color developer dis-persion is preferred because the proper size of the bis-phenol and CaCO3 is more readily achieved with it. Inthis method a bisphenol emulsion is mixed with a CaCO3 slurry to make the dispersion. The bisphenol emulsion is made by grinding an aqueous slurry of the bisphenol, dis-persant and protective colloid until the proper size for the bisphenol is reached. To avoid increased dispersant demand, it is preferable to use a high-purity bisphenol starting material. Any suitable dispersant and protec-tive colloid can be used. It is preferred to use Tamol 731~ as the dispersant and a mixture of carboxyme-thyl cellulose and carboxyethyl cellulose as the protective colloids. The amount of bisphenol is an amount, which when mixed with the CaCO3 slurry, will comprise the 4~

preferred ratio of 4 to 12 parts bisphenol per 100 parts CaCO3 In general, this means the bisphenol is about 35-45 wt. % of the bisphenol emulsion. A preferred bis-phenol emulsion formula is 6.856 grams Bisphenol A, 2869 grams of 4~ NATROSOL LR~, 2869 grams 4% CMC 7L~, (carboxy methyl cellulose~, 80 grams Tamol 731~ and 4145 grams water. This results in a 40.76 wt. % Bisphenol A emul-sion.
The bisphenol emulsion is then mixed by blending with a calcium carbonate slurry having the appropriate amount of CaCO3, which in general is in the same range as for the feed slurry discussed above, to produce the color developer dispersion. A preferred CaCO3 slurry is 70-75 wt. % CaCO3 containing 5 to 25 lbs. Colloid 230 per ton CaCO~. Such a slurry is available commercially as ULTRAMITE, from Thompson-Weinman Company. For example, mixing 50 grams of a 74 wt. % CaC03 ULTRAMIT~
slurry with 7.74 grams of the above preferred Bisphenol A
emulsion produced a color developer dispersion having 8 parts BPA per 100 parts CaCO3.
The coating color is produced by adding to the color developer dispersion the adhesive binder and, if desired, additional dispersion agent, an antibacterial agent, an antifoaming agent, and antioxidant to protect the bis-phenol. It is preferred that the amount of adhesive binder added on a dry solids basis is about 5 to about 30 parts per 100 parts of CaCO3 and bisphenol solids, because below 5 parts, the binder is insufficient to affix the CaCO3 and phenol to the paper and above 30 parts interferes with image development~ Preferably, the amount of binder is about 5 to about 15 parts per 100 parts solids, which is an advantageous low binder pigment ratio. Conventional antifoaming agent, such as fatty acid esters, or petroleum distillates, is added in an amount of about 0.1-D 5 parts per 100 parts by weight bisphenol since larger amounts can ause agglomeration.
~e dispersant agent is added as needed if an extender *Trademark ~ z~

pigment such as coating clay is added. The coating color is mixed until uniform to produce the coating color com-prising the color developer composition of the invention.
The coating colors comprising CaCO3 and the solid bisphenol according to the invention preferably have a total solids content (CaCO3, bisphenol, and other solids such as the binder) of abou,t 50 to about 75 weight ~ of the color, although lesser amounts can be used, and more preferably about 55 to about 65 wt. % of the color.
These preferred ranges are based on the desired rheology for coating colorsO The critical feature for coating rheology is that the color must be fluid enough at high shear rates to be coated. Because paper coating machines operate at shear rates about 50,000 sec. 1, color vis-cosity at 10,000 sec. 1 is measured. The coating colors of the invention within the range of 50-75 % total solids showed excellent high shear viscosity well below about 1.5 poise. The examples list some of the test data. The more preferred range of 55 to 65 wt % was chosen because below this range the color can be too thin at high shear rate for proper coating, thus requiring addition of a viscosity builder, and above this range the color can be too thick or pasty at low shear rate, thus leading to mixing and pumping problems. Applicants consider the high solids colors containing the bisphenol and CaCo3 admixture very significant, because the bisphenol does not appear to affect the rheology to any significant degree. The high solids colors are also preferable because they save energy by reducing coating drying time and they increase coating machine throughput.
The wt. ~ of calcium carbonate in the coating color is preferably above about 30 wt. % on a dry solids basis, and more preferably above about 50 wt. %, to ensure good polarization of the bisphenol and thus good image den-sity. In general, use of greater amounts of the bis-phenol permits some decrease in CaCO3. Calcium carbonate above 50 wt. ~ is more preferred since it yields high image density with 5 ~ Bisphenol A.
Supplementary fillers and extenders can be added to the coating color to improve adsorption of the color former solution by the CF sheet. These fillers can be used in an amount up to about 50 weight % of the CaCO3.
Useful fillers include coater kaolin, talc, silica, and the like.
To produce the CF sheets, the coating color is coated onto a support such as plastic or paper sheets and allowed to dry. The paper used can be any desired paper product. Any technique for coating the slurry onto the paper can be used, and such techniques are known in the paper art. For example, roll coating, air-doctor coating, blade coating, or cast coating can all be used.
Blade coaters are particularly preferred for high-solids content coating slurries and thus find particularly desirable use with the coating slurries of the invention.
The paper is dried to evaporate liquid from the coating to yield any suitable coating density which preferably comprises within the range of about 4 to about 10, and more preferably about 6 to about 8, grams per square meter. Coating weights of at least 4 9/m2 are preferable with above 8 wt. % bisphenol, and at least 6 g/m2 are preferable with below 8 wt. ~ bisphenol colors.
The produced CF sheets are paired with CR sheets containing the microencapsulated color former as described above. The carbonless paper manifold of the invention comprising the CF sheet with the color devel-oping composition is then ready for use.
In another less preferred preparation method, the color developing composition is prepared by dissolving the bisphenol in a water miscible, adsorbing solvent to produce a color developer solution which is mixed, such as by spray coating, with the CaCO3. This method is less preferred because of additional solvent costs.
Useful adsorbing solvents include water and lower molecular weight organic solvents of carbon number 5 or ~z~

less such as alcohols, acetates, and ketones. Although it is possible to use water as the adsorbing solvent for the phenol, some phenols are not soluble to an appreci-able extent in water~ therefore necessitating an organic solvent in which adsorption occurs. It is thus preferred to use an organic solvent to dissolve the bisphenol, and isopropyl alcohol is a suitable solvent.
The amount of adsorbing solvent used is generally an amount sufficient to dissolve the desired quantity of phenol, which is the same as that used in the grinding method. The exact amount of solvent also depends on whether a powdered composition is to be prepared. Where the powder is desired, only an amount of solvent suffi-cient to dissolve the bisphenol is added. Where a coatin~ color is to be made after the adsorption directly from the color developer dispersion, the amount of sol-vent is determined by the desired weight percent of solids in the coating color. It is here preferred that the amount of solvent used is in the range of about 5 to about 25 percent, and more preferred about 10 per cent, by weight of the coating slurry. For example, in a coating color comprising 1 gram of the phenol adsorbed onto 14 grams of pigment, 7 grams of binder, and 28 mil-liliters of water, 28 milliliters of isopropyl alcohol are used, which is about 25 weight percent of the coating color.
The color developer solution is mixed with the pig-ment for a period of time sufficient for adsorption of the bisphenol onto the CaC03 to occur. The adsorption is believed rapid and, for example, a slurry of the color developer solution and CaC03 is mixed for a period of time in excess of about 1 minute and preferably for about 1/2 hour.
Water is then added to form the color developer dis-persion. The amount of water added depends on whetherthe dispersion is used directly to make the coating color. Where the coating color is prepared directly, enough water is added to produce the desired solids content by weight in the coating color For example, 0.7 grams of Bisphenol A in 37 milliliters IPA was added to 14 grams calcium carbonate; fifty-two milliliters of water was then added to produce the dispersion; 7.6 grams of adhesive latex binder, which was 50 percent solids by weight, was then added to produce a 20 weight percent solids coating slurry. Where the dispersion is instead to be dried to produce a powder color developer composi-tion, sufficient water is added to disperse the slurry.This amount is typically an amount equivalent to the amount of solvent used to dissolve the color developer compound.
Production of the powder involves evaporation of the organic solvent and/or water contained in the dispersion.
The drying can be performed in any desired manner. For example 7 a dispersion of water, isopropyl alcohol, and adsorbed color developer composition are run through a spray dryer and then dried at 87C for approximately 10 hours.
To generate the color developer dispersion from the dry powder, sufficient water, dispersant, and preferably protective colloid, to produce the desired weight percent solids in the coating color, as described above, is added. The adsorbing solvent can also be added along with the water in the dispersion of the dry powder, but this is not preferred because of cost. If added, the amount of alcohol is about 5 to about 25 weight percent of the coating color.
The following examples are presented to illustrate the invention.
EX~MPLES 1-4 Examples 1 through 4 determined the background color developing property of the pigments, CaCO3, talc, a Mon-tana chlorite, and a kaolinite clay from Aiken, S. Caro-lina. In each example, a coating color comprising about 30 weight ~ pigment and sufficient binder was coated on paper and dried to produce CF sheets. Each CF sheet was then paired with commercially available CB sheets from Appleton (A, blue image), Nashua Black (NB, black image), and Boise Cascade (BC, blue image) to form a manifold.
Sixty pounds per linear inch pressure was applied by passing the manifold through rollersl and the resulting image density on the CF sheet was measured by densitom-eter at 500 nm. Table I lists the pigments and optical densities. Surface areas and average particle sizes of the pigments were CaCO3 7 m2/g, .65 ~m; chlorite - 11 m2/g., 1.7 ~m; clay - 15 m2/g., .4~m; and talc - 15 m /g., 2 ~m.

TABLE I

ANB BC
CaC03 0.11 0.14 0.10 2 Chlorite 0.24 0.23 0.13 3 Clay 0.24 0.25 0.18 4 Talc 0.23 0.24 0.20 As seen, none of the pigments produced optical den-sities above 0.25, and ~xample 1 with CaCO3 produced the lowest optical density with all three CB sheets. All of these pigments thus cannot ordinarily be used as a color developer.
Unless otherwise noted the experimental procedure for Examples 5-27 was as follows: a phenol was dissolved in isopropyl alcohol (15 ml.) and mixed with an inorganic pigment (14.0 gr.) of Examples 1~4 for about 1/2 hour.
No pigment was added in Example 5. Water (21 ml.) was then added to form the color developer dispersion. To the dispersion was added Dow 670 styrene butadiene latex adhesive binder (7.6 gr. per 14.0 gr. pigment; 50~ solid by wt.) a dispersant agent (.05 gr.), an antibac-terial agent l.05 gr.), and an antifoamer agent (.05 gr.), and the resulting coating color was stirred until uniform.
The coating color was coated on a paper substrate using a No. 5 or No. 6 wire wrapped rod, and the coated paper was allowed to air dry~ The produced CF sheet was placed in contact with a commercially available CB sheet, for example, Nashua (black image former) or Appleton (blue image former). Pressure was applied to the produced manifold by passing them through a pair of rollers set at 60 pounds per linear inch pressure. The density of the image developed on the CF sheet was measured with a den-sitometer at 500 nm. The measurement error in the image density is considered to be plus or minus 0.05.
Table II lists the details of Examples 5-27, including the color developer compound, pigment, and color former used, the weight percent of color developer and pigment, and the resulting image density.

49~D~

TABLE II
Ex. ColorPIG~ENT Wt. % CB Sheet Developer Col.Dev. Type

5 Bisphenol ~ - 5 NB

6 " CaCO3 10 NB

7 " Clay 4.8 NB

8 " Chlorite 4.8 NB

9 " Talc 4.8 NB
" CaCO3 4.8 NB
1011 " Clay 4.8 A
12 " Chlorite 4.8 A
13 " Talc g.B A
14 " CaCO3 4.8 A
15 4-phenylphenol Clay 5 A
15 16 4-penty phenol Clay 5 A
17 pyrogallol Clay 5 A
18 nonylphenol Talc 5 BC
19 dodecylphenol Talc 5 BC
20 o-chlorophenol Talc 5 BC
20 21 4-n-butylphenol Talc 5 BC
22 octylphenol Clay 5 A
23 4-n-dodecylresorcinol Chlorite 5 A
24 phenol Talc 5 BC
25 resorcinol CaCO3 5 A
25 26 4-t-butylcatechol Talc 5 A
27 phloro~lucinol Talc 5 BC

~Z~4~
2g~

TABLE II (cont'd~L
Ex. Wt % Pigment Wt . ~ Total O.D.
In Coating Solids In Color _ Color - - 0.20 6 30.7 ~0.0 0.70 7 26.0 32.0 0.47 B 26.0 32~0 0.57 9 26.0 32.0 0.50 26.0 32.0 0.58 11 25.0 33~0 0.39 12 25.0 33.~ 0.45 13 25.0 33.0 0.45 14 25.0 33.0 0.50 30.8 41.7 0.30 16 31.0 41.7 0.30 17 31.0 41.7 0.30 18 31.0 41.7 0.30 19 31.0 41.7 0.30 31.0 ~1.7 0.30 21 31.0 41.7 0.30 22 30.8 42.0 0.30 23 31.2 41.0 0.40 24 31.0 41.0 0.30 ~6.2 32.0 0.40 26 31.0 32.0 0.40 27 31.0 32.Q 0.40 Examples 5-14 illustrate use of a color developing composition comprising the most preferred bisphenol, Bis-phenol A. Examples 1 and 5 illustrate that CaCO3 or Bis-phenol A alone are not effective as a color developer in a CF sheet, but that an admixture of Bisphenol A with CaCO3 shows a surprising, synergistic increase in color developing ability. The synergistic improvemPnt of admixing CaCO3 and the bisphenol of Formula I is seen because the optical density developed with Nashua Black and Appleton CB sheets on an additive basis of the phenol and CaCO3 equals 0.34 and 0.31, respectively, but the optical density actually developed by the admixture is 0.58 and 0.51, respectively. This synergistic increase over the additive optical density of Bisphenol A and CaCO3 of 0.24 and 0.19 is greater than any of the increases seen from the phenol admixed with the other pigments, although the other pigments also showed some synergistic increases. However, the synergistic increase with clay with both A and NB paper, and talc and chlorite with A paper could be within the measurement error, while the increases with CaCO3 are clearly outside any mea-suring error. Note that Examples 10 and 14 in partic-ular, both admixtures with CaCO3, generated optical den-sities better than commercially available CF sheets.
Furthermore, CaCO3 is preferred with the bisphenol over chlorite and talc because it can be dispersed in high solids aqueous slurries while they cannot.
Examples 6 and 10, taken with another Example, 6' (duplicating Example 6 except that 14 wt. % Bisphenol A
was used), show the preferred wt. ~ ranges of bisphenol used. Example 6' at 14 % BPA developed image density of 0.74 compared to Example 6 at 0.70. Thus, increasing the bisphenol content above 10 % had minimal effect. Com-paring Example 10 at 4.8 % BPA, O.D. of 0.58 to Example 6's O.D. of 0.70 showed that doubling the amount of phenol did improve image density, but Example 10 devel-oped commercially acceptable densities at lower cost.
Examples 15-27 illustrate that other monomeric poly-phenols admixed with pigments are not as effective as a bisphenol of Formula I in CF sheets. Note that Examples 17, 23, 25, 26, and 27 used biphenols different from the preferred bisphenol structure and that none had optical density higher than 0.40. Example 25 of resorcinol (with two OH groups) and CaCO3 is significant since only low density developed. Example 25 indicates the superiority of the bisphenol of Formula I with CaCO3. The single phenols had even poorer image development.

It should be noted that Examples 5-27 use commercial CB sheets and CB solvents which are used with adsorbed admixtures of phenol and CaCO3~ The data show commercial image densities were developed. However, later studies by Applicants showed that although initially active with present commercial CB solvents, an adsorbed admixture of phenol/CaCO3 can lose color developing activity with time, resulting in lower image densities. Thus~ both adsorbed and admixed bisphenol/CaCO3 compositions require a suitable solvent for commercial image densities, and are each believed to react similarly with color formers dissolved in such a suitable solvent.
Examples 28-30 were infrared (IR) spectrum analysis run in KBR pellets of CaCO3 (No. 28), Bisphenol A, (BPA) lS (No. 29) and the color developing composition comprising B% of the CaCO3 weight BPA admixed with CaCO3 (No. 30).
The BPA treated CaCO3 was produced by spray coating a slurry of 8% BPA in isopropyl alcohol and CaCO3. Anal-ysis of the IR spectra showed only a broad absorption over 1000-1800 cm 1 and a CaCO3 peak at 2500 1 for CaCO3 in No. 28 and multiple diagnostic peaks for BPA in No. 29 at about 560, 840, 1180, 1240, 1510, 1600 and 2990 cm 1.
Number No. 30 also had unobscured peaks attributed to BPA
at 560, 840 and 2990 cm 1. These examples show that the color developing compound BPA is admixed with CaCO3.
Example 31 illustrates preparation of the dry powder by spray coating. Bisphenol A, B83 gr., was dissolved in 3840 ml. IPA and spray coated onto 15920 gr. CaCO3. The resulting solvent wet powder was dried at 87C to produce a white, fluffy powder. This powder has a Bisphenol loading of 5 weight % on the CaCo3.
Examples 32 and 33 were scanning electron micro-scopic analysis at xlO00 magnification of CF sheets coated with 4.8% BPA on CaCO3, No. 32, and 10~ BPA on CaCO3, No. 33. The CF sheets were produced according to the procedure for Examples 5-27. Example 33 with 10~ BPA
showed not as good an admixture as Example 32 since dis-~2~

crete crystals of BPA could be seen, whereas in Example 32 no discrete BPA could be seen. Compared to a commercially available Boise Cascade CF sheet of phenolic resin, the CF coatings in all three appeared less porous.
Examples 34, 35, and 36 illustrate the first method of making the color developing composition An aqueous feed slurry comprising CaCO3 having a particle size dis-tribution of 99~ less than 12~m, Bisphenol A, and suffi-cient Colloid-230* available from Colloid Co., to be at a dispersant level of 20 lb. per ton of CaCO3 was wet milled starting at ambient temperature in two passes in a 4 liter Netsch mill with ceramic media. Table III shows the details of the feed slurries used to produce color developer dispersions comprising CaCO3 and Bisphenol A.
The amount of BPA i5 % of CaCO3. About 3 gallons of each dispersion were produced.

TALLE ITI
Ex.Wt.~ CaCO~ Wt % 3PA

The color developer dispersion from Example 36 was studied for slurry stability and aging at 120F. Table IV shows the results of the stability studies.

TABLE IV
TimeViscosity pHConductivity 30 Day (50 rpm) _ (Ohm/cm) 0 265 cps 9.76 700 1 287 9.30 622 2 314 9.48 690 388 9.69 770 9 357 9.26 780 *Trademark .

., ~L2~

As seen, pH, viscosity, and conductivity do not change wi~h aging. The slight increase in viscosity is normal and expected for CaC03 slurries. Therefore the disper-sion is stable. This is an advantage of the invention because it can be desirable to produce the dispersion at a pigment mill site and then ship the dispersion to a distant paper mill site for production of CF sheets.
Coating colors and CF sheets were then produced from the color developer dispersion of Example 34 to examine optical density development and coating uniformity. To the color developer dispersion was added Dow 670 latex and starch as binders, Tamol~ 850 dispersant, and suffi-cient water to produce various ~ solid coating slurries.
Optionally, Number 2 coating clay from Englehardt Min-erals or an amorphous silica (Cab-o-Sil EH-5) as fillers in an amount of 25 parts by weight per 100 parts CaC03 were added.
For example, a 40% solids coating color was formu-lated by mixing until uniform 29.4 grams of the 70.4%
solids dispersion of 5% BPA, CaC03 and Colloid 230 at 20 lb./ton CaC03; 17.9 grO H20; 3.0 gram Cab-o-Sil or No. 2 clay; 2.5 gr. Dow 670 latex (50~ solids); and 6.25 gr.
starch (20~ solids). The coating color 601id weights and the resulting coating weights were 30% solids and 8 g/m2;
40~ and 10 g/m2; 50% and 13.5 g/m2; and 58% and 17 g/m2.
The reason some of these coating weights are outside the preferred 4-10 g/m2 coating weight range given above is that the laboratory coating equipment could not effi-ciently coat these high solids colors. Conventional coating equipment does not have this problem.
The produced CF sheets were then placed in contact with a solution of 2% by weight of solution of a color former mixture of 1.9 gr CVB, 1.9 BLMB, and 0.3 gr Per-gascript Red~, available from Ciba-Geigy, in a solvent system comprising a transfer fluid mixture of methyl iso-butyl carbinol (3-dimethyl-2-butanol) and Sursol~, a dibutyl biphenyl available from Koch Refining Co., and a *Trademark 4~
-3~-diluent kerosene. Table V shows details and the image densities developed.

TABLE V
Filler (wt.%) (wt.~) (wt.%) (wt.%) Optical Ex. Pigment Kerosene Sursol Alcohol Solids Density 37 Clay 50 25 25 40 0.45 38 Clay 50 30 20 40 0.35 39 Silica 50 30 20 40 0.48 " 50 25 25 40 0.48 41 " 50 20 3d 40 0.48 42 " 50 10 40 40 0.48 As seen, the added pigment fillers did not signifi-cantly decrease optical density. Appli~ants consider that Example 40's decrease is due to the decrease in the amount of alcohol for dissolving the Bisphenol A. As was expected, the silica seemed to counteract the effects of changes in the solvent since it has some color developing ability. Example 39 is considered very significant because of good optical density from the color developing composition and CF sheet of the invention and a lower cost alcoholic solvent system.
The CF sheets without a~ded pigment were also devel-oped with prepared CB sheets. A leuco dye mixture of Crystal Violet Lactone (CVL: 1.9 g), Benzoyl Leuco methy-lene blue (BLMB: 1.9 g.) and Pergascript Red I-6B (0.3 g) from Ciba-~eigy were dissolved in pentyl acetate (190 cc). At room temperature catalyst (Desmondue N-100, 7.5 g and Mondur MRS, 6.0 gO from Mobay Chemical Co.) were added to the above solution and solubilized. This mix-ture constitutes the oil phase. The aqueous phase was made by dissolving 11 g Rlucel L (Hydroxypropyl cellu-lose, from Hercules) in 400 cc water. A catalyst, Cymel 301, (1.0 g), from Cyanamid and a surfactant, sulfated Castor oil (1.0 g) were added to the aqueous mixture.
The oil phase was added after the aqueous phase had been adjusted to ph 4 with 16~ acetic acid solution. The mix-ture was blended with a Waring* blender from 1-3 minutes, transferred to a reactor and stirred gently for 16 hours at 50-55C.
Microscapsules formed were 6-10 microns in diameter.
The microcapsule mixture was adjusted to pH = 7 with 1%
NaOH solution. Then it was coated on base stock paper and imaged with the CF sheet of Example 34 (40% solids).
Image intensity of 0.45 was obtained. With the dye con-centrations of 3% used commercially, higher image inten-sity is expected. For comparison the CB sheet was imagedwith CF sheets of Appleton, Mead, Boise Cascade (all phe-nolic resin type) and Koehler (acid treated clay), and O.D. of 0 45-0.55 were obtained A second CB sheet was made as above with the excep-tion that instead of using 190 cc pentylacetate, the fol-lowing solvent mixture was used: 57 cc pentylacetate and 133 cc Sursol-290 (isobutylbiphenyl) manufactured by Koch Refining Co.). Image development was 0.40. A third CB
sheet was prepared as above except that 57 cc of 4-methyl-2-pentanone and 133 cc Sursol 290 were used as the color former solvent. Image intensity was also 0.40.
The CF sheets of Example 34 and 36 were also solu-tion developed with the above 2% dye mixture dissolved in dimethylnapthalene. The image intensity was 0.45 with Ex. 34 (5% BPA) and 0.55 with Ex. 36 (8% BPA) Exam les 43 - 47 Dilution of the 5% BPA/CaCO3 color developer disper-sion with water can cause problems with flocculation of the bisphenol. Examples 43-47 are stability tests of diluted dispersions containing various levels of protec-tive colloid.
A 73.77% solids slurry containing CaCO3having a par-ticle size distribution of 99.8% < 12 ym and Colloid 230 at 20 lbs./ton CaCO3 level were mixed for 30 minutes with sufficient Bisphenol A to be 5 ~ by weight of the CaCO3.
The feed slurry was then milled in 3 passes through a 4 liter Netzsch mill operating at 85% volume with 1/32"

*Trademark ~l2~ 4 ceramic media at 1500--2100 rpm. Maximum temperature was 46 C. The resulting color developer dispersion (Example 43) had a particle size of 99.8% ~ 4 ~m and was th~n mixed with protective colloid, and diluted 1/1 by weight with water. Table VI gives amounts of colloid added, the calculated % solids before dilution, the thixotropic index, measured viscosities, and the extent of floccula-tion. The polyvinyl alcohol (PVOH) was a 20% solution of VINOL~ 205 and the carboxymethyicellulose (CMC) was a 5%
solution of ~ercules CMC 7LT.

~z~

TP~BLE V I

Brookfield Vis.
Calc at Var.. RPM
.
Ex. Solids % 2,5 20 T/I

43 7~.5 3,80~ ~50 4.47 ~4 69.3 20,480 3,S05 5.61 (.2% CMC3 ~5 72.0 1~,0003,200 5.0 (.2% PVOH) 46 72.3 9,3602,350 3.98 (o1% PVOH~

Ferranti-Shirley BPA Flocculation BPA Flocculation 20Poise at Fresh 1-1 ~fter 2 Weeks 1-1

10 000 Sec-l Water ReductionWater Reduction r ,, . .

(43) .551 Severe Severe 25 (44) .S67 None Moderate (45) .725 None Slight (~6) .667 Very Slight Moderate -- ~mounts of PVOH and ~C are on active basis of total calc;um carbonate wei~ht.

-3~-The results show that the color developer dispersion can be stabilized by a protective colloid for extended periods. As seen in the flocculation results, 0.2 wt. ~
polyvinyl alcohol was more effective than 0.2 wt. % car-boxymethyl cellulose, although both are adequate. CMCwas slightly more effective than 0.1 wt. % PVOH. The thixotropic index is the ratio of the Brookfield 2.5 rpm viscosity to the 20 rpm viscosity~ and all 4 dispersions showed good thixotropic behavior, i.e., thinner at higher shear. The Ferranti-Shirley high shear rate viscosities are also good.
Examples 47 - 49 Examples 47, 48 and 49 are coating colors made from the dispersions of Examples 43, 44 and 45, respectively.
The colors were made the same day as the dispersions by mixing on a dry solids basis 100 parts of the undiluted dispersion with 5 parts starch and 10 parts DOW 620 styr-ene-butadiene latex. The physical data of all three colors were: pigment volume content, 74~; pigment/binder weight ratio, 6.7/1; binder/pigment weight ratio, 15/100;
and total solids, 60 weight %.
The rheology and stability of the colors was then examined by measuring viscosity at 25C and diluting the colors with an equal wt. of water. T~le VII gives the details.
TABLE VII
Ex. Brookfield Visc. ICI Cone & Floccul. Floccul.
~20 rpm) Plate Poise Initial After _ Poise 10,000 sec 1 Dilution 2 Wks.
30 47 2,225 .28 Severe Severe 48 4,170 .4 None Slight 49 2,180 o29 None Slight The results show excellent rheological properties in all three colors. The critical high shear viscosities were measured on a cone and plate instrument and are ideal since high shear rate (10,000 sec 1) viscosities below about 1-1/2 poise must be achieved to permit r~ *Trademark 4~
~39-coating. The high shear viscosities were also examined by rheogram plots of EIercules viscosities which also showed close to ideal behavior. The low shear rate Brookfield viscosities are acceptable although below S about 2000 poise at low shear rate is more desirable. In sum, these 60 wt.~ solid~ coating colors show close to ideal coating rheology.
The dilution tests showed both CMC and PVOH as effective protective colloids for preventing significant degradation of the color. Because of the lower vis-cosity, particularly at low shear rates, colors with PVOH
are preferred.
Other coating colors using only the Dow latex as a binder were formulated at p~ 8 and 9.5, % solids of 59, 66, 68 and 71, and pigment/binder ratios of 7/1 and 24/1.
The rheology of these coatings at high shear rates was also excellent.
Example 50 Example 50 illustrates the second and preferred method of making the color developer dispersion and prep-aration of a coating color and CF sheet therefrom. A
Bisphenol A emulsion was prepared by Netzch mill grinding an aqueous slurry of Bisphenol A, carboxymethyl and car-boxyethyl cellulose and Tamol dispersant~ in the amounts listed above in the discussion of the preferred method, until the BPA particle size was 100% less than 4~. This BPA emulsion, 7.7~ gr. was then blended with 50 grams of 74 wt. ~ CaC03 ULTRAMITE slurry by stirring. To the resulting color developer dispersion was added 9.85 Ethylex 3030 starch, 3.94 gr. DOW 620A styrene butadi~ne latex7 and 2.15 gr. H2O, and the color mixed until uni-form. The color had a solids content of 60 wt. %, a binder/pigment ratio of 10/100 and a BPA/CaCO3 ratio of 8 parts/100 parts.
The coating color was blade coated unto paper sheets and allowed to dry to produce CF sheets. The coating weight was 5-6 gr./m2.

Example 51 CB sheets were produced as follows: 25 gr. ethyl maleic anhydride was mixed with 66 gr. H2O, 5 gr. urea, and 0.5 gr. resorcinol, and the pH adjusted to 3.5 with 20~ NaOH. Various color former solutions, each 30 gr., were then added and mixed at high shear in a blender for one minute. One hundred gr. H2O was added-and the beaker kept at 55C. for two hours~ The resulting micro-capsules in each example were filtered and found to be 5 - 10~ in size. The micro~apsules were then coated onto paper sheets to produce CB sheets.
The CB sheets were paired with CF sheets of Example 50 and ima~ed. Table VIII gives the color formers and their wt. percent, the solvent mixture and developed image density. The densities were calculated from reflectance measurements of the image taken on a Hunter Lab instrument which measures reflectance on a scale of 0.0 Iblack) to 100 n 0 (white). The reflectance values are converted to image density usin~ known conver-sion tables.

~2~3~

TABLE VIII

Ex. Dye(wt.~) Solvent (wt.%) O.D.

51 BASF Crystal Violet Santosol 340 (50) 0.37 Lactone ~2.3) Texanol (25) Ethylbenzoate (25) 52 BASF Crystal Violet Santosol 34~ (62. 0.37 Lactone (2.3) Texanol (37.3~

53 BASF Crystal Violet Santosol 34~ (34) 0.39 Lactone (3.0) Texanol (66) 15 54 BASF Crystal Violet Santosol 34~ (34) 0.39 Lactone (4.0) Texanol (66) Black former Santosol 340 (60) 0.4 : produced Texanol (25) 20 from equal mixture Ethylbenzoate (15) of BASF olive, red, and blue (4.0) 56 Black former Santosol 340 (6205) 0.4 produced Texanol (37.5) from equal mixture of BASF olive, red, and blue (4.0) 30 57 Black former Santosol 340 (34) 0.4 produced Texanol (66) from equal mixture of BASF olive, red, and blue (4.0) As seen in TABLE VIII~ the image development with the Texanol solvent system was acceptable considering the low *Trademark ,-, , amounts of color former used1 Example 58 Example 58 illustrates the preferred CB solvent, n-butylbenzoate. The microencapsulation technique of Examples 51~57 was used to encapsulate 5 wt.% BASF-684 dye (a blue forming flouran) dissolved in 75 wt.% n-bu-tylbenzoate and 25 wt.% odorless mineral spirits. A CB
sheet was then prepared and matched with a CF sheet of Example 50. The manifold was imaged and Table IX shows image development as measured by Hunter Lab reflectance with time. The paper had a background reflectance of 91.64 and the human eye can discern a difference of 3.0 units on the Hunter scale.
TABLE IX

TimeReflectance 0 91.64 3 minutesa79.12 45 minutes49.85 4 hours 41.54 32 days 47.34 First measurement was taken as soon as practical.

For comparison a commercially available carbonless paper manifold was imaged and the development and decline monitored with time. The commercial manifold had its darkest image of 51.32 reflectance after 7 hours which declined to 53.20 after 32 days~
Thus, Example 58 developed a discernible image immediately and a darker imag~ than a commercial sample.
- Further, even though the image decline was almost 6 units compared to only almost 2 units for the commercial, the image of Example 58 was still discernibly darker after 32 days~

~l21~3~4~4 As is seen in the Examples, the bisphenol/CaCO3 admixture of the invention is useful in developing image density above 0.50 when formulated in a coating color, coated onto a CF support sheet, and paired with a leuco dye CB sheet. In addition, coating colors comprising the admixture have excellent high shear rate viscosities below about 1.5 poise even at high solids contents above 50 wt. ~ which have not previously been used in carbon-less paper coating colors.
However, the above discussion is intended to be illustrative only and is not to be considered as lim-iting. Rather, the scope of the invention is given by the following claims.

Claims (11)

WE CLAIM:

1. A color developing CF sheet for pressure sensi-tive recording systems comprising a support coated with an admixture which is substantially responsible for color development comprising calcium carbonate and a monomeric bisphenol having a general formula:

wherein N is 1, 2, 3, 4, or 5, and R1 and R2 are the same or different and are hydrogen, alkyl, substituted alkyl, amino or substituted amino, wherein weight ratio of bis-phenol to calcium carbonate is about 2 to about 20 parts per 100 parts calcium carbonate and the calcium carbonate content of the admixture is at least 50 dry weight %.

2. The CF sheet of Claim 1 wherein R1 and R2 are hydrogen or unsubstituted alkyl up to 3 carbon atoms, N is 1, and the OH groups are located at the 4 and 4 positions relative to the shared carbon atom.

3. The CF sheet of Claim 1 wherein the bisphenol comprises 4,4'-isopropylidenediphenol.

4. A manifold for pressure sensitive recording comprising:
a) at least one CF sheet comprising a support coated with an admixture of calcium carbonate and mon-omeric bisphenol having a general formula:

wherein N is 1, 2, 3, 4, or 5, and R1 and R2 are the same or different and axe hydrogen, alkyl, substituted alkyl, amino or substituted amino; wherein weight ratio of bisphenol to calcium carbonate is about 2 to about 20 parts per 100 parts calcium carbonate; and calcium carbonate comprises at least 50 dry weight percent of the admixture; and b) at least one CB sheet comprising a support coated with a microencapsulated solution of a color former in a solvent in which sufficient bisphenol reacts with the color former to form an image having an image density, measured at 500 nm., greater than about 0.40.

5. The manifold of Claim 4 wherein the bisphenol is 4,4'-isopropylidenediphenol.

6. The manifold of Claim 4 wherein the microencap-sulated solvent comprises an ester having at least 7 carbon atoms.

7. The mainfold of Claim 6 wherein the ester is an alkyl benzoate.

8. The manifold of Claim 4 wherein the solvent comprises n-butyl benzoate.

9. The manifold of Claim 8 wherein the solvent further comprises odorless mineral spirits.

10. The manifold of Claim 4 wherein the solvent comprises 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.

11. A method for making a pressure-sensitive re-cording manifold capable of developing an image having an image of at least 0.50, as measured at 500 nm, comprising:
a) forming a coating color comprising an admixture of 4,4'-isopropylidenediphenol and CaCO3 wherein weight ratio of the phenol to CaCO3 is about 2 to about 20 parts per 100 parts CaCO3 and CaCO3 comprises at least 50 dry weight % of the coating color;
b) coating the color onto a support and drying to produce a CF sheet;
c) pairing the CF sheet with a CB sheet comprising a support coated with microcapsules containing a leuco dye color former dissolved in an alcohol having a carbon number of 4 to 12.