Reactive pigments and methods of producing the same

Abstract

Reactive pigments and methods of producing the same for use in manifold copy systems is provided in which a member from the group consisting of bentonite and montmorillonite is admixed with kaolinite, added to an aqueous solution of a polyvalent cation, a ligand is added and the solids separated, dried and pulverized.

Description

This invention relates to methods of producing reactive pigments and particularly to the production of pigments for use in pressure sensitive record materials.

The use of pigments in paper coatings for manifold copy systems is not in itself new. Such manifold copy systems have, however, been based upon the use of oxidizing clays and special acid leached bentonites as the basis for the pigment. Such systems are disclosed in U.S. Pat. Nos. 3,753,761; 3,622,364; 3,565,653; 3,455,721; 2,712,507; 2,730,456; 3,226,252; 3,293,060 and Canadian Pat. No. 780,254.

These pressure sensitive record materials are frequently termed "carbonless carbon papers" and are, in general, highly successful in reproducing copies.

The present invention provides a marked improvement over these prior art pressure sensitive record materials. It provides an excellent dye development and light fastness without the necessity of an acid leached bentonite. It provides improved intensity of dye development as compared with present pigments. Improved rheology in the coating mixture results so that it can be coated at high solids on a blade coater. It provides sufficient flexibility so that both image intensity and color can be varied and controlled to a degree unthought of with prior art materials. Finally, but not least in importance, improved coated sheet properties such as brightness, whiteness index, opacity, smoothness and gloss are obtained.

The improved reactive pigments of this invention comprise in combination a metal ion or proton, a ligand, a bentonite or montmorillonite and a kaolinite. The preferred metal ion is copper derived from CuCl.sub.2. The preferred ligand is 1,6-hexanediamine. Other metal ions and protons may be used, e.g. Ba, Cd, Cr, Fe, Co, Li, Mn, Ni, Sn, Zn, Na and Al preferably as a mineral acid salt such as the chloride or a proton such as H.sup.+ derived from HCl, H.sub.2 SO.sub.4, acetic acid, citric acid, boric acid, tartaric acid, HNO.sub.3, H.sub.3 PO.sub.4. The same is true of the ligand, where other ligands such as gluconic acid, isostearic acid, sodium dimethyl dithiocarbamate, and others may be used. The term bentonite is used generically to describe the unrefined rock from which montmorillonite, a swelling clay, is fractionated.

The process of producing such reactive pigment is illustrated in the following example:

EXAMPLE I

Forty-five grams of montmorillonite (or bentonite) is combined with 135 g. of kaolinite and dispersed in 900 g. water. To this mixture, 1.98 g. CuCl.sub.2 in 50 g. H.sub.2 O is added and allowed to stir for 15 minutes, at which time 1.80 g. 1,6-hexanediamine in 50 g. H.sub.2 O is added and allowed to stir for an additional 30 minutes. The slurry is then filtered and dried at 90.degree. C. overnight. The dried filter cake is pulverized three times on a Mikro Samplmill.

The above procedure can be illustrated as follows: ##EQU1##

Various reactive pigments were prepared using different metal ions, different ligands, different bentonites and kaolins.

The various reactive pigments were evaluated using the following coating formulation:

In a 200 ml. tall beaker, place 65 ml. water and (0.5%) 0.40 g. Calgon (sodium hexametaphosphate). Place on Hamilton Beach mixer and mix to dissolve Calgon. Add pigment slowly until all pigment is incorporated and blunge for 5 minutes. At this point, clay-water viscosity measurements can be taken.

To the clay-water dispersion, 19.5 g. Dow Latex 638 is added and mixed on a low speed mixer for 5 minutes. At this point, the coating color viscosity measurements are taken. Hand sheets are made using a blade applicator. The coat weight on the hand sheet was 3.0 lbs./ream (3300.sup.2 ft.).

The hand sheets were evaluated for image intensity and color using a Spectronic 505. The image intensity is recorded as the optical density at 6140 A on the developed sheet minus the optical density at 6140 A on the undeveloped sheet. The hand sheets were developed first by calendering the sheet using only the pressure of the rolls and then passing the sheets through a second time with a 2 inch square of CB sheet taped on top of the hand sheet or CF sheet. The CB sheet is coated on the backside with microcapsules containing dye precursor of the following types:

TYPE I DYES

Colorless dyes which develop intense colors immediately upon contact with Bronsted acid-and/or Lewis acid-type substrates. The color development is influenced by environmental pH and/or polarization of the dye. Examples of type I dyes are crystal violet lactone and other triarylmethane dyes, such as malachite green lactone. Michler's ketone and Michler's hydrol as well as other diphenylmethanes are also examples of type I dyes.

TYPE II DYES

Colorless dyes which do not immediately develop an intense color upon contact with a reactive pigment, but, with time, an intense color will develop by means of oxidation and/or an electron transfer mechanism. Examples of the type II dyes are thiazines, such as benzoyl leuco-methylene blue, and triarylmethane, such as leuco-crystal violet and leuco-malachite green.

The optical density data reported in the following examples were based on a diphenylmethane type I dye precursor. The brightness and whiteness index were measured in accordance to the TAPPI procedures. Redness is the ratio of the optical density at 5300 A to the optical density at 6140 A times 100. The redness of the image is of importance because a red image will xerox better than a blue image.

The effect of changing metal ions and proton sources on the reactive pigment is set out in Tables I and II below:

TABLE I__________________________________________________________________________Effect of Metal Ions__________________________________________________________________________ ##STR1##__________________________________________________________________________ BROOKFIELD Viscosity OPTICAL (cpe) HERCULES DENSITY % 10 RPM 100 dynes 1 Hour Redness__________________________________________________________________________ 3.96 g. CrCl.sub.3 . 6 H.sub.2 O 180 86 6.5 0.683 52.0 3.96 g. FeCl.sub.3 . 6 H.sub.2 O 1720 236 0.9 0.747 43.6 3.50 g. CoCl.sub.2 . 6 H.sub.2 O 180 80 0.6 0.713 44.7 3.50 g. NiCl.sub.2 . 6 H.sub.2 O 200 80 0.6 0.691 47.0 1.98 g. CuCl.sub.2 180 64 0.7 0.642 39.2 1.98 g. ZnCl.sub.2 260 112 0.6 0.686 44.9 0.99 g. ZnCl.sub.2 + 80 56 0.5 0.720 40.1 0.99 g. CuCl.sub.2 9.90 g. Al.sub.2 (SO.sub.4) . 18 H.sub.2 O 100 68 0.6 0.680 32.1 3.60 g. CuSO.sub.4 . 5 H.sub.2 O 80 64 0.8 0.667 40.510. 1.81 g. CaCl.sub.2 . 2 H.sub.2 O 880 296 1.7 0.642 33.6 TABLE II______________________________________Preparation of Carbonless Carbon Pigments______________________________________ % Optical% Metal Salt 1,6 Hexanediamine Density______________________________________CrCl.sub.3 . 6 H.sub.2 O 1.45% 0.5 0.758CoCl.sub.2 . 6 H.sub.2 O 1.59% 0.5 0.807NiCl.sub.2 . 6 H.sub.2 O 1.24% 0.5 0.765MnCl.sub.2 . 4 H.sub.2 O 1.03% 0.5 0.922FeSO.sub.4 . 7 H.sub.2 O 1.03% 0.5 0.753SnCl.sub.2 . 2 H.sub.2 O 1.51% 0.5 0.879SnCl.sub.4 . 5 H.sub.2 O 1.43% 0.5 0.903LiCl 0.57% 0.5 0.901ZnSO.sub.4 . 4 H.sub.2 O 1.19% 0.5 0.881NaCl 0.78% 0.5 0.908HCl 0.71% 0.5 0.940H.sub.2 SO.sub.4 0.95% 0.5 0.987KCl 1.00% 0.5 0.833BaCl.sub.2 2.36% 0.5 0.838MgCl.sub.2 . 6 H.sub.2 O 1.66% 0.5 0.854CdCl.sub.2 1.53% 0.5 0.842Acetic Acid 1.16% 0.5 0.751H.sub.3 PO.sub.4 0.63% 0.5 0.740HNO.sub.3 1.22% 0.5 0.748Citric Acid 1.36% 0.5 0.744Tartaric Acid 1.45% 0.5 0.754Boric Acid 0.40% 0.5 0.730VOSO.sub.4 1.93% 0.5 0.719CONTROLAcid Leached Clay 0.578______________________________________

As shown in Table I, the metal ion is capable of effecting the rheology, image intensity, and image color or redness.

The effect of varying the metal ion or proton source is shown in Table II.

The effect of varying the ligand composition is set out in Table III.

TABLE III__________________________________________________________________________Effect of Ligands__________________________________________________________________________ ##STR2## BROOKFIELD Viscosity Optical (cpe) HERCULES Density %Sample 10 RPM 100 dynes 1 Hour Redness__________________________________________________________________________2.25 g. Tartaric Acid 19,200 3360 -- 0.677 67.71.80 g. 1,6-Hexanediamine 60 46 0.9 0.663 44.95.58 g. Gluconic Acid 1040 328 1.8 0.568 56.73.96 g. Isostearic Acid 880 252 1.7 0.612 44.60.25 g. Sodium Dimethyl Dithio- 2760 712 2.3 0.548 54.9carbamate0.77 g. 2-4 Pentanedione 700 260 2.4 0.744 53.21.13 g. Adipic Acid 1300 460 3.7 0.702 58.40.69 g. B Alinine 560 240 2.9 0.728 50.11.04 g. DL-Aspartic Acid pH = 3.0 32,000 3840 6.0 0.667 55.01.04 g. DL-Aspartic Acid pH = 4.6 1,260 472 5.4 0.696 46.01.04 g. DL-Aspartic Acid pH = 6.3 900 368 4.3 0.670 39.70.73 g. 2 Aminopyridine 80 68 1.6 0.677 49.51.91 g. Aminoguanidine Sulfate 200 104 2.4 0.706 42.11.41 g. 4-Nitroanthanilic Acid 230 120 2.3 0.689 56.60.84 g. 2-Amino-6-Methyl Pyridine 40 50 1.2 0.718 46.50.92 g. Benzimidazole 80 72 1.5 0.701 45.8__________________________________________________________________________ The influence of the ligand is primarily on the rheological properties. There appears to be no correlation between rheology and imaging intensity and image color or redness.

The effect of varying the concentration of the preferred ligand is set out in Table IV.

TABLE IV______________________________________Effect of 1,6-Hexanediamine Content______________________________________ ##STR3## ##STR4##______________________________________ BROOKFIELD Viscosity Optical1,6-Hexane- (cpe) Hercules Density %diamine 10 RPM 100 dynes 1 hour Redness______________________________________0.00 g. 1920 725 3.4 0.592 48.60.36 g. 720 272 1.7 0.922 53.70.72 g. 240 124 1.4 0.907 45.51.08 g. 60 52 0.7 0.872 35.21.44 g. 30 52 0.5 0.733 31.01.80 g. 30 44 0.4 0.674 27.91.62 g. 10 36 0.4 0.563 26.1______________________________________ The redness is greatest with 0.36 g. 1,6-Hexanediamine per 180 g. pigment (0.2%), as well as the highest image intensity. The rheology is substantially improved over that of the acid leached bentonites.

The effect of different extender pigments on the reactive pigment is illustrated in Table V.

TABLE V______________________________________Effect of Different Kaolinites and Calcium Carbonate______________________________________ ##STR5## ##STR6##______________________________________BROOKFIELDViscosity Optical(cpe) Hercules Density %Sample 10 RPM 100 dynes 1 hour Redness______________________________________Premax 40 46 0.6 0.713 40.0KCS 60 52 0.6 0.678 39.2WP 80 64 0.6 0.711 40.2Astra plate.RTM. 100 72 1.0 0.734 39.5Glomax 40 52 0.8 0.829 37.0PJDGlomax JD 40 52 0.8 0.858 41.8Atomite 60 60 0.6 0.591 35.0______________________________________

This Table shows that extender pigments, such as hydrous kaolinites, calcined kaolinites, and calcium carbonate, exert only minor influence on rheological properties, but drastically influence image intensity. The calcined clays give the greatest improvement in image intensity.

In Table VI the effect of different bentonites or montmorillonites is set out.

TABLE VI______________________________________Effect of Different Bentonites or Montmorillonites______________________________________ ##STR7## ##STR8##______________________________________BROOKFIELDViscosity Optical(cpe) Hercules Density %Sample 10 RPM 100 dynes 1 hour Redness______________________________________Gelwhite.RTM. 60 46 0.9 0.663 44.9K-4 20 44 0.2 0.698 32.4K-2 10 38 0.4 0.768 32.0910 60 56 0.8 0.638 30.7Mississippi 20 36 0.4 0.400 32.5______________________________________

The Gelwhite sample has the greatest redness which would Xerox better than the other bentonite samples. Improved Xerox capability means that a sample with greater redness will be reproduced with equal intensity even though its image intensity may be lower than that of a blue sample. The term bentonite is used to refer to a rock, while the term montmorillonite refers to a type of swelling clay recovered by means of fractionating a bentonite. Experiments were carried out using both bentonite and montmorillonite showing that the rheology, image intensity, and image color were the same. Only the amount of grit in the final samples varied. When the bentonite was used, greater grit or 325 mesh residue was obtained.

The variation of bentonite content and its effect on the reactive pigment are shown in Tables VIIa and VIIb.

TABLE VIIa__________________________________________________________________________Effect of Bentonite Content__________________________________________________________________________ ##STR9##__________________________________________________________________________ BROOKFIELD Viscosity Optical (cpe) Hercules Density %Samples 10 RPM 100 dynes 1 Hour Redness__________________________________________________________________________15% 27 g. Bentonite 30 40 0.4 0.617 30.185% 153 g. Kaolinite20% 36 g. Bentonite 120 64 0.7 0.655 34.480% 144 g. Kaolinite25% 45 g. Bentonite 300 128 1.1 0.664 38.275% 135 g. Kaolinite30% 54 g. Bentonite 2120 690 2.9 0.634 38.270% 126 g. Kaolinite35% 63 g. Bentonite 5120 1600 5.2 0.609 38.865% 117 g. Kaolinite__________________________________________________________________________ TABLE VIIb__________________________________________________________________________Effect of Montmorillonite Content ##STR10## ##STR11## BROOKFIELD Viscosity Optical % (cpe) Hercules Density RednessSamples 10 RPM 100 dynes 1 Hour 1 Hour__________________________________________________________________________25% Montmorillonite 420 198 2.2 0.807 52.375% Calcined Kaolinite20% Montmorillonite 140 84 1.4 0.804 47.080% Calcined Kaolinite15% Montmorillonite 40 46 0.6 0.780 39.185% Calcined Kaolinite10% Montmorillonite 20 40 0.3 0.572 32.390% Calcined Kaolinite__________________________________________________________________________ The bentonite was fractionated by sedimentation in order to remove everything greater than 5 microns, thereby resulting in a montmorillonite

Tables VIIa and VIIb show that the optimum amount of bentonite with regard to image intensity was obtained with 25% bentonite and 75% kaolinite.

In order to show the improved properties of the reactive pigment as compared with acid leached bentonites, several samples of each were examined in detail with regard to image intensity, image color and rheology.

The aqueous viscosity and coating color viscosity data were obtained on compositions similar to those of the new reactive pigment of this invention but were made down at 45% solids instead of 60% solids.

TABLE VIII__________________________________________________________________________Clay - Water Viscosity cpe Dispersing % % BrookfieldSample Agent D.A. Solids 10 RPM 100 Hercules__________________________________________________________________________MBF 530 Calgon 6.8 45 2920 1144 12.5 dynesMBF 530 Dispex N-40 4.4 45 4640 1808 15.6 dynesSilton Calgon 3.5 45 180 148 5.0 dynes*Reactive Pigment No. 1 Calgon 0.5 62 7000 1640 775 rpmReactive Pigment No. 1 Dispex N-40 0.53 62 4320 1412 560 rpm**Reactive Pigment No. 2 Calgon 0.5 62 700 193 14.5 dynesReactive Pigment No. 2 Dispex N-40 0.53 62 900 280 13.2 dynes__________________________________________________________________________*Reactive Pigment No. 1 ##STR12##**Reactive Pigment No. 2 ##STR13## TABLE IX__________________________________________________________________________Coating Color Viscosity Brookfield Viscosity Dispersing % % (cpe)Sample Agent D.A. Solids 10 rpm 100 rpm Hercules__________________________________________________________________________MBF 530 Calgon 6.8 45 28,600 6080 670 rpmMBF 530 Dispex N-40 4.4 45 3,920 1200 5.1 dynesSilton Calgon 3.5 45 80 92 2.1 dynesReactive Pigment No. 1 Calgon 0.55 60 3,200 896 5.4 dynesReactive Pigment No. 1 Dispex N-40 0.58 60 1,960 524 6.2 dynesReactive Pigment No. 2 Calgon 0.55 60 850 25 2.1 dynesReactive Pigment No. 2 Dispex N-40 0.44 60 520 152 2.0 dynes__________________________________________________________________________ TABLE X__________________________________________________________________________ Optical Density Dispersing % % %Sample Agent Immediate Redness 20 mins. Redness 1 hour Redness__________________________________________________________________________MBF 530 Calgon 0.589 51.6 0.593 52.4 0.583 53.0MBF 530 Dispex N-40 536 65.3Silton Calgon 0.501 77.6 0.501 80.0 0.481 82.1Reactive Pig. No. 1 Calgon 0.642 31.6 0.668 34.1 0.692 37.7Reactive Pig. No. 1 Dispex N-40 0.684 35.2 0.694 36.7 0.715 38.9Reactive Pig No. 2 Calgon 0.574 28.2 0.588 27.5 0.649 32.7Reactive Pig. No. 2 Dispex N-40 0.584 27.7 0.612 29.7 0.673 32.7__________________________________________________________________________

The image intensity is better for the reactive pigment when compared to the acid leached bentonites while the redness appears to be somewhat lower for the active clays.

I have also discovered that slurry stabilization and color intensity of the image can be effectively controlled by a combination of an inorganic (e.g. sodium hexametaphosphate) and an organic dispersant (e.g. polyacrylate, sodium salts of bisulfite regulated oligomers, etc.).

The effect of dispersing agent on viscosity and optical density are set out in Tables XI and XII hereinbelow. In these tests the inorganic dispersant used was Calgon (sodium hexametaphosphate). The organic dispersants were Polywet ND-1 and Polywet ND-2, supplied by Uniroyal, Inc., and Dispex N-40, supplied by Allied Colloids.

Polywet ND-1 and ND-2 are sodium salts of a bisulfite regulated oligomer which only vary in molecular weight. The molecular weight of Polywet ND-1 is ca 1500, while Polywet ND-2 has a molecular weight of ca 1000. Dispex N-40 is a polyacrylate which has a molecular weight of approximately 5000.

The carbonless carbon pigment used in this investigation was formed using 0.9% CuCl.sub.2 and 0.5% 1,6 hexanediamine.

The coating colors were made at 55% solids.

TABLE XI__________________________________________________________________________ Brookfield Viscosity Optical cps Hercules DensityDispersing Agent 10 RPM 100 dynes 20 mins.__________________________________________________________________________Calgon Imm. 960 300 2.1 0.668Calgon 24 hrs. 1400 416 2.4Polywet ND-1 Imm. 3160 824 4.1Polywet ND-1 24 hrs. 4480 1096 4.3 0.647Polywet ND-2 Imm. 640 210 2.3Polywet ND-2 24 hrs. 880 270 2.5 0.633Dispex N-40 Imm. 420 140 1.4Dispex N-40 24 hrs. 600 196 1.9 0.694__________________________________________________________________________

The use of Polywet ND-1 is of interest when thixotropy of a coating color is desired.

The Dispex N-40 results in the lowest viscosity and highest image intensity. The effect of Dispex N-40 and Calgon as dispersing agents as a function of time should be considered and the results are shown below using several different combinations of Calgon and Dispex N-40. The carbonless carbon pigment used in this study is composed of 25% montmorillonite, 75% GLOMAX JDF, 0.95% H.sub.2 SO.sub.4 and 0.50% 1,6-hexanediamine.

The clay-water slips as well as the coating colors were aged for a period of up to 32 days at 50.degree. C. The clay-water slips are at 55% solids, while the coating colors are at 50% solids.

TABLE XII______________________________________ Brookfield Viscosity Elrepho 5400 A.degree. Clay/Water Coating Optical 10 RPM Color Density cps cps 20 mins.______________________________________100% CalgonImm. 3,000 700 0.6061 day 2,000 4,000 0.6022 days 12,500 6,100 0.5733 days 14,000 6,400 0.5696 days 12,000 5,800 0.58510 days 15,000 17,600 0.59995% Calgon/5% N-40Imm. 4,400 1,800 0.5591 day 6,000 5,800 0.6142 days 5,400 3,600 0.5833 days 5,100 3,200 0.5776 days 4,700 2,600 0.59010 days 4,800 4,400 0.60292% Calgon/8% N-40Imm. 4,700 2,200 0.5901 day 6,000 4,000 0.5902 days 4,800 2,600 0.5783 days 4,800 3,000 0.6026 days 5,500 3,200 0.58510 days 4,600 5,600 0.58290% Calgon/10% N-40Imm. 3,500 1,100 0.5671 day 3,000 2,000 0.6002 days 4,200 2,300 0.5693 days 3,700 2,100 0.5806 days 3,600 1,800 0.58310 days 4,800 3,400 0.61680% Calgon/20% N-40Imm. 4,800 2,000 0.5581 day 4,500 2,200 0.5832 days 5,600 2,400 0.5783 days 5,200 2,400 0.6166 days 5,500 2,000 0.59510 days 4,700 3,800 0.58050% Calgon/50% N-40Imm. 3,800 1,400 0.6071 day 4,200 1,600 0.6062 days 5,200 2,000 0.5923 days 5,600 2,000 0.6146 days 6,200 2,100 0.60610 days 4,500 3,400 0.600100% Dispex N-40Imm. 1,500 500 0.6351 day 2,400 800 0.6562 days 3,000 1,000 0.6183 days 2,800 1,000 0.6316 days 3,400 1,100 0.65610 days 5,000 1,200 0.636______________________________________

The mixture of 90% Calgon (sodium hexametaphosphate) and 10% Dispex N-40 resulted in the optimum combination of slurry stabilization and development of image intensity. This mixture also results in excellent coating color stabilization. The optimum image intensity is developed with Dispex N-40.

While I have illustrated and described certain presently preferred embodiments and practices of my invention it will be understood that this invention may be otherwise embodied within the scope of the following claims.

Claims

1. A reactive pigment for manifold copy systems consisting essentially of a mixture of a member from the group consisting of metal ions and hydrogen ion, a ligand, a member selected from the group consisting of bentonite and montmorillonite and a kaolinite.

2. A reactive pigment as claimed in claim 1 wherein the kaolinite is calcined kaolinite.

3. A reactive pigment as claimed in claim 1 wherein the ligand is 1,6-Hexanediamine.

4. A reactive pigment as claimed in claim 1 wherein the metal ion is Cu derived from CuCl.sub.2.

5. A reactive pigment as claimed in claim 1 wherein the ratio of the member selected from the group montmorillonite and bentonite to kaolinite is 25% to 75%.

6. A reactive pigment as claimed in claim 1 wherein the ratio of the member selected from the group montmorillonite and bentonite to kaolinite is in the range 20% to 35% montmorillonite to 80% to 65% kaolinite.

7. A method of producing reactive pigments for manifold copy systems comprising the steps:

a. mixing a member from the group consisting of bentonite and montmorillonite with kaolinite in aqueous suspension,

b. adding to and dispersing in said mixture a member from the group metal ions and protons,

c. adding a ligand to and dispersing the same in the mixture of said member from the group consisting of bentonite and montmorillonite with kaolinite and a member from the group consisting of metal ions and hydrogen ion,

d. separating the solids, and

e. drying and pulverizing the solids.

8. The method of claim 7 wherein the kaolinite is a calcined kaolinite.

9. The method of claim 7 wherein the metal ion is Cu derived from CuCl.sub.2.

10. The method of claim 7 wherein the ligand is 1,6-Hexanediamine.

11. The method of claim 7 wherein the mixture of a member from the group consisting of bentonite and montmorillonite and kaolinite are dispersed in aqueous solution with a mixture of inorganic and organic dispersing agents.

12. The method of claim 11 wherein the inorganic dispersing agent is sodium hexametaphosphate and the organic dispersing agent is a polyacrylate.

13. The method of claim 11 wherein the mixture of dispersing agents consists of about 90% sodium hexametaphosphate and about 10% of a polyacrylate having a molecular weight of about 5000.

14. The method of claim 11 wherein the ligand is 1,6-Hexanediamine.

15. The method of claim 11 wherein the metal ion is Cu derived from CuCl.sub.2.