Color developing coating using unrefined clays on paper

Abstract

A color developing coating and coated paper are provided in which a paper sheet is coated with a mixture of dispersing agent, adhesive and a reactive pigment made up of essentially from the group bentonite and montmorillonite admixed with kaolinite, a polyvalent cation and a ligand.

Description

This invention relates to color developing coatings and coated papers and particularly to the production of such coatings and papers for use in pressure sensitive record materials.

The use of color developing 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 Patent 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 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 coatings. 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 coatings of this invention comprise in combination a polyvalent cation, a ligand, a bentonite or montmorillonite, a kaolinite, a dispersing agent and an adhesive. The preferred polyvalent cation is copper as CuCl.sub.2. The preferred ligand is 1,6-hexanediamine. Other polyvalent cations may be used, e.g. Cr, Fe, Co, Ni, Zn and Al preferably as a mineral acid salt such as the chloride. 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 composition may include extender pigments such as calcium carbonate and water retention aids such as sodium alginate and hydroxyethyl cellulose. Among the dispersing agents which we prefer are sodium hexametaphosphate (e.g. Calgon Corp.'s Calgon), metal salts of polyfunctional oligomer such as the sodium salt of polyfunctional oligomer (e.g. Uniroyal, Inc.'s ND-1 and ND-2) and the sodium salt of polyacrylonides (e.g. Allied Colloids' Dispex N-40). The preferred adhesives or binders are the latex types.

The practice of this invention can perhaps be best understood by reference to the following examples.

Two active clay specimens were prepared and incorporated into a general coating formulation involving the active clay, water, dispersing agent and binder. The two clay samples were as follows:

SAMPLE I

Forty-five grams of montmorillonite was 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 was added and allowed to stir for 15 minutes, at which time 0.9 g. 1,6-hexanediamine in 50 g. H.sub.2 O was added and allowed to stir for an additional 30 minutes. The slurry was then filtered and dried at 90.degree. C. overnight. The dried filter cake was pulverized three times on a Mikro Samplmill.

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

SAMPLE II

This sample was precisely the same as Sample I except that 1.80 grams of 1,6-Hexanediamine was employed.

The above procedure can be illustrated as: ##EQU2##

These two clay specimens were evaluated in color coating formulations using Dow Latex 638 as the adhesive and the optimum amounts of different dispersing agents.

The two samples were made down at 62% solids using the optimum amount of dispersant required. The aqueous viscosity data are given in Table I.

TABLE I______________________________________Clay-Water Viscosity Brookfield Viscosity (cpe)Sam- Dispersing % % RPMple Agent D.A. Solids 10 100 Hercules______________________________________1 Calgon 0.50 62 7,000 1,640 775 rpm2 Calgon 0.50 62 700 193 14.5 dynes1 ND-1 0.45 62 28,800 6.400 330 rpm2 ND-1 0.39 62 1,680 460 16.4 dynes1 ND-2 0.65 62 4,800 1,400 540 rpm2 ND-2 0.35 62 700 200 910 rpm1 Dispex 0.53 62 4,320 1,412 560 rpm N-402 Dixpex 0.35 62 900 280 13.2 N-40 dynes______________________________________

To the clay-water dispersion, 19.5 g. Dow Latex 638 was added and mixed on a low speed mixer for 5 minutes. At this point, the coating color viscosity measurements were taken.

The coating color viscosities are given in Table II.

TABLE II______________________________________Coating Color Viscosity Brookfield Viscosity Her-Sam- Dispersing % % (cpe) culesple Agent D.A. Solids 10 RPM 100 dynes______________________________________1 Calgon 0.55 60 3,200 896 5.42 Calgon 0.55 60 850 26 2.11 ND-1 0.52 60 16,800 3,328 8.82 ND-1 0.45 60 1,280 354 2.71 ND-2 0.71 60 2,120 588 6.42 ND-2 0.42 60 440 136 1.91 Dispex N-40 0.58 60 1,960 524 6.22 Dispex N-40 0.44 60 520 152 2.0______________________________________

The dispersing agents also effected the image intensities and rates of color development as shown in Table III.

TABLE III__________________________________________________________________________Image Intensity OPTICAL DENSITY Dispersing Immediate % 20 min. % 1 hr. % 24 hrs. %Sample Agent CVL Redness CVL Redness CVL Redness CVL Redness__________________________________________________________________________1 Calgon .642 31.6 .668 34.1 .692 37.7 .710 41.52 Calgon .574 28.2 .588 27.5 .649 32.7 .771 39.01 ND-1 .636 31.9 .647 34.6 .694 38.3 .723 42.62 ND-1 .595 28.7 .624 30.0 .668 31.3 .738 36.31 ND-2 .625 33.0 .633 35.4 .634 39.0 .692 41.92 ND-2 .612 29.2 .642 30.7 .673 33.0 .749 38.51 Dispex N-40 .684 35.2 .694 36.7 .715 38.9 .720 42.42 Dispex N-40 .584 27.7 .612 29.7 .673 32.4 .736 37.0__________________________________________________________________________

The best dispersing agent appears to be Dispex N-40 because it gives the most rapid image development while maintaining good rheological properties in coating color.

The effects of different binders were also examined and their influence on image intensity, color and rheology are shown in Table IV. The coating color viscosities are those for a 45% solids coating color. The amounts of binder used were 12% Dow Latex 638 and 16% Stayco M Starch on the weight of pigment.

TABLE IV______________________________________Effects of BindersBrookfieldViscosity(cpe) Her- %RPM cules Optical Density RednessBinder 10 100 dynes 1 hr. 24 hrs. 1 hour______________________________________Starch 3480 992 5.6 .274 .365 31.4Latex 40 46 0.6 .713 .723 40.0______________________________________

The effects of extender pigments like calcium carbonate have been found to be beneficial when used in certain proportions. This is illustrated in Table V. The several reactive pigments used in this study varied in the percent montmorillonite content.

TABLE V__________________________________________________________________________Effect of Extenders Brookfield Viscosity (cpe)% % RPM Hercules % Redness Optical DensitySample Montmorillonite CaCo.sub.3 10 100 dynes Imm. 20 min. 1 hr. Imm. 20 min. 1 hr.__________________________________________________________________________3 15 0 30 40 0.4 23.3 26.0 30.1 .480 .561 .617 25 30 44 26.6 28.5 33.9 .503 .540 .683 40 20 40 25.3 28.5 30.6 .407 .470 .5024 20 0 120 64 0.7 24.0 28.7 34.4 .524 .596 .655 25 120 78 28.5 31.2 37.0 .586 .621 .683 40 100 70 25.6 30.7 34.3 .496 .577 .6335 25 0 300 128 1.1 28.4 33.2 38.3 .574 .626 .664 25 320 144 33.2 34.2 41.1 .655 .698 .728 40 120 80 28.9 33.6 37.3 .577 .660 .6916 30 0 2120 690 2.9 28.1 33.9 38.2 .541 .602 .634 25 680 252 32.3 36.8 40.6 .647 .687 .726 40 220 92 30.0 35.6 39.9 .587 .674 .7147 35 0 5120 1600 5.2 31.5 35.4 38.7 .558 .590 .609 25 1520 560 36.7 39.2 44.2 .646 .665 .692 40 440 190 35.5 40.7 43.2 .664 .712 .740__________________________________________________________________________

The effect of other different extender pigments than calcium carbonate on the reactive pigment is illustrated in Table VI.

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.

TABLE VI__________________________________________________________________________Effect of Different Kaolinites ##STR1## Brookfield Viscosity (cpe) Optical RPM Hercules Density %Sample 10 100 dynes 1 hour Redness__________________________________________________________________________Premax (96% less than 2.mu. kaolin) 40 46 0.6 0.713 40.0KCS (80% less than 2.mu. kaolin) 60 52 0.6 0.678 39.2WP (58% less than 2.mu. kaolin) 80 64 0.6 0.711 40.2Astra Plate.RTM. (80% less than 2.mu. kaolin, 100 72 1.0 0.734 39.5delaminated)Glomax PJD (85% less than 2.mu. kaolin, 40 52 0.8 0.829 37.0partly calcined)Glomax JD (85% less than 2.mu. kaolin, 40 52 0.8 0.858 41.8calcined)Atomite (ground calcium carbonate) 60 60 0.6 0.591 35.0__________________________________________________________________________

The effects of water retention aids were also investigated, and it was found that the Kelgin F (sodium alginate) was better than Cellosize QP-4400 (hydroxyethyl cellulose) in that the Kelgin F did not reduce the image intensity of the pigment and, therefore, resulted in better rheology. Coating colors were made at 55% solids. The results are set out in Table VII.

TABLE VII______________________________________Effect of Water Retention Aids Brookfield Viscosity -(cpe) Her- Optical RPM cules Density % 10 100 dynes 1 hour Redness______________________________________Control 700 218 2.5 0.655 36.00.1% HEC 1200 376 3.6 0.620 32.92.0% HEC 4000 1056 5.6 0.663 35.10.4% Sodium 4600 850 2.7 0.670 35.2 Alginate______________________________________

Hand sheets were 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 densitometer. 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 Michler's hydrol type. The brightness and whiteness index were measured in accordance to the TAPPI procedures. Redness, in all examples set out in this application, is the ratio of the optical density at 5300A 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 on the reactive pigment is set out in Table VIII below:

TABLE VIII__________________________________________________________________________Effect of Metal Ions ##STR2## Brookfield Viscosity (cpe) Optical RPM Hercules Density % 10 100 dynes 1 hour Redness__________________________________________________________________________1. 3.96 g. CrCl.sub.3 . 6 H.sub.2 O 180 86 6.5 0.683 52.02. 3.96 g. FeCl.sub.3 . 6 H.sub.2 O 1720 236 0.9 0.747 43.63. 3.50 g. CoCl.sub.2 . 6 H.sub.2 O 180 80 0.6 0.713 44.74. 3.50 g. NiCl.sub.2 . 6 H.sub.2 O 200 80 0.6 0.691 47.05. 1.98 g. CuCl.sub.2 180 64 0.7 0.642 39.26. 1.98 g. ZnCl.sub.2 260 112 0.6 0.686 44.97. 0.99 g. ZnCl.sub.2 + 0.99 g. CuCl.sub.2 80 56 0.5 0.720 40.18. 9.90 g. Al.sub.2 (SO.sub.4) . 18 H.sub.2 O 100 68 0.6 0.680 32.19. 3.60 g. CuSO.sub.4 . 5 H.sub.2 O 80 64 0.8 0.667 40.5__________________________________________________________________________

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

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

TABLE IX__________________________________________________________________________Effect of Ligands ##STR3## Brookfield Viscosity (cpe) Optical RPM Hercules Density %Sample 10 100 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 2760 712 2.3 0.548 54.9 Dithiocarbamate__________________________________________________________________________

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 X.

TABLE X__________________________________________________________________________Effect of 1,6-Hexanediamine Content ##STR4## Brookfield Viscosity (cpe) Optical RPM HERCULES Density %1,6-Hexanediamine 10 100 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 bentonites or montmorillonites was also studied and the results are set out in Table XI.

TABLE XI__________________________________________________________________________Effect of Different Bentonites or Montmorillonites ##STR5## Brookfield Viscosity (cpe) Optical RPM Hercules Density %Sample 10 100 dynes 1 hour Redness__________________________________________________________________________Gelwhite.RTM. (Texas betonite from 60 46 0.9 0.663 44.9Helms deposit)K-4 (Wyoming bentonite from 20 44 0.2 0.698 32.4Midwest deposit)K-2 (Wyoming bentonite from 10 38 0.4 0.768 32.0Brock deposit)910 (Texas bentonite) 60 56 0.8 0.638 30.7Mississippi (Mississippi 20 36 0.4 0.400 32.5bentonite)__________________________________________________________________________

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 Table XII.

TABLE XII__________________________________________________________________________Effect of Bentonite Content ##STR6## Brookfield Viscosity (cpe) Optical RPM Hercules Density %Samples 10 100 Dynes 1 hour Redness__________________________________________________________________________15% 27 g. Montmorillonite85% 153 g. Kaolinite 30 40 0.4 0.617 30.120% 36 g. Montmorillonite80% 144 g. Kaolinite 120 64 0.7 0.655 34.425% 45 g. Montmorillonite75% 135 g. Kaolinite 300 128 1.1 0.664 38.230% 54 g. Montmorillonite70% 126 g. Kaolinite 2120 690 2.9 0.634 38.235% 63 g. Montmorillonite65% 117 g. Kaolinite 5120 1600 5.2 0.609 38.8__________________________________________________________________________

Table XII shows 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. The aqueous viscosity data are set out in Table XIII. The coating color viscosity data are set out in Table XIV. The comparative optical properties appear in Table XV.

TABLE XIII__________________________________________________________________________Clay - Water Viscosity cpe Brookfield Dispersing % % RPMSample Agent D.A. Solids 10 100 Hercules__________________________________________________________________________MBF 530 (acid leached bentonite) Calgon 6.8 45 2920 1144 12.5 dynesMBF 530 Dispex N-40 4.4 45 4640 1808 15.6 dynesSilton (acid leached bentonite) Calgon 3.5 45 180 148 5.0 dynes *Reactive Pigment #1 Calgon 0.5 62 7000 1640 775 rpm Reactive Pigment #1 Dispex N-40 0.53 62 4320 1412 560 rpm**Reactive Pigment #2 Calgon 0.5 62 700 193 14.5 dynes Reactive Pigment #2 Dispex N-40 0.53 62 900 280 13.2 dynes__________________________________________________________________________ *Reactive Pigment #1 ##STR7## **Reactive Pigment #2 ##STR8## TABLE XIV__________________________________________________________________________Coating Color Viscosity Brookfield Viscosity (cpe) Dispersing % % RPMSample Agent D.A. Solids 10 100 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 #1 Calgon 0.55 60 3,200 896 5.4 dynesReactive Pigment #1 Dispex N-40 0.58 60 1,960 524 6.2 dynesReactive Pigment #2 Calgon 0.55 60 850 25 2.1 dynesReactive Pigment #2 Dispex N-40 0.44 60 520 152 2.0 dynes__________________________________________________________________________ TABLE XV__________________________________________________________________________ Optical Optical Optical Dispersing Density % Density % Density %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 0.536 65.3Silton Calgon 0.501 77.6 0.501 80.0 0.481 82.1Reactive Pigment #1 Calgon 0.642 31.6 0.668 34.1 0.692 37.7Reactive Pigment #1 Dispex N-40 0.684 35.2 0.694 36.7 0.715 38.9Reactive Pigment #2 Calgon 0.574 28.2 0.588 27.5 0.649 32.7Reactive Pigment #2 Dispex N-40 0.584 27.7 0.612 29.7 0.673 32.7__________________________________________________________________________

The data accumulated from these examples shows that 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.

The term DISPEX N-40 is an Allied Colloid Corporation trademark for sodium polyacrylate and the term Dow Latex 638 is Dow Chemical Company's trademark for their latex adhesive.

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 color developing coated paper comprising a paper sheet having applied thereto a coating consisting essentially of a mixture of a dispersing agent, a paper coating adhesive and a reactive pigment consisting essentially of a mixture of a salt of a polyvalent cation, a ligand, kaolinite and a member selected from the group unrefined bentonite and unrefined montmorillonite.

2. A color developing coated paper as claimed in claim 1 wherein the ligand is 1,6-Hexanediamine.

3. A color developing coated paper as claimed in claim 1 wherein the salt of polyvalent ion is CuCl.sub.2.

4. A color developing coated paper as claimed in claim 1 wherein the ratio of the member selected from the group bentonite and montmorillonite to kaolinite is in the range 20% to 35% bentonite and montmorillonite to 80% to 65% kaolinite.