Dye or color developing inorganic pigments

Abstract

An oxidizing clay for pressure sensitive record materials is provided by treating an acid leached clay with cupric salts.

Description

This invention relates to dye or color developing inorganic pigments and particularly to an improved oxidizing clay produced from bentonite.

The use of alumino-silicates in pressure sensitive record materials is well known. Typical of the various patents relating to this subject are, U.S. Pat. Nos. 3,455,721; 2,712,507; 2,730,456; 3,226,252; 3,293,060; and Canadian Pat. No. 780,254.

The pressure sensitive record materials are frequently termed "carbonless carbon papers" and are based upon use of oxidizing clays which react with another chemical to produce a colored product.

I have found that the oxidizing capacity of clays as well as their reactivity can be markedly enhanced. I have discovered first that by controlling leaching time, the oxidizing capacity of a clay can be varied. Secondly, I have found that the addition of cupric ions in the form of a cupric salt to acid leached bentonites will markedly improve their activity for pressure sensitive record materials and that the amount of cupric ion picked up will vary depending upon leaching time. For example, I have found that the most active clay, as determined by the oxidation of leuco methylene blue, was found to be the 4 hour leached sample, exchanged with cupric ion. The most reactive, non-exchanged clay was found to be the 16 hour leached material. The reactivity of pigment towards aniline (converting aniline to aniline black) was found to be highest on the bentonite which had been acid leached for four hours and exchanged with cupric ion.

The subject matter of this invention can, however, best be understood by reference to the following examples:

EXAMPLE I

Two hundred grams of bentonite was added to a solution of H.sub.2 SO.sub.4 and water (200 g. H.sub.2 SO.sub.4 in 800 ml. H.sub.2 O). This mixture was then heated at 90.degree. C. for a period of 4 hours, after which the slurry was then filtered. The filter cake was then reslurried and 12 g. of CuCl.sub.2 was added and the slurry was allowed to stir for 15-30 minutes. The Cu(II) saturated clay was then filtered, rinsed, and dried at 105.degree. C.

EXAMPLE 2

One gram of the material prepared in Example 1 was weighed out in a watchglass and 2.0 ml. of a 1% solution of leuco methylene blue in xylene was added and allowed to stand exposed to the air for 24 hours and the intensity of the color was compared visually among the various samples. The results appear as item 12 on Table I.

Other color reactive materials were incorporated into the clay and color intensity was compared using xylene and DBP as solvent. The results appear in Table I.

TABLE I__________________________________________________________________________ Acid Activated Bentonite Oxidizing ClayCompound Solvent (after 72 hours in dark) Cu(II) Acid Activated Bentonite__________________________________________________________________________ m-phenylenediamine xylene light brown pink few seconds, dark red 10 minutes DBP light brown dark brown few minutes, black-brown 10 minutes p-phenylenediamine xylene green light green ca.10 minutes DBP green fringe, light brown dark green ca. 10 minutes center with black specks dark blue after 72 hours o-phenylenediamine xylene light pink pink, 10 minutes DBP light pink, brown center light brown, 10 minutes p-nitroaniline xylene light yellow initially light yellow few seconds and 72 hours and 10 minutes DBP light yellow initially light yellow-green and 72 hours 10 minutes p-aminophenol xylene very faint yellow no color DBP pale violet very pale brown bis-cyanoethyl aniline xylene yellow yellow, 10 minutes DBP light blue center, light green, 10 minutes yellow fringe m-diethylamino xylene light brown gray, 10 minutes phenol DBP gray slight gray, 10 minutes aniline pink black with green rim ca. 10 minutes N,N dimethylaniline no color light green, 10 minutes (dark blue after 1 week)10. N,N diethylaniline no color dark blue, 10 minutes (dark green after 1 week) m-choroaniline very pale yellow with pink fringe dark gray, 10 minutes leuco methylene blue dark blue dark blue, 10 minutes__________________________________________________________________________

The same results are obtained using montmorillonite for bentonite.

It can be seen fron the foregoing test data that the materials of this invention using cupric ion exchange produce more intense colors in shorter times than do oxidized clays alone. This is, of course, highly desirable.

In the foregoing specification I have illustrated and described certain preferred embodiments and practices of my invention, however, it will be understood that this invention may be otherwise embodied within the scope of the following claims.

Claims

1. An oxidizing clay for pressure sensitive record materials comprising an acid leached clay from the group consisting of bentonite and montmorillonite carrying ion exchanged cupric ions.

2. An oxidizing clay as claimed in claim 1 wherein the clay is bentonite.

3. An oxidizing clay as claimed in claim 1 wherein the clay is montmorillonite.

4. An oxidizing clay as claimed in claim 1 wherein the acid leached clay is exchanged with cupric ions from CuCl.sub.2.

5. An oxidizing clay as claimed in claim 4 wherein the cupric chloride constitutes about 1% to 6% by weight of the clay.

6. An oxidizing clay as claimed in claim 1 wherein the clay has been leached for about 4 hours with sulfuric acid.

7. The method of producing an oxidizing clay for pressure sensitive record materials comprising the steps of

(a) leaching a selected clay from the group bentonite and montmorillonite with mineral acid, and

(b) affixing cupric ions to the exchange sites of the treated clay by ion exchange.

8. The method as claimed in claim 7 wherein the cupric ions amount to about 0.5 to 1.6%.

9. A pressure sensitive record material comprising an acid leached clay having attached thereto ion exchanged cupric ions.

10. A pressure sensitive record material as claimed in claim 9 wherein the clay is bentonite.