FI61840B - BILDGIVANDESYSTEM - Google Patents

Description

r, ADVERTISING PUBLICATION, * Λ λ n jfäföfk ^ UTLAGG NIN GSSKRI FT OI 840 • C (45) Patent born 11 10 1932 Ä2 s2tj Patent meddelat V ^ (51) Kv.lk?/lnt.CI.3 B 41 M 5/12 FINLAND —FINLAND (21) P »t« nulh »k * mu« - Patanunsdknlng 751181+ (22) Hakamitptivl - An «öknlngid» g 21.01+. 7 5 (13) The beginning of the cloud —Giltlghetxdag 21.0li.75 (41) Tullut] ulki * «kil - Bllvlt offantilg 2l * 07.76 ^ ** ®n * ^ · I * Registry Board / 44) -

Patent · och registerstyrelsen Antdkan utlagd och utl.jkrlftan publlcerad 30.06.82 (32) (33) (31) Pyydetty etuoikeus— Begird priorltet 23.01.75

England-England (GB) 2928/75 (71) Ciba-Geigy AG, CH-1 + 002 Basel, Switzerland-Switzerland (CH) (72) James Kenneth Skelly, Wilmslow, Cheshire, James Harry Astbury,

This invention relates to an imaging system comprising paper impregnated or coated with a dispersion of a color former in water and a water-miscible organic substance of the color former. Stockport, Cheshire, England-England (GB) (7 * 0 Jalo Ant-Wuorinen Ab (5 ^) Imaging System - Bildgivandesystem in a solvent mixture, and an organic acid carrier saturated with a solution in a low-volatile high-boiling solvent.

Our Patent Application No. 751182 describes an ink containing a neutral or substantially neutral aqueous or anhydrous carrier, a liquid organic base and a color former. The ink is applied to selected areas of the substrate and when these are contacted with the acid, the printing changes color as the color former is activated.

In the system of the invention, the organic solvent should be one that dissolves the selected color former and is miscible with water. Suitable solvents include ketones, e.g. acetone; alkoxyethanols, e.g. methoxyethanol and ethoxyethanol; dimethylformamide and dimethyl sulfoxide. However, it is preferably non-flammable or has a relatively high flash point and is preferably 2,61840 non-toxic. It is also preferred to use a relatively low boiling solvent, for example one having a boiling point below 150 ° C.

The color former is preferably an azo compound of the general formula R1V-V yV κ (-ΧΊ) ρ „(-Η) O VN 12 n_1 X ^“ X ^ 2-r / "° Vn-l ^ K3 Λ_ / L Jn-1 -H 2] L 1c J 2 -n wherein, R 2 and R 2 each represent hydrogen, halogen, alkyl, alkoxy, aryloxy, alkoxycarbonyl, dialkylaminocarbonyl-Y 1, acylamino, acyl (alkyl) amino, -SO 2 -N, wherein Y 1 and R 2 v 1 * 2 Y 2 each represent alkyl or aryl, or wherein Y 1 and Y 2 together form an alkylene group, represents hydrogen or alkyl, X 2 represents alkyl, cyanoalkyl or arylmethylene, or X 1 and X 2 together represent an alkylene group, X 1 represents alkyl or aryl, and n is 1 or 2, preferably 1.

The amount of color former in the dispersion varies depending on the particular color former used and the desired effect, i.e., whether or not a dark color is desired. In general, the amount used may be 0.01 to 2, preferably 0.01 to 1, or more particularly 0, 5, e.g. 0.2% by weight.

Impregnated or coated paper is prepared by treating the pulp in a cholester or coating the paper with a color former dispersion as defined above.

The paper can be coated in any suitable manner, such as in an adhesive press, on a roll, using air-sweep coating, blade coating, brush coating, or by printing.

When using a dispersion to treat paper in a cholester, it is preferred to add the color former solution in the organic solvent directly to the cholester, which already contains a substantial amount of water, whereby the dispersion is formed in situ.

The paper must be either neutrally or alkaline bonded 3 61840 to prevent the color former from reacting prematurely with the paper. The pH of the paper used should not be less than 6.5 and this can be achieved, for example, by gluing with aluminum sulphate, rosin and sodium aluminate to provide a neutral sizing, or with a ketene dimer to produce an alkali-glued paper.

In some cases, it has been found that the dispersion is not stable enough to perform long treatment cycles using any of the coating techniques described above. In these cases, it is advantageous to add the polymer latex to the dispersion, with acrylic latex being particularly suitable. They can be added in amounts of 0.1-5%, preferably 0.5-2%. In addition, the dispersion may also contain starch in an amount of 1-10%, preferably about 5%.

The dispersion may further contain a dye or pigment. This will color the paper with its own color if a colorless color former is used, or with a different color if a colored, especially yellow, color former is used. In this way, different colors can be obtained when the treated paper is contacted with a color former activating agent.

Suitable activating agents include organic acids such as maleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tricarballyl acid, diglycolic acid, lactic acid, formic acid, tartaric acid, citric acid, citric acid, citric acid, citric acid, citric acid phenol-4-sulfonic acid, poly-maleic acid, co- and terpolymer of maleic acid with ethyl acrylate and vinyl acetate, hydroxyethane-diphosphonic acid, methylamino-N, N-dimethylenephosphonic acid, and acids known under the trademarks Dequest 2000 and Dequest 2010.

The method for forming an image impression comprises impregnating or coating a paper substrate with a dispersion as defined above, impregnating a carrier with a solution of an organic acid in a low-volatile high-boiling solvent, and transferring the organic acid to said impregnated or coated substrate.

The carrier impregnated with an organic acid may be a tissue, for example one used in typewriter ribbons, paper material, optionally in the form of a ribbon such as crepe paper, wet or dry woven paper, or a felt or tissue pad such as 4 61 840 used in conjunction with a rubber stamp, or a felt tip pen . The organic acid is preferably absorbed onto the fabric tape to make a typewriter tape, or into a felt or fabric pad. The organic acid is then transferred to the substrate by typing on the typewriter using the tape in question, or the pad by means of a rubber stamp. The carrier can be impregnated with 5-200% of an organic acid solution, preferably 5-100% of its dry weight.

The solvent used to dissolve the organic acid may be any low volatility, high boiling solvent having a boiling point of at least 150 ° C, preferably at least 300 ° C. Suitable solvents include, for example, partially hydrogenated terphenyl, liquid paraffin, tricresyl phosphate, di-n-butyl phthalate, dioctyl phthalate, trichlorobenzene, glycerol nitrobenzene, trichloroethyl phosphate, or glycol-insoluble alcohols such as water, pentyl, hexyl or preferably butyl phthaloyl butyl glycolate, ethylene glycol, diethylene glycol, triethylene glycol or polyethylene glycols having a molecular weight of 200 to 600, e.g. 400, or mixtures thereof.

The amount of organic acid in the solution is preferably such that a saturated solution is formed. Smaller amounts may be used, but these are less preferred. A small amount of water must be present in the organic acid solution obtained if the azo compound of the formula I is used, but this amount can be very small, in which case even the trace amounts are sufficient.

When the dispersion is used to impregnate the paper, the dye used in the cholester can be a water-soluble substantive dye or a dispersion of a water-insoluble dye or pigment. When a dispersion is used to coat paper by any of the above methods, the dye may be any water-insoluble dye or a dispersion of a water-insoluble dye or pigment.

The toner can be of any desired color, provided, of course, that it does not obscure the color that is formed when the color former is activated.

Several color changes are possible using different colors and color formers. Some of the many possible color changes include:

Yellow - * · blue This can be accomplished by using a yellow color former that turns blue upon activation, either as such or in combination with yellow dye. Alternatively, a colorless color former that turns blue upon activation together with the yellow dye can be used.

Yellow -> red

Same as yellow - * blue, except that colorformers are used that turn red when activated.

Colorless - »blue Colorless color former that turns blue when activated.

Colorless -> · red Colorless color former that turns red when activated.

Blue - »red

Blue toner + colorless color former that turns red when activated.

Red - * · blue

Red toner + yellow or colorless color former that turns blue when activated.

Green - »blue

Green toner + yellow or colorless color former that turns blue when activated.

Green · * · red

Green toner + yellow or colorless color former that turns red upon activation or blue toner + yellow color former that turns red upon activation.

Yellow - »green

Yellow toner + colorless color former that turns green when activated.

Blue · »green

Blue toner + colorless color former that turns green when activated.

Red - * · green

Red toner + colorless color former that turns green when activated.

Colored or colorless * black Color + a mixture of color formers which, when activated together with a toner, form black.

It should be noted that when a dye is present, the final color is the combined effect of the dye and the color formed by the activated color former.

When the color formers are azo compounds of formula I, they preferably have the general formula £ 61640

O

hJ-Vn-i Χ ^) 2. „(- ϊ) η, R6 \ _f (II) hl„ “wherein R1, R5 and R8 each represent lower alkyl, lower alkoxy, halophenoxy, phenoxy, lower alkoxycarbonyl, lower dialkylaminocarbonyl , acetylamino, halogen,

Yo style (lower alkyl) amino, 0 wherein Yo and Yu are each

~ bU2_w \ Y »H

means lower alkyl or phenyl, or wherein Yg and Y2 together form an alkylene group having * + or 5 carbon atoms, wherein up to two of the radicals R1, R8 and R8 are hydrogen, is hydrogen or lower alkyl, X8 is lower alkyl, lower cyanoalkyl or benzyl, or X 1 and X 9 together form an alkylene group having 4 or 5 carbon atoms, X 8 is lower alkyl or phenyl and n is 1 or 2.

Of particular interest are azo compounds of the formula O> -!: =]: - <V-i: 72 n 1 r9 \ _ / (Hi) K] L * - * 2-n where R? , Rg and Rg each represent methyl, methoxy, phenoxy, dichlorophenoxy, methoxycarbonyl, dimethylaminocarbonyl, γ 'acetylamino, chlorine, acetyl (methyl) amino, gg ^ 5 2 "> 6 joBsa y, and Y6 each represents methyl, ethyl or phenyl, or wherein Yg and Yg together represent a pentylene group, wherein up to two of the radicals R7, R8 and R8 are hydrogen, X2 is methyl or ethyl, Xg is methyl, 2-cyanoethyl or benzyl, Xg is methyl or ethyl, and n is 1 or 2 .

61 840 7

Advantageous results are obtained with color formers of the formula RV / X?

() ~ N = N- (Vn IV

ΚβΛ ^ / \ r9 where Ry, Rg, Rg, Xy and Xg have the same meaning as above, and color formers of the formula are particularly suitable.

Ri ^ <D

R 12 is wherein R 1q, R 1 and each represent methoxy, methoxycarbonyl, chlorine, diethylaminosulfonyl or acetylamino, wherein up to two of the radicals R 1g, R 2 and R 2 are hydrogen and Xy and Xg are as defined above.

The terms "lower alkyl" or "lower alkoxy" in the definitions of color-forming radicals mean radicals having 1 to 5, in particular 1 to 3, carbon atoms, such as methyl, ethyl, propyl, benzyl or amyl.

For example, when one or more of the R radicals contains acyl groups, the acyl radical may be derived from an aliphatic monocarboxylic acid having 1 to 4 carbon atoms, such as acetic acid.

When one or more of the R radicals is halogen, this is e.g. iodine, bromine but preferably chlorine.

When Yy and Y2 or Yg and Y1 together represent an alkylene group, they form a heterocyclic ring with a nitrogen atom, such as a piperidine or pyrrolidine ring.

Aryl radicals in the definitions of color formers refer in particular to naphthalene, diphenyl and preferably benzene radicals.

These color formers can be prepared by methods known in the art, e.g., by diazotizing the substituted aniline and coupling it to the N-subs tattooed aniline.

8 61840

Specific examples of compounds of general formula I for use in this invention are given in Table I, where n in formula I is 1, and in Table II, where n in formula I is 2.

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61 S40 14 The paper treated with the dispersion according to the present invention can be printed using the ink described in our patent application No. 751182 and provided that the ink used contains a color former whose color change differs from that already on the paper or which produces a different color change due to the ink containing a different colorant or pigment. , two color changes are observed when the paper is treated with acid.

The invention is illustrated by the following examples, in which parts and percentages refer to parts by weight and percentages by weight. Example 1: 0.1 part of color former no. 32 in Table I of formula f ~ \ N = N ^ yN / C2H5 \ = J W ^ CB2C6H5 COOCH3 was dissolved in 5 parts of 2-ethoxyethanol. This solution was then poured into 50 parts of water while stirring to form a dispersion.

This dispersion was added to a cholester containing 50 parts by weight of pulp dispersed in 2,500 parts of water. Then, 1 part of ketene dimer was added as an adhesive, and a sheet of paper was prepared in a conventional manner. The yellow paper turned red when it was stamped with citric acid on a stamp pad using a rubber stamp. Example 2:

Example 1 was repeated except that the color former solution was added directly to the pulp dispersion. Similar results were obtained. Example 3:

Example 1 was repeated except that the water contained 5% nonionic starch and 0.5% acrylic latex. The resulting dispersion had improved stability.

When added to the pulp as in Example 1, similar results were obtained.

Example 4:

Example 2 was repeated using the color former shown in Table 1.

61840 1 5

table 1

Pre- Paper mark_Color format and _color change 4 CH-.0 -f f- N = N yellow - ♦ · \ = J V = / \ CH blue 0CH3

Examples 5-15:

A dispersion was prepared according to the method described in Example 1 except that the dye was pre-dissolved in water. The combination of dyes and color formers and the color changes produced by the dispersion impregnated paper are shown in Table 2.

Table 2

Pre-color former Toner Color change mark eg No. | as% _________ _ 5 1 1 0.6% Direct Yellow 4 yellow - * red 6 1 0.5% "» yellow -> · red 7 4 0.5 0.5% "" yellow - 1 0.1 black 8 1 0.2% "mu yellow -► blue 9 0.5 0.5% Direct Blue 199 blue - + red 10 4 1 0.4% Direct Red 23 orange - * blue 11 1 0.5% Direct Blue 199 blue - * · green 12 1 0,1 0,1% Direct Blue 199) green - *

Acid Yellow red 13 1 1 0.5% Direct Blue 199) green - *

Acid Yellow 5) red 14 1 0.5% Direct Yellow 4 yellow green ^ 7 0.5% Direct Yellow 4 yellow + _ 7_ __ black_

Direct Yellow 4 = C.I. 24890

Direct Blue 199 = C.I. 74180

Direct Red 23 = C.I. 29160

Acid Yellow 5 = C.I. 47035 61 840 16

Examples 16-24:

An aqueous mixture of 500 parts of 4% aqueous starch, 2.5 parts of acrylic latex and 0.033 parts of the sodium salt of the naphthalenesulfonic acid / formaldehyde condensation product was formed. In some cases, dye was also added. To this mixture was added a color former solution in 11.8 parts of 2-ethoxyethanol to form a stable dispersion.

The resulting dispersion was applied to the paper by roll coating at 60 ° C using an amount of 0.2% by weight based on the fiber of the paper.

The color formers, dyes, and color changes obtained are shown in Table 3.

Table 3

Pre- Color former Toner Color change mark e.g., no. as f% ___ 16 1 0.5 - yellow - * · red 17 1 0.1 0.1% Direct Blue 199) green + red

Acid Yellow 5) 18 4 0.5 - yellow - * blue 19 4 0.1 0.2% Direct Yellow 4 yellow - * · gray / green 20 1 0.5 0.6% Direct Yellow 4 yellow - * red 21 1 0.2 0.05% Direct Blue 76 green> red 22 4 0.5 0.2% Direct Red 23 orange - + blue 23 1 0.5 0.25% Direct Blue 199) green -►

Acid Yellow 5) blue / black 24 1 011 4 θ'4 0.5% Direct Yellow 4 yellow -► black

Claims (2)

61 84 0 17 Claims;