DE1961921A1 - Pressure sensitive copier paper - Google Patents

Description

ΓΑΤΕ NTA NWÄIT3

DR. E. WIEGAND DIPL-ING. W. NIEMANN / DR. M. KÖHLER DIPL-ING. C. GERNHARDT 1 ΰ 0 I 3 Z 1 MÖNCHEN HAMBURG TELEPHONE: 555 476 8000 MÖNCHEN 15, TELEGRAMS KARPATENT NUSSBAUMSTRASSE 10

Ip. December 1969

W. 14 598 / 6-9 7 / RS

Fuji Photo PiIm Co., Ltd, Kanagawa (Japan)

Pressure sensitive copier paper

The invention relates to pressure sensitive copier paper. A pressure sensitive copy paper is a material to which the principle is applied the one electron donating, color-reactive, colorless, organic substance (hereinafter referred to as color former) usually with an electron-accepting substance Substance in a medium of a non-polar oily solvent reacts to take on a color.

Leucomethylene blue can be used as color formers, Crystal violet lactone, rhodamine-B-lacturn, acidic bhodamine-S-sultone etc., and as a substance capable of accepting electrons, e.g. acid clay, active earth, A & tapulgite, aluminum sulfate, natural

009835/1293

natural zeolite, kaolin, bentonite, silicon dioxide gel, Feldspar, pyrophyllite, halloysite, magnesium trisilicate, ' Zinc sulfate, zinc sulfide, calcium fluoride and organic Acids or their salts, such as calcium citrate, tannic acid, Benzoic acid, etc.

The pressure-sensitive copier paper generally includes a combination of a sheet of paper, the surface of which has a coating of the above-mentioned color former, which is in a non-polar solvent, such as 3enzene, toluene, trichlorodiphenyl or the like. solved and then transferred into microcapsules, and a sheet of it Paper, the surface of which is electron-absorbing Substance is coated together with a binder. In certain cases a sheet can be one of its surfaces is coated with the microcapsules and the other side has a coating of the electron-absorbing Substance must be applied between the above two sheets. Occasionally a Sheet covered with the microcapsules and the electron receptive substance on the same surface, Find application. In each of the cases, the microcapsules become torn by the pressure of writing or printing and the color former solution contained in them becomes brought into contact with an electron receptive substance to give a colored copy image. The principle, the design and manufacture of such a material as described above are known (see U.S. Patents 2,548,366, 2,711,375, 2,730,256, 2 812 5o7, 2 8oo 457 and 2 8oo 458).

The above pressure-sensitive copier paper must be long

Time can be saved for some uses. The usual j

However, before color formers does not have the necessary requirements!

satisfactory because of the coloring |

009835/1293

Formers only poor weather resistance properties and is limited in terms of color. '

The object of the invention is to provide a pressure-sensitive copier paper that is not the aforementioned Has disadvantages of the known materials and characterized by special durability, stability and good color tint in use.

The pressure-sensitive copier paper according to the invention is characterized in that it is a compound of the general formula as a color former

(CH ₂ ) _n C00H

contains, in 4's η is an integer from 1 to 4, R ^ and R ₂ each represent an alkyl group with 1 to 4 carbon atoms or a phenyl group "and R ~ a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group , represents an alkoxy carbonyl group (wherein the alkyl has 1 to 4 carbon atoms) or a halogen atom.

It is sufficient if the above compounds in a solvent such as benzene, soluene, dioctyphthalate, Chlorodiphenyl or the like., Dissolved and then in the form of microcapsules as a coating on the surface of the paper. be applied. In use, the product can with that Sheet coated with the above-described electron receptive substance. Ge

009835/1293

-be applied as a coating on the paper surface. _O

The microcapsules made from the color former solution teönnea according to the US Pat described process can be produced *

The invention also includes the new compound according to the above formula.

The one represented by the above formula; links can generally be obtained by the following procedure.

and R ₁ R ₂ CHCOCH, are reacted in the absence of a solvent to produce a phenylhydrazone derivative. The phenylhydrazone derivative is then refluxed in the presence of ZnClg in ethyl alcohol

2
In the absence of solvent or using a suitable solvent at 10o to 15o ° C, reacted to form the quaternary salt. The thus obtained quaternary salt and ** · -formyl-β-naphthol can be refluxed together with triethylamine added in the calculated amount in absolute ethanol to obtain a compound represented by the above formula. The reactions under consideration can be represented by the following equations!

009835/1293

^R 3 ' ¹ ^ J-NHNH ₂ ⁺ CH ₃ COGh;

NHN = C-CH

. '' ^Λ 1

ί_ΝΗ. N = C-CH ^χ ZnOl "R ₂

·. 52

CH,

V-CH ₃ + Br (CH ₂ ) _n C00H H 1.1 +

CH

± jr (CHg) _n COOH-

RR ^{CH0 R} 1 ^R 2 OH

(CO ₂ ) 00OH

COOH

The pressure-sensitive copier paper according to the invention is excellent in durability. the preservation before and after use, because the compound according to the general formula given above has excellent solubility and stability, and therefore to a material with better weather resistance properties in comparison with the usual pressure-sensitive copier paper. Also is the above Connection excellent in terms of color shade.

009835/1293

Example 1 .

6.2 g of l-ß-carboxyethyl-2,3,3-trimethylindolenium bromide and 3 »4- g of oCA-pormyl-ß-naphthol were dissolved in 50 ml of ethanol, and after the addition of 2 g of triethylamine for 2 hours under reflux at about Boiled 78 ^{0 C.} Nach.der reaction, the ethanol was distilled off, white crystals were obtained, which were then recrystallized from ethanol, 3.6 g of l-ß-carboxyethyl-3 _s 3-dimethylspiro- (indoline-2,2'-2Ή-ß The melting point of this compound was from 203 to 208 ° C. A solution of the aforementioned compound in ethanol was encapsulated in microcapsules by the process described in US Pat. No. 2,800,457 Paper applied and combined with a sheet of paper coated with an acidic clay and a binder and written on with a typewriter, the pressurized areas being immediately colored red.

Example 2

To 100 g of an oxygenated aqueous solution of methyl cellulose was added 10 g of a solution of Vfo of the compound obtained in Example 1 in chlorinated diphenyl, and the mixture was vigorously stirred to form an emulsion. The emulsion was then coated onto a paper surface and dried. * The thickness of the coating layer was about 100 / rev. When the color-forming paper was placed one on top of the other on a paper provided with an ion coating, which was produced similarly to Example 1, and subjected to writing pressure, the areas under pressure were immediately colored red.

009835/1293

Example 3

In the same way as described in Example 1, 3.3 g of 1-ß-carboxyethyl-2,3,3> 5-tetramethylindolenium bromide and 1.7 g of ct- ^ ormyl-ßnaphthol were reacted to 2 , ο g of l-ß-carboxyethyl-3,3,5-trimethylspiro- (indoline-2, 2 '-2' H-ß-naphthopyran) in the form of white crystals. The melting point of this compound was 196 to 197 ^° C. When writing pressure was exerted after application of this compound, as described in Example 2, the areas placed under pressure were colored red.

Example 4

In the same way as described in Example 1, 3.5 g of 1-ß-carboxyethyl-2,3 »3-trimethyl-5-chloroindolenium bromide and 1.7 g of cC-formyl-ß-naphthol 'were reacted, with 1 , 3 g * l-ß-0arboxyethyl-3,3-dimethyl-5 "° ebl @ ro ° © pir @ = {i®i © lis. '=' 2 ₉ 2 ^fl <=> 2 ^e Hi-aa, phtliopyraß) was obtained in the form of white crystals. The melting point of this compound was from 2o6 to 2o8 ° C. A solution of this compound in chlorinated diphenyl was applied as a coating to a paper surface, which was then placed over the surface of a paper coated with clay and was pressurized. The pressurized areas were immediately colored red.

r Example 5 .

The compound obtained in Example 4 was put into microcapsules by the method of Japanese Patent 493,064 encapsulated. The microcapsules were

009835/1293

applied as a coating on paper and dried. The color-forming paper thus obtained was on a with Paper with a clay coating is placed on top and underneath Pressure put »The pressured bodies were immediately colored red.

009835/1293

Claims (4)

Claims le Pressure sensitive copy paper with a. Coating layer made from microcapsules containing a compound capable of producing a color-forming Reaction with an electron-accepting material is suitable, characterized in that the Compound of a compound of the general formula where η is an integer from 1 to 4-, R ₁ . and R ₂ each represent an alkyl group having 1 to 4 carbon atoms or a phenyl group and R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group (the alkyl having 1 to 4 carbon atoms), an alkoxycarbonyl group (the alkyl Has 1 to 4 carbon atoms) or represents a halogen atom. 2. Pressure-sensitive copier paper according to claim 1, characterized in that the compound of 1-ß-carboxyethyl-3,3-dimethyl-spiro- (ind (olin-2,2 · -2Ή-ß-naphthopyran),; l-ß -Carboxyethyl-3,3,5-urimethylspiro- (indoline-2,2 '· 2 ^l H-ß-naphthopyran) or 1-ß-0arboxyethyl-3,3-dimethyl-5-chlorospiro- (indoline-2,2 ^l -2 ^l H-ß-naphthopyran). 009835/1293 - Io - 3. Pressure-sensitive copier paper according to claim 1 or 2, characterized in that the β would take lektronenauf · capable material of sour clay, active clay or active earth, Attapulgite, zeolite, roline, bentonite, silicon dioxide gel, Aluminum sulfate, feldspar, pyrophyllite, halloysite, magnesium trisilicate, Zinc sulfate, zinc sulfide, calcium fluoride, calcium citrate, tannic acid or benzoic acid. where η is an integer from 1 to 4, R ₁ and H ₂ each represent an alkyl group with 1 to 4 carbon atoms or a phenyl group and R ^ a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group ( where the alkyl has 1 to 4 carbon atoms.), an AXkoxycarbony group (where the / klkyl 1 to Has 4 carbon atoms) or one Ha / ogenatom represents 009835/1293