DE2031488B2 - PRINT SENSITIVE COPY PAPER - Google Patents

Description

30th

-C = O

represents wherein Ri and R2 represent an alkyl group with 1 to Carbon atoms, R3 is an acyl group and R. is an aryl group.

2. Pressure-sensitive copier paper according to claim 1, characterized in that the fluoran compound from one of the compounds

3-diethylamino-7- (N-acetoanilino) -fluorane,

3-Dimethylamiro-7- (N-aceto-p-toluidino) -

fluoran,

3-diethylamino-7- (N-aceto-m-toIuidino) -

fluoran,

4-diethylamino-7- (N-aceto-o-toluidino) -

fluoran,

4-diethylamino-7- (N-aceto-m-xylidino) -

fluoran,

3-diethylamino-7- (N-aceto-o-anisidino) -

fluoran,

3-diethylamino-7- (N-aceto-p-anisidino) -

fluoran,

3-N-ethyl-N-isopropylamino-7-

(N-acetoanilino) -fluorane,

3-diethylamino-7- (N-benzoylanilino) -

fluoran and

3-diethylamino-7- (N-benzoyl-p-toluidino) -

fluoran
consists

45

The invention relates to pressure-sensitive copier

Cr, consisting of a carrier with one on it indigenous layer of microcapsules that contain a color former, which on contact with a solid acid forms a color.

Pressure-sensitive copier papers usually consist of a combination of two papers, where the top paper by dissolving an electron-accepting color-forming and practically colorless one organic compound, hereinafter referred to as "color former", in an organic solvent, Encapsulation of the solution in microcapsules and application of the microcapsules to a carrier for 6 seconds and the bottom paper was made by applying an electron donating solid acid to it another carrier was made. In some cases, the pressure sensitive copy paper is made of a combination of an upper paper, a lower paper and an intermediate paper that can be formed by application of microcapsules that contain a solution of the color former in an organic solvent one surface of the support and by applying the solid acid to the other surface of the same Carrier was made.

Furthermore, pressure-sensitive copier papers are known in which the above-mentioned Microcapsules and the solid acid as a mixture or in the form of two layers on one side of a support are upset.

In use, pressure-sensitive papers are made of a combination of two or more Papers The papers are stacked so that the microcapsule layer is in contact with the solid acid layer where it can then be locally pressed, and in the case of pressure-sensitive paper, from the monolayer Type, the drawn-up layer can be pressed locally, whereby the microcapsules break open and the Dye solution in the microcapsules comes into contact with the layer of solid acid, so that a Forms paint on the locally pressurized parts.

As solid acids, for example, inorganic acidic materials such as bentonite, zeolite, acidic clay, Active clay, magnesium trisilicate and the like, and organic acidic materials such as benzoic acid, benzenesulfonic acid. Naphthol and the like can be used.

Rhodamine lactone and rhodamine anilinolactam are used as color formers and the like known

These known color formers with the ability to form red have the following disadvantages: Rhodamine lactone itself is unstable when it is in the surrounding atmosphere so that it is colored in a short time, d. H. is colored spontaneously before it comes into contact with the solid acid, which is hereinafter referred to as "color-forming Veil ”. On the other hand, if rhodamine aniline lactam is used, it should be brought into contact of the color former with the solid acid takes a considerable time for complete color development necessary.

Color formers, which are used for pressure-sensitive copier papers, should be carried out before they are implemented When in contact with the solid acid, it is colorless and, on exposure to the atmosphere, without the formation of a haze be stable, the color development should take place immediately upon contact with the solid acid, and they are said to provide images of high color density with excellent lightfastness and water resistance.

In this regard, the aforementioned color formers are unsatisfactory.

In the older DT-PS 16 71 545 pressure-sensitive copier papers are described as color formers Contain 3,7-substituted fluorans. The images produced with the known color formers are however, not yet satisfactory in terms of their quality.

The object of the invention is therefore to provide a pressure-sensitive copying paper from a carrier with a layer of microcapsules thereon, which contain a color former, which on contact with a solid acid forms a color, with images excellent in color density and excellent Lightfastness and water resistance can be preserved and color haze can be reliably avoided.

The solution to this problem is carried out according to the contain a color former, which on contact with Invention through the creation of a pressure-sensitive solid acid that forms a color Chen copier paper, consisting of a carrier is marked with that the color former is a fluoranciner thereon a layer of microcapsules, the compound of the general formula

'n

R ₂ I i: ü; R,

^N \ / ^X C "'NA /

I 'Ό

A \ ^R '

- V-C = O

represents wherein R 1 and R 2 represent an alkyl group of 1 to 7-position through an acyl group or an aryl group

Carbon atoms, R3 is an acyl group and R4 is 20 substituted

Means aryl group. Examples of suitable color schemes are given below.

The feature regarding the structure of the by the creators who apply within the scope of the invention

The general formula given above is given:
bonds lies in the fact that the amino group of the

l-arb- General 1-orniel Chemical Bc / eichnuni:

sculptor

No. R, R: R. » Ra

C ₁ H, CH ₅ —C —OH, - <> 3-diethvlamino-7- (N-acetoanilino) -fluorane

Il O

CH ₃ CH., —C — CHj - / V-CH ₃ 3-Dimelhylamino-7- (N-aceto-p-toluidino) -

II ^ = ¹ - "fluorane
O

CH ₅ C ₁ H ₅ -C-CH ₃ ~ \ / 3-diethylamino-7- (N-aceto-m-toliiidino) -nuorane

⁰ CH,

C ₁ H ₅ C ₂ H ₅ -C-CH ₃ - <f ρ 4-Diethylamino-7- (N-aceto-o-toluidino) -fluorane

I.
CH ₃

C ₂ H ₅ C-, H ₅ -C-CH ₃ -CH ₃ 3-diethylamino-7- (N-aceto-m-xylidino) -fluorane

Il p

⁰ CH ₃

C ₁ H, C ₁ H ₅ -C - CH, - <(/ 3-Diethylamino-7- (N-aceto-o-anisidino-fluorane

⁰ OCH,

CH ₅ C ₁ H ₅ -C-CH ₃ - <f 'V-OCH ₃ 3-diethylamino-7- (N-aceto-p-anisidino) -fluorane

Il ^{x /}

C ₁ H ₅

Il
ο

C ₁ H ₅ ISo-C ₁ H ₇ —C - CH, - <S y 3-N-Ethyl-N-isopropylamino-7- (N-acetoanylino) -

Ii = fluoran

■ = - fluorane

Continue us

Coloring General formula

sculptor

No.R ₁ R, R,

Chemical name

9 C ₂ H ₅ C ₁ H ₅ -C- <

10 C ₁ H, CH ₅

-C— <f
O

3-Diachvlamino-7- (N-benzoylaniIino) -fluorane

- / f ^X V CH, 3-diethylamino-7- (N-benzoyl-p-to! uidino) -

^ = - '' fluoran

The production of the above-mentioned color former will now be explained in general.

1 mole of the intermediate A o- (4-Dia! Ky! Amino-2-hydroxybenzoyl) benzoic acid and 1 mole of the intermediate B p- (N-acyl-n-arylamino) phenol are in the presence of a dehydrating agent, such as. B. sulfuric acid, fuming sulfuric acid, phosphoric anhydride, anhydrous zinc chloride or phosphorus oxychloride, for 3 to 50 hours at 20 to 90 ⁰ C under-throw a condensation reaction. The reaction liquid is poured into a large amount of ice water, and then an aqueous alkaline solution such as. B. aqueous sodium hydroxide solution, added to the mixture to render the resulting mixture weakly alkaline. The material precipitated by the procedure described above is extracted with acetone, and the extract is concentrated and dried to give the compound.

The intermediates A and B used above are prepared according to the following procedures manufactured

The intermediates A used to prepare the above compounds can be used in a known manner Manner, for example, by refluxing 1 mole of an m-dialkylaminophenol and 1 mol of phthalic anhydride in toluene for a few hours, according to Friedländer, Volume 4, p. 260. The intermediate product B can also be produced by known processes, for example by Performing a dehydration condensation with an aniline and hydroquinone to form a p- (N-arylamino) phenols according to the following equation

H ₂ NR ₄ + HO-

> —OH conc. H ₂ SOj

HO

-N-

wherein R4 is an aryl group, or through Acylation of the above product in the usual way according to "Chemical Abstracts", Vol. 52.7184.

The production of the color formers used in the context of the invention is explained below.

Production example 1
(Color former 1)

1 mole of o- (4-diethylamino-2-hydroxybenzoyl) benzoic acid with the structure of intermediate A, in which Ri is the group C2H5 and R2 is the group C2H5, and 1 mole of p- (N-acetoanilino) phenol having the structure of intermediate B, wherein R3 is a moiety

—C — CH ₃ and R _{4 are} a group— <f ¹ ^

I! " ^x '· -'

Il

means, were for 24 hours at about 50 ° C in 10 moles of concentrated sulfuric acid condensed. Then, ice water became the reaction product Poured in, the mixture made weakly alkaline with sodium hydroxide and the product with toluene extracted, concentrated and dried, taking 3-diethylamino-7- (N-acetoanilino) fluorane was obtained as an amorphous solid product.

Production example 2
(Color formers 2 to 10)

By using the intermediates A and B in accordance with the color formers desired in each case as in Example 1, the following color formers were obtained.

The absorptions of the color formers in the visible range in 95% acetic acid are shown in the table below specified:

Color formers Absorption of the Color screeners Λ, λι 386 1 502 539 388 2 507 550 387 3 503 544 391 4th 506 535 390 5 507 539 393 6th 511 534 391 7th 507 530 389 8th 511 544 387 9 503 540 389 10 509 551

For the production of pressure sensitive papers according to the invention using the in the

The color formers shown in the general formula listed above can be those in the US patents 25 48 366, 28 00 457 and 28 00 458 are used, d. H. the procedure the manufacture of microcapsules using composition coacervation. However, since the present invention from the point of view of applying the compounds according to is based on the above general formula, the properties of the pressure-sensitive paper are not influenced by the way it is manufactured. So there are no such limitations on the production of the pressure-sensitive papers in the context of the invention. The amount of color former is usually 1 to 5 percent by weight of the oily solvent.

The pressure-sensitive papers according to the invention are colorless and before the color-forming reaction can be stored stably under atmospheric conditions without the formation of spontaneous Color fogging occurs If the pressure sensitive papers are colored by pressing, this will Color image instantly formed, i.e. h, the speed of color formation is extremely high. Furthermore, the color density of the copied image is high, and the image has excellent lightfastness and water resistance

Since the color formed here has an absorption in the spectral range of about 350 to 420 πιμ, what the photosensitive area of a photosensitive diazo paper, the copied image can be on copied from a photosensitive diazo paper.

The color formers shown in the general formula given above provide dyes Red formation, but by mixing the color formers with other known yellow, purple, blue or green-forming color former, pressure-sensitive copier papers that are dyed in different colors are to be produced.

example 1

3 g of the color former 1 were dissolved in 100 g of diphenyl trichloride and the solution by adding a aqueous solution of 20 g of gum arabic emulsified in 60 g of water

Then, an aqueous solution of 20 g of an acid-treated gelatin in 160 g of water was added to the emulsion, and after the pH was lowered to 5, 500 g of water was added for coacervation, thereby forming dense liquid films of gelatin and gum arabic around the oil droplets, in which the Color formers were dissolved, were formed. The pH was further reduced to 4 and then 4 g of a 37% formalin was added for hardening. During the above process, maintaining the temperature of the system at 5O ⁰ C, however, then the system to 1O ⁰ C was cooled for gelation of the dense liquid film, the pH is increased to 9 for increasing the Härtungseffektes and then the system was allowed to stand for a few hours , thereby completing the encapsulation operation.

The capsule-containing liquid obtained in this way was printed on a paper by any winding method, for example drawn up by roller application or air sheet application and dried. That The upper paper formed was placed on a construction paper (lower paper produced by applying a clay material on a piece of paper) and then both locally pressed together by labeling, what the red Record was instantly obtained on the construction paper.

When the resulting red dye record was wetted with water or exposed to sunlight for a long period of time, no fading occurred. Also, when the upper paper was heated to 100 ⁰ C for 20 hours and was exposed to sunlight for a long period, the color-forming power of the upper paper was not deteriorated Thus, according to show the pressure-sensitive papers of the invention, a sufficient light-fastness and water resistance before and after the color formation, the sufficient for all practical purposes

Example 2

It was prepared according to the same procedure as in Example 1 using color formers 2 to 10 Place of Color Former 1 Worked In each case, when the color former was used, it was instantaneous a red record formed on the construction paper The properties of the pressure-sensitive paper before and after color formation were excellent as in Example 1.

409 518/35:

Claims (1)

Patent claims: 1. Pressure-sensitive copier paper, consisting of a carrier with an on it Layer of microcapsules that contain a color former that reacts on contact with a solid acid forms a color, characterized in that the color former is a fluoran compound of the general formula <