DE2518871A1 - SECURITY DOCUMENTS - Google Patents

Description

The invention relates to security documents and a method for checking the authenticity of a security document.

Security documents have contained security features for many years like watermarks and security threads. There were already threads, ζ. B. made of silk or nylon, or small Fragments or platelets with different colors entered into paper for security purposes. Invisible or visible fragments of such materials have been incorporated, some of which appear visible when exposed to ultraviolet light to be viewed as. Other methods of checking security documents rely on machines to read the documents check using optical or magnetic devices.

Such methods, which should be pointed out in particular, are passive examinations which involve the inspection of the security document by a person or a machine. The invention relates to a security document in which a security device provided by the presence of

Kcmfen: D «uti = h» BankAG, 509846 / Q987 Munich MO «0-807

Substances that can participate in a color formation reaction in and / or on the document.

Color formers have been at pressure sensitive for several years Transfer copy sets comprising a transfer sheet and an adsorbent sheet have been used. The transfer sheet has on one surface thereof that is in contact with the adsorbent sheet is a coating. The coating contains a solution of the color former, which in the coating or the Coating is retained by tearable microcapsules or a tearable, solid film. The absorbent sheet carries a substance that reacts with it on its surface, which reacts with the color former during a color-forming reaction can participate. When localized pressure is applied to the transfer sheet, the microcapsules will tear or the film and a solution of the color former is released and reacts with that which reacts with it Substance of the absorbent sheet with which it is in contact. An image corresponding to the applied pressure is generated on the adsorbent sheet as a result of the color forming reaction. Such pressure sensitive transfer copy sets are in U.S. Patents 3,488,20? and 3,244-728 described.

Color formers are also for use in typewriter tapes known, e.g. B. as in GB-Pat ent writing 664 4-56 is described. The tape, which is generally white, carries a non-evaporable, inert liquid which is the Contains color former. When used in a typewriter with a paper containing a substance that reacts with it carries on its surface, the color former reacts with the substance that reacts with it and a Color change. The tape can be a number of lengthways have running stripes or bands, wotoe. each one

609 8 46/098

_ 3 -

Contains color-reactive substance that is effective in transmission from the tape to the surface of a paper that has a substance that reacts with the color-reactive substances, assumes a distinctive coloration characteristic of that stripe or band.

An advantage of the invention is that color-forming reactions used in security documents, creating a method of verifying the authenticity of security documents is possible in an active test.

According to the _# invention, a security document is provided comprising a substrate, or a support, a first substance which is incorporated into the support or the support or respectively the support is applied to the substrate, said first substance to participate in a Color formation reaction in the

and
Is / a second substance, which is applied to the base or the carrier, this second substance to participate in a different color formation reaction in the

includes, ..

Is able to / whereby when carrying out the review of the Security document by applying a reagent or reagents to the security document, this first substance and this second substance changes its color through color-forming reactions.

The term "security documents" as used in the description is used, z. B. negotiable securities that are valid in cash on presentation at any time can be converted, e.g. B. checks, travelers checks, postal orders, lottery tickets, commercial checks, bearer bonds and similar financial documents; Documents which leave the owner valuable rights, z. B. Passports, admission tickets, travel tickets include. This expression should also Include banknotes.

509846/0987

The base or carrier which is used in security documents according to the invention can be made of paper and / or Cardboard made from natural or synthetic materials. The document or the carrier is a continuous sheet of plastic material be which, if necessary, z. B. has a paper strip glued to it.

The first substance can comprise one or more color formers, and it can also contain one or more colored ones in each jail Substances, e.g. B. contain a pigment or dye that does not change color when the document is checked. Such colored substances can be entered to allow a wide range of color changes.

The first substance can be completely contained in a paper support be introduced by passing the pad through a solution or dispersion of this substance, e.g. B. by means of a sizing press. Alternatively, the substance can be applied to all or part of one or both surfaces printed on the document. Other coating methods can be used, e.g. B. the procedure below Use of the known per se calendering or by coating by means of a doctor blade or air knife.

The first substance can also be entered at the time of preparation of the pad, e.g. B. by adding to a Starting paper mass during the production of a paper base.

The colored substances and the color former can be entered separately at the time of production of the base or the color formers can be in or on the substrate, as before

509846/0987

■ described, installed or applied. Alternatively the color former or the color former can be incorporated during the production of the base, and the colored ones Substances can be entered into or applied to the substrate as described above.

In general, the ingredients of the first substance can be used separately or in any combination during manufacture added to the base or introduced into the base or applied to the base, as described above.

It should be noted that the paper or other support does not contain any ingredients which are in any way required Would interfere with the color formation reaction, and also no ingredients of any kind that would cause the required color change, which would interfere with the review of the document.

The security document can incorporate a band or several bands of the first substance into the substrate or onto the Have applied to the surface of the base. The second substance can be on the backing on top of the first Substance to be applied. One or more coatings or prints of the second substance can be applied. The second substance can be any of the ingredients or combinations of ingredients as the first substance, as before described, included. One or more second substances can be applied to the base. The coatings or the print jobs for the first or second substance can take place in different arrangements.

At least two substances that change color are employed in accordance with the invention, and more may be required

509846/0987

to be applied separately as a reagent to produce the changes required in the test. In some Cases a reagent causes two or more color changes, and ■ also causes application of a mixture of reagents in other cases the desired effect.

It is preferred that the reagent or reagents be colorless, and it is further preferred that an exterior applied, colorless reagent is used to activate any color changes on and / or in the document.

The colorless reagent or reagents can be referenced to the security document by any suitable means Funds are raised. Specific examples of such means for bringing the reagent or reagents into contact with the Security documents are a stamp and an ink pad, a felt pen, a roller device through which the Security document is sent through, a roller or a brush to apply the reagent directly to the document or a stamp with ink supply, ζ. Β. a plunger containing a reservoir for the reagent and a capillary tube for supplying the reagent from the reservoir includes the working surface of the stamp.

A security document according to the invention has the property that it can be checked and confirmed, d. H. that its authenticity is examined when the document is presented will, d. H. the owner wants to take advantage of the advantages given by the document by simply adding the simple Application of the required reagent or reagents is carried out to produce the required color change or to produce the necessary color changes.

509846/09 8 "?

The security document according to the invention has the advantage that it is very difficult for a potential forger is to determine the nature of the first and the second substance which are present in and / or on the security document, and also determine which reagent or which Reagents are required to produce the required color changes.

The invention may be in addition to or in combination with others Use is made of security features which are built into the base and / or which are applied to the base are. In the document, such security features are z. B. watermarks, security threads, threads, platelets and like that. On the document, such security features include the print design, e.g. B. Rainbow coloring and types of printing inks, ζ. Β. fake printing inks.

The invention also includes a method for reviewing and confirming a security document of the type described above Kind, this process comprising applying the required reagent or reagents to the security document to effect the desired color change or change to produce desired color changes.

In the field of dye chemistry, numerous substances are known per se to the person skilled in the art which have the property of changing color when brought into contact with a reagent, e.g. B. Disazo dyes. The substance can may be initially colorless, but usually a change from one color to another occurs during the color forming reaction with a suitable reagent. It should be noted that the substances involved in the color formation reactions participate, must be present on one surface of the substrate, so that one of the in the original

509846/0987

Document present image received different colored image when the final colors are developed, the color difference comprising at least two color changes.

In British patent application 2928/75 by Ciba-Geigy-AG is a composition for incorporation into a paper pulp or for the complete or partial coating of paper described, wherein the composition is a dispersion of a color former in a mixture of water and one with water miscible organic solvents for the color former.

British patent application 18199 / 74- from Ciba-Geigy AG relates to a printing ink which has a neutral or practically neutral dye carrier, a non-volatile, liquid, organic base and a color former. The printing ink is used for printing on selected areas of an underlying surface and when it is brought into contact with an acid, the pressure changes color as a result of activation of the color former.

Those described in British Patent Applications 2928/75 and 18199/74 Color formers are in the present invention as components of the first and second substances, which incorporated into the base of the security document or applied to it, is suitable.

The organic solvent for the composition for incorporation in a mass of paper, as previously described, should be a solvent that contains the selected color former dissolves and is miscible with water. Suitable solvents include ketones, e.g. B. acetone, alkoxyethanols, e.g. B. methoxyethanol and 1thoxyethanol, dimethylformamide and dimethyl sulfoxide.

509846/0987

However, it is preferably a non-flammable solvent or a solvent with a relatively high flash point, which is preferably non-toxic. Furthermore, it is preferred to use a solvent with a fairly low boiling point, e.g. B. a solvent with a boiling point below 150 ⁰ C.

The amount of color former in the dispersion varies depending on the particular color former used and the effect desired, d. H. depending on whether a dark one Coloring is desired ■ or not. In general, the amount used from 0.001 to 2% by weight, preferably from 0.01 to 1% by weight and particularly preferably from 0.1 to 0.5% by weight, z. B. 0.2 wt .-%.

The paper can be coated in any suitable manner, e.g. B. in a size press, by roller application (Calendering), by coating with an air knife, by coating with a knife, by brush application or by Imprint.

If the dispersion is used to treat paper stock in a grinder, it is advantageous to use the solution of color former in organic solvent directly into the grinding device, which already has a significant amount of water to enter in situ to form the dispersion.

The paper used must be either neutral or alkaline sized or coated to prevent premature reaction to prevent the color former with the paper. The pH value of the paper used should not be below 6.5, and this can e.g. B. by painting with aluminum sulfate a resin size and sodium aluminate to make a

5098A6 / 0987

neutral sizing or with a ketene dimer for production an alkaline coated paper can be achieved.

If the treated paper with a color former activating Substance is treated, and activating substances can according to the invention as a reagent or as Eeagentien which participate in the color forming reaction with the appropriate constituents of the first and second substances participate in and / or on the document of the security document, a color change is caused.

Suitable activating substances or reagents are organic acids such as maleic acid, oxalic acid, malonic acid, succinic acid, Glutaric acid, adipic acid, tricarballylic acid, diglycolic acid, Lactic acid, malic acid, tartaric acid, citric acid, pyrophosphonic acid, Benzenesulfonic acid, naphthalene-2-sulfonic acid, 1-phenol-4-sulfonic acid, Polymaleic acid, copolymers and terpolymers of maleic acid with ethyl acrylate and vinyl acetate, hydroxyethandipho sphonsäur e, methylamino-N, N-dime thy 1 enpho sphonsäure and the substances known under the trade names Dequest 2000 and Dequest 2010.

If the color former is a triazene compound of the formula II, it must also be in contact with a Δζο coupling component are brought, which can be present in a mixture with the activating substance.

Such organic acids are volatile generally weak in a dissolved high boiling solvent having a boiling point of at least 150 ⁰ C and preferably at least 300 C. Suitable solvents include e.g. E.g .: partially hydrogenated terphenyl, liquid paraffin, tricresyl phosphate, di-n-butyl phthalate, dioctyl phthalate, trichlorobenzene, glycerine, nitrobenzene, trichloroethyophosphate or water-insoluble

509 8 4 6/0987

Hydrocarbon oils, alkyl phthaloyl butyl glycolates such as Propyl, pentyl, hexyl or preferably butyl phthaloyl butyl glycolate, Diethylene glycol, triethylene glycol or polyethylene glycols having a molecular weight of 200 to 600, e.g. B. 400, or mixtures thereof.

The amount of organic acid in the solvent is preferable so that a saturated solution is obtained. Lower amounts can be used but are less than satisfactory. The organic acid solution obtained may contain water if the amount of water present is very small can be.

The dispersion can also contain a dye or pigment of any desired color. When the dispersion is used is used to impregnate the paper in a grinder, the dye used can be a water-soluble one Be a noun dye or a dispersion of a water-insoluble dye or pigment. When the dispersion is used is used to coat paper according to one of the specified procedures, the dye can be any water-soluble Dye or a dispersion of a water-insoluble dye or pigment.

Suitable dye carriers for those in the British patent application 18199/74 described printing inks are those which have a pH of about 7. If the pH doesn't is exactly 7, it is preferably slightly above than below 7.Examples of such carriers are nitrocellulose, Zinc resinate, vinyl acrylic polyamide and alkyd resins, ethyl cellulose, stand oils and resin-modified stand oils. the liquid organic base can be an amine or an alkanolamine, e.g. B. triethanolamine or diethanolamine. The color can other conventional ingredients such as an alcohol, e.g. B.

509846/0987

Ethanol, propanol or especially denatured with methyl alcohol Alcohol, in amounts up to the amount of the color carrier, preferably up to 80% by weight of the color carrier, if one liquid color is desired, e.g. B. a rotogravure or IFl exo printing ink e.

When the printing ink is printed on a paper substrate or the like, the color former is organic Base is prevented from producing a coloring, and coloring is only produced when the print on the paper with an activating Substance that counteracts the organic base is treated.

Suitable activating substances are the organic acids described above.

The amount of color former in the printing ink varies depending on of the particular color former used and of the desired effect, d. H. depending on whether a dark color is desired or not. In general, the used

/ ew - %
, preferably from 0.01 to 5% by weight and

particularly preferably from 0.1 to 1% by weight, e.g. B. 0.5% by weight be.

The amount of organic base in the printing ink can vary within a wide range, but it should be sufficient to ensure that no reaction occurs between the color former and the substrate on which the printing ink is printed. The amount can be up to 40% by weight, although amounts up to 10 % will suffice on most substrates. The amount used is preferably from 0.2 to 6%, and more preferably from 0.2 to 2 %.

In the British patent application 18200/74 of Ciba-Geigy AG, an image-generating system is described that has a

509846/0987

Solution of a color former in a slightly volatile, high-boiling one Solvent and a substance which deactivates the color former, preferably a volatile, organic one Base-impregnated carrier material comprises, as well as a substrate which is incorporated therein or has at least one surface, which at least partially with a color former activating substance or such a system and a reactivating substance is coated, which counteracts the deactivating substance.

The reactivating substance can be an organic acid as previously described.

The first and second substances involved in the color formation reactions according to the invention can participate, as components in the above-mentioned patent applications and include color formers known in the art.

The first and second substances or the color formers can be of the lactone type, the spyropyran type or related compounds, be of the leuco type or the metal complex type, but preferably they are azo compounds of the following general ones Formula I:

(I)

n-1

2-n

509846/0987

where IL, R _? and R, in each case hydrogen, a halogen atom, an alkyl, alkoxy, aryloxy, alkoxycarbonyl, dialkylaminocarbonyl, acylamino, acyl (alkyl) amino radical, the radical -SOp-N ^ - ^ 1

in which Y ^ and Yp each represent an alkyl or aryl radical or in which Ty and Y ~ together form an alkylene group, X ^ is hydrogen or an alkyl radical, X ~ is an alkyl, cyanoalkyl or arylmethylene radical or X. and Xp together form an alkylene group, X, an alkyl or aryl radical and η = 1 or 2 and preferably 1, or they are compounds of the general formula II:

(II)

n-1

wherein Z, Z ~ and Z ₇ , each represent a hydrogen atom, an alkyl, substituted alkyl, alkoxy, halogen, nitro, acylamino, aminoacyl or alkoxycarbonyl radical, A _x . and Ap each represent an alkyl or phenyl radical or A ^ and Ap together with the nitrogen atom to which they are bonded form a heterocyclic ring system, and η = 1 or 2.

Different color changes are different using Dyes, pigments and color formers possible. Some of the many possible color changes are as follows:

blue

This can be achieved by using a yellow color former, which turns blue when activated changes, either alone or with a yellow dye. Alternatively, a colorless color former can be used when activating blue will be used along with a yellow dye.

509846/0 9. 87

Yellow - ^ red

The same applies here as stated previously in connection with the change from yellow to blue, with the exception that color formers, which turn red when activated.

garbless - > blue

A colorless color former is used, which turns blue when activated.

Colorless - > Red

A colorless color former is used when activating red .will.

Blue -> red

It can be a blue dye plus a colorless color former

which turns red when activated.

Red -> blue

A red dye can be used plus a yellow or colorless color former which turns blue when activated.

Green - ^ - Blue

A green dye can be used plus a yellow or colorless color former which turns blue when activated.

arün -> red

It can be a green dye plus a yellow or a colorless one Color former are used, which turns red when activated, or a blue dye plus a yellow color former, which turns red when activated.

Yellow -> green

It can be a yellow dye plus a colorless color former

which turns green when activated.

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Blue green

It can be a blue dye plus a colorless color former

which turns green when activated.

Eot ■■■■■ Green

It can be a red dye plus a colorless color former

which turns green when activated.

Colored or colorless -> black

A dye plus a mixture of color formers can be used which, when activated, form colors which together with the dye result in the color black.

It should be noted that in the presence of a dye and / or a pigment, the final color from the addition effect of the color of the dye and / or pigment and that by the activated color former is formed.

If the color formers are azo compounds of the formula I, they are preferably those of the general formula III:

^c J 2-n

wherein R ,,, Rc and R ^ are each hydrogen, a lower alkyl, lower alkoxy, halophenoxy, phenoxy, lower alkoxycarbonyl, lower dialkylaminocarbonyl, acetylamino, halo, acetyl (lower-alkyl) amino radical, the Radical -SO ₂ -: in which Y ₇ , and Yy, each represent a lower alkyl or phenyl radical

S09846 / 0987

or in which Ϊ and Y ^ together represent an alkylene group with 4 or 5 carbon atoms are, and where

at most two the remainder R,

S ₁ - and

Are hydrogen,

Is hydrogen or a lower alkyl radical, Xr is a lower one Is alkyl, lower cyanoalkyl or the benzyl radical, or X ^ and Xc- together are an alkylene group having 4 or 5 carbon atoms form, Xg is a lower alkyl or the phenyl radical and η = 1 or 2 means.

Azo compounds of the formula IV are of particular interest:

-N = N

(IV)

where Rr ₇ , Rg and Rg each have a hydrogen atom, the methyl, methoxy, phenoxy, dichlorophenoxy., methoxycarbonyl, dimethylaminocarbonyl, acetylamino, chlorine, acetyl (methyl) amino radical,

/ Y
the radical -SOo-NC _x y5> where Y ^ and Y ^ are each a methyl,

/ 6
Mean ethyl or phenyl radical, or in which Y, - and Y ^ together form a pentylene group, where at most two of the radicals Rr ₇ , R _g and Rq are hydrogen, Xr _{7 is} the methyl or ethyl radical, Xg is the methyl, 2 -Cyanoethyl or benzyl radical, Xq is the methyl or ethyl radical and η = Λ or 2 means.

Advantageous results are obtained with color former of the following formula V:

N = N

(V)

509846/0987

wherein Rr ,, Hg, Rq, Xn und.Xq have the meanings given above own, and very advantageous color formers have the general formula VI:

(VI)

^R 11 V
R ₁₁ = / ^X x j ¹

where R ^ ₁₀ , ~ ^ aa ^ηη ^ - ^ p each represent a hydrogen atom, the methoxy, methoxycarbonyl, chlorine, diethylaminosulfonyl or acetylamino radical and where at most two of the radicals Rx | ₀ 5 ^ -aa ^{un <3} · ^R ip are hydrogen, and Xr ₇ and Xg have the meanings given above.

The expression “lower alkyl” or “lower alkoxy” in the definitions of the radicals of the color formers means radicals with 1 to 5 and especially 1 to 3 carbon atoms, e.g. B. Hethyl, ethyl, propyl, butyl, benzyl or amyl.

If one or more of the radicals R contains acyl groups, the acyl radical can, for. B. of aliphatic monocarboxylic acids with 1 to 4 carbon atoms, e.g. B. acetic acid.

If one or more of the radicals R is halogen, it is iodine or bromine, but preferably chlorine.

When Y ^ and Y ₂ or Y ^ and Y ^ together form an alkylene group, they can form a heterocyclic ring together with the nitrogen atom, e.g. B. the piperidine or pyrrolidine ring.

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Aryl radicals in any of the definitions of the color formers mean in particular the naphthalene, diphenyl and preferably the benzene radical.

These color formers can be prepared by conventional methods known per se, e.g. B. by diazotization of a substituted aniline and its coupling to an N-substituted aniline.

Specific examples of compounds of the general formula I which can be used in the present invention are given in Table 1 below, in which η in formula I denotes «■ Λ , and in Table II in which η in formula I «2 is.

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Table I.

No.

1 2

5 6 7 8

9 10 11 12 13 14 15 16

17 18

Substituents in formula I.

-H 2 -CH -H -H 2 -OCH -H 2-OCH 2-OCH -H -H -H

2-CH

2-OCH ₃ 2-0C ₆ H ₅

-H

-H

3-CH ₃

-H

-H

-H

-H

-H

3-Cl

-H

3-Cl

-H

-H

4-0CH-

-H

-H

-H

R-

4-CH, CONH 3

-H

-H

4-CH ₃

-H

4-OCH ₃

4-OCH ₃

5-OCH ₃

-H

4-Cl

4-CH, 3 4-Cl

5-Cl 5-Cl 5-Cl

-H

-H 4-CH,

-CH, -CH-

-CH ₃
-CH ₃
-CH ₃
-CH ₃

-CH,
3

-CH,

-CH-, 3

-CH, 3

-CH, 3

-CH, 3

-CH, 3

-CH, 3

-CH,

-CH, -CH-

CH

-CH, -CH-3

-CH ₃ -CH _:

-CH, -CH-

3:

-CH ₃ -CH-

-CH, -CH-

-CH-, 3

-CH,

Absorption maximum "λ max. In nm

free base protonated

411 401 406 404 413 404 412 425 416 415 413 414 418 420 43Ο 418

417 420

550

506

520

528/542

540

556

578

560

510

519 510 5Ο6 506 574 518 518

518 514

Color of

protonated

Dye +

violet

orange

Red

Red

violet

violet

blue-gray

Gray

orange

orange

orange

orange

orange

green grey

orange

orange

1X3

cn

cherry red ^? orange - 3

^R 1 Substituents in the formula Tabel I. ^X 1 I (continued) Absorption maximum
λ max. in nm protonated Color of
protonated
"FT οTiT-i o + nf f οα" ^ * No. -H E ₂ E ₃ -CH _x
3 free base 517/535 TdXUbvUXlCo -H 3-SO ₂ -N (CH ₅ -CH _x
3 X ₂ 419 542 orange 19th -H 3-CH ₃ 4-0CH _x
3 -CH, -CH ₅ 408 520 Brown 20th -H -H 4-n ( ⁵
COCH _x
3 -CH, -CH _x
3 418 516 orange 21 -H -H 4_C0-Nv ⁵
CH ₃ -CH _x
3 -CH ₃ 421 556 orange 1
ro 22nd -H -H 4 N ^{/ H}
3 -CH ₃ -CH _x
3 405 522/538 1
violet 23 -H 3-CH ₃ -H -CH ₃ -CH ₂ CH ₂ CN 356 534 Red 24 2-OCH ₃ -H 4-CH ₃ • -CH ₃ -CH ₂ CH ₂ CN 396 542 Brown 25 ' 2-OCH ₃ -H -H -CH ₃ -CH ₂ CH ₂ CN 400 566 Brown 26th -H -H 5-OCH ₃ -CH, -CH ₂ CH ₂ CN 416 513/534 gray K ₅ 27 -H 3-Cl -H -CH ₃ -CH ₂ CH ₂ CN 406 523/541 orange ^ 28 -H -H 4-Cl -CH, -CH ₂ CH ₂ CN 404 523/540 orange OO 29 3-ci 4-CH _x
3 -CH ₂ CH ₂ CN 404 OO
orange ^ j 30th -CH ₂ CH ₂ CN

cn ο co <x>

Substituents R ₁ R ₂ Tabel I (continued) X ₂ From absorption maximum
"N. max. In nm 524/543 Color of
protonated
Dye ⁺ No. -H 3-CH ₃ in formula I. -OH ₂ OgH ₅ free base protonieri 527/542 brown-orange 2-COOCH ₃ -H R ₃ ^X 1 ■ - ^^ S
-CH ₂ C ₆ H ₅ 400 500 Red 31 2-CH _x 3-Cl -H -C ₂ H ₅ -CH ₃ 418 526 orange 32 -H -H -C ₂ H ₅ -CH ₃ 413 555 orange 33 -H -H -H -CH ₃ -CH ₂ CH ₂ CN 416 574 Brown 34 2-OCH _x
3 4-0CH _x "
3 5 - CC ₅ H ₁₁ -CH ₃ -CH ₂ CH ₂ CN 398 522 Brown Green 35 2-0CH _x
3 -H 4-OCH ₃ -CH ₃ -CH _x
3 412 ro
purple ^w 36 5-Cl -CH _x .
3 427 37 _5-so ₀ -nC ^{2 y}
c. O ₂ H

) The color given here refers to the

Protonation in a solution of 95% acetic acid

Table II

«Η ο co OO

co OO

No. Substituents in of formula I. ^X 3 Absorption maximum
"λ · max. in nm 540 Color of
proton S ₁ B ₂ ^E 3 -C ₂ H ₅ free base protonated th color
fabric 101 -H 3-SC ₂ -O 4-CH _x -C ₂ H ₅ violet 102 / ** l TT
X ν Xl * y
-H 3-SOp-Nx ₀₁ J- ⁵
3 4-CH _x
3 -C ₂ H ₅ violet 103 2-CH _x -H
3 4-Cl 466 violet

ro ν> ι

K5 cn

GO OO

If the color former is a compound of the general formula II given above, the alkyl and alkoxy radicals in the definitions of Z., Zp, Z, A ^ and A2 are usually lower alkyl or lower alkoxy radicals, whichever applies contain more than 4 carbon atoms, e.g. B. η-butyl, n-butoxy, n-propyl, isopropyl, ethyl, ethoxy, methyl or methoxy. The substituents for alkyl in Z ^, Z ^ or Z ^ are e.g. B. halogen, hydroxy or lower alkoxy.

The term "halogen" can mean iodine, but preferably it means bromine or chlorine. The term "acylamino" means preferably a radical of an aliphatic or aromatic sulfonic or, in particular, carboxamide, the amide nitrogen may be substituted by lower alkyl. Residues of an alkanecarboxamide are particularly preferred, where the amide nitrogen is optionally substituted with methyl, e.g. B. a formic acid amide, acetic acid amide or propionic acid amide residue or residues of a benzene carboxamide, e.g. B. of benzoic acid amide.

The term "aminoacyl" generally stands for an amine, which is substituted with a -CO- or -SOp- group. The amine residue can be derived from a primary or secondary, aliphatic or heterocyclic amine. Preferred Triazenes correspond to the following general formula VII:

7 17 17 ■

(VII) Y n-1

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- ClT? -

wherein Z ^, Z ₁ - and Zg are each hydrogen, an alkyl radical having 1 to 4 carbon atoms, an alkoxy radical having 1 to 4 carbon atoms, halogen, nitro, -N (-X _x .) - CO-X ₀ or -G-Nf 3

7 | - ^ J A

or COOX ₇ . mean, where X _x . and X ~ are each hydrogen, 4-an alkyl radical having 1 to 4 carbon atoms or the phenyl radical, X ₇ . denotes an alkyl radical with 1 to 4 carbon atoms, G = -CO- or -SOp-, A ₇ ^, A ^ ,, Ai and A ^ each denote alkyl with 1 to 4 carbon atoms or phenyl or A ₇ . and A ^, or Ai and A \ together with the nitrogen atom to which they are bonded, form a heterocyclic ring system with one or two rings, each ring having 5 to 7 ring members and η = 1 or 2.

Triazenes of the following formula VIII are of particular interest:

(VIII)

n-1

where Z ₁ - and Zg each represent a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms, an alkoxy radical having 1 to 4 carbon atoms or halogen, and Zg, A _7. , A ^ and η have the meanings given above.

Advantageous results are obtained with color formers of the following general formula IX:

509846/0987

^Z 9 ^Z 1O ^Z 11

N = N-N

n-1

(IX)

wherein Zq is a hydrogen atom, an alkyl radical with 1 or 2 carbon atoms, an alkoxy radical with 1 or 2 carbon atoms, a halogen radical, the nitro radical, -N (-X _{,.), -CO-X n} -, -GN \. or -COOXg denotes, X ^, a hydrogen atom, an alkyl group with 1 or 2 carbon atoms or the phenyl group "denotes, X ₁ - an alkyl group with 1 or 2 carbon atoms, Xg an alkyl group with 1 or 2 carbon atoms or the phenyl group, Z ^ ₀ and Zy.y. each have a hydrogen atom, an alkyl radical with

1 or 2 carbon atoms, an alkoxy radical with 1 or 2 carbon atoms or a halogen radical ", G: -CO- or -SO ^ - represents, A, -, Ag, AA and kl each represent an alkyl radical with 1 or

2 carbon atoms or the phenyl radical or A, - and Ag "or An and AJ- together with the nitrogen atom to which they are attached are bound, a heterocyclic ring system with one or two Eingen, the carbon, nitrogen and at most one Contains oxygen as ring members, each ring having 5 to 7 ring members and the ring system at most 10 Contains ring links.

Triazenes of the following general types are very advantageous color formers Formula X:

N = N-N

n-1 509846/0987

where Z ^ _{2 is} hydrogen, the methyl, methoxy, chlorine or nitro radical or one of the following radicals:

-NC-X ₉ ) -CO-Xo, -SOp-N ( ' , -SOp-N, -SOp-N>",

^L 8

-K f

-SO ₂ -N J , -CO-N (CH ₅ ) ₂ or -COOCH ₅ ,

Z ^ is hydrogen, methyl, methoxy or chlorine, Z _x . ^ Is hydrogen or methoxy,
AA is methyl, ethyl or phenyl,
AA is methyl, ethyl or hydrogen,
A _{7 is} methyl, ethyl or phenyl,
Ag is methyl or ethyl, or

A ₇ and Ag together with the nitrogen atom to which they are attached represent the following radicals:

-O

X _{1 is} -, hydrogen or methyl,
Xg is methyl or phenyl, and
η * means 1 or 2.

.'These color formers are known as such, or they can be prepared by conventional methods well known in the art. One common method is z. B. the following:

The primary, aromatic amine is dissolved in hydrochloric acid and water, then the solution is ^{cooled to 0} ° C. with ice. Sodium nitrite is added below the surface at such a rate that a slight excess of nitrous acid is always added

S09846 / 0987

is available. When the diazotization is complete, the reaction mixture is added to a solution or suspension of the secondary amine and sodium hydrogen carbonate in water at 10 ° C. The reaction mixture is stirred and allowed to warm to room temperature. Stirring is continued until no diazonium compound can be detected. The product is precipitated from the solution and is filtered off or extracted into an organic solvent, washed with water and dried in vacuo at a temperature below 50 ⁰ C dried.

As such, these color formers are colorless and can produce colored images if they are brought into contact with a typical azo coupling substance and the organic acid.

Suitable color images of the formula II are, for. B .:

509846/0987

Table III

No. Symbols in the formula (II) ^No. 1 • • • _m ^Z 2 • - H • • η • • • position
-N = N ... • • • - • • .... - ■ • ·
• mm «·· A- Ap • O • · 6.1 3-SO ₂ K (CH ₃ ) ₂ 3-SOpN (C ₂ ) Ir) ^ 4-CIl ₃ I. I. -CH ₃ -CH ₃ ' O. 6.?. . • ·. - -CH ₃ -CH ₃ t ».3 a α α 6.A • O ■ O 6; 5. · ■
• ο- ^r O 6.6 O ⁰ O. 6.7 ~ Cli ₃ -CH ₃ -Cl ₃ -ClL. 6.8 / 6.9 j 6.10 ' O i ! 6. II ο .- I 6.12 • O ³ 6.13 .6.14. 6.15 · 6.16 6.17 6.18 6.19 6.20.

5098A6 / 0987

ORIGINAL INSPECTED

Table III (continued)

No. Symbols in the formula (II) ^No. 1 CH _V • ^Z 2 • C. t • ^Z 3 • • • η • Position
-N = N • • O ~ CH, -cn, α ■ 6 5 H I. I. ¹ ö 6.21
6.22 ·· 3-SO ₂ -JiC ² ^ O O 6.23 O ⁰ 6-, 24
6.25 ² fc> f 1 O ■ 6.26 6.27 6.28 6.29 -CpH, 6.30 α 6.31- ο 6.32
6.33 6.34 6.35 6.36

509846/0987 OR! G! NAL SHSPECTED

Ta'oelle III (continued)

No. Symbols in ■ CO-CIl
4-KC ₁ . ^Z 2 H H • of formula (II) I.
i • 5-Cl • η • position
-N »H ... ■ A ₁ A ₂ • ■ 0 • 4-NH-CO-O ₆ H ₁ . * 2-CH ₃ 2-OCJl ₃ ^Z 5 ι H I. I. O 6.37 2-COOCH, H ? .- OCH ₃ 5-OCFf ₃
1 ·
H O 6.38 2-0CH, • 6-39
6.40 4-Cl H H . CJ 6.41 5-OCH ₃ 6. « 4-OCH ₃ 6.43 • 6.44 /, - SO ^ (C ₂ H ₅ ) 6.45 6.46 fm Uz-Hl- 6.47 ³ - ^S0 r ^! 'O 6.48 6.49 6.50 6.51- 6.52

509846/0987

ORIGINAL INSPECTED

Table III (port setting)

No. 53 S. 4-Cl Symbols in the Z ₂ • ^Z 3 Formula (II) position
-N = N ... -CH ₃ A ₂ ^ CH ₃ 54 / 1-OCH ₃ 2-CH ₃ I. 6th 55 5-OCH ₃ 2-OCH ₃ 6th 56 5-Cl 6th 57 • 2-Cl 6th 5S 2-CH ₃ -CH ₃ 6th 59 /, - SO ₂ -N H -CH ₀ 6th 60 5-EO ₂ -N c ₂ iy ₂ . -C ₂ H ₅ 6th 61 -H C3 - ^C 2 ^H 5 6th 62 5-SO ₂ -N (c ₂ , y ₂ cz> 6th 63 4-S0 _? -N 6th 64
65 5-SO ^ -h (C ₂ Iy ₂ 6th 66 5-SO ₂ -4 O 6th
6th -CH ₃ 6th η I. 2

509846/0987

When a triazene compound of formula II is used as a color former is, the azo coupling component is preferably a Naphthalene, benzene, fyrazolone or quinoline or, in particular, a naphthol or a naphthylamine.

Among the naphthols, those of the following general formula XI are of particular interest:

CONH

CXI)

n-1

where M * is -NH-, -S- or -0-, Q ^, and Q ~ are each hydrogen atom, a nitro radical, a halogen radical, an alkyl radical with 1 to 4 carbon atoms or an alkoxy radical with 1 to 4 Are carbon atoms, and m and r are 1 or 2, respectively.

Naphthylamines, which are very beneficial, correspond to the following general formula XII:

(XII)

wherein Q-, and Q ^ each represent a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, the benzyl radical or phenyl radical, or if Q ^, Q ₂ , and the nitrogen atom to which they are bonded, together a heterocyclic ring system with form one or two rings, this consisting of carbon, nitrogen or at most one oxygen as ring members

509846/0987

and each ring 5 to 7 ring members and the ring system at most Has 10 ring members, and wherein Qc is hydrogen or one Is sulfonic acid group.

Any azo couplers useful in the invention can be used are known couplers which are used for the preparation of azo dyes, and they are therefore known as such and are produced by methods known per se.

The following naphthols of the formula XI are e.g. B.- as coupling components very suitable.

Table IV

No. position
from -OH Symbols in formula M. (XI) Q ₁ Q ₂ 8.1 2 position
by -CONH- m _ n H H 8.2 2 3 1 - 1 4-Cl H 8.3 2 3 1 - 1 4-Cl 2-CH ₃ 8.4 2 3 1 - 1 H 2-OCH ₃ 8.5 2 3 1 - 1 H 2-CH, 8.6 2 3 1 - 1 3-NO ₂ H 8.7 2 3 1 - 1 5-OCH ₃ 2-OCH, 8.8 2 3 1 - 1 4-OCH ₃ H 8.9 2 3 1 - 1 4-OCH ₃ 3-Cl 8.10 2 3 1 - 1 5-ci 2-CH ^ 8.11 2 3 1 - 1 4-CH ₃ H 8.12 3 3 1 NH 1 4-Cl H 8.13
8.14 2
2 4th 2 0 1 5-OCH ₃
H 2-OCH ₃
H 3
3 2
1 1
2

509846/0987

Naphthylamines of the formula XII are, for. B. the following connections:

NH

HO _x S NH 5

(9.1)

(9.2)

Further suitable azo couplers correspond to the following formulas:

CH.,

(10.1)

(10.2)

(10.3)

(10/4).

(10.5)

509846/0987

KII-CO-Hiv

. ■ OH

(.10.7)

(10.6)

(d.O. η)

HII '

COC! I _v J

(10.9)

With these color formers a large number of different ~ shades ranging from orange to purple can be produced. Mixtures of such color formers are suitable to neutralize Shades like gray. A special advantage of the triazenes is the lightfastness of the colorations they produce.

The paper treated with a dispersion according to the invention can be printed using an ink such as that described in British Patent Application 18199 / 74- and if the printing ink used has a color former with a

ßAD ORIGINAL

509846/0987

a different color change to that already present on the paper or a different color change Color change thanks to the color containing a differently colored dye or pigment forms two color changes observed when the paper is treated with an acid.

The invention is explained in more detail below with the aid of examples, all parts and percentages being based on weight.

example 1

0.1 part of Color Former No. 32 of Table I with the following general formula:

COOCH

were dissolved in 5 parts of 2-ethoxyethanol. This solution was then in 50 parts of water with stirring and formation of a dispersion poured.

This dispersion was made in a grinder that made 50 parts Paper stock dispersed in 2500 parts of water was entered. Part of the ketene dimer was then used as a sizing agent was added and the paper sheet was then made in the usual manner. The yellow paper changed color to red when Citric acid was stamped on it by means of a rubber stamp from an ink pad.

509846/0987

Example 2

The procedure of Example 1 was repeated with the exception that the color former solution was added directly to the paper stock dispersion. The same results were obtained.

Example JS

The procedure of Example 1 was repeated with the exception that the water contained 5% of a non-ionic starch and 0.5% of an acrylic latex. The resulting dispersion possessed improved stability.

When added to paper stock, as in Example 1, were similar Get results.

Examples 4-8

The procedure of Example 2 was repeated using different color formers. The color formers used and the color changes obtained are as follows Table V compiled.

Table V

Color formers

Change of color of the paper

Crystal violet lactone

3,3-bis (2-methyl-1-n-octylindol-3-yl) phthalide

2-Dibenzylamino-6-diethylaminofluoran

2-Dibenzylaπlino-6-diethylaminofluoran

3,3-bis- (2-methyl-1-n-octylindol-) 3-yl) phthalide)

yellow

colorless colorless colorless gray-white

blue

blue red

green > black

509846/0987

Examples 9 "to 19

A dispersion was made according to that given in Example 1 Procedure made except that a dye was previously dissolved in the water. The combination of Dyes, color formers and the color changes produced on paper impregnated with the dispersions are in compiled in the following Table VI.

Examples 20 to 42

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

The resulting dispersion was coated on paper by Walζenbeschichtung at 60 ⁰ C in an amount of 0.2 wt .-% of the fibers in the paper.

The color formers, dyes and the color changes obtained are listed in Table VII below.

509846/0987

Table VI

cn ο co οο

ο co co

sp. Color formers
of example in % 1 dye 4th 9 1 1 0.6% direct yellow 4th 10 6th 0.5
0.1 0.5% direct yellow 4th 11 4th
1 1 0.5% direct yellow 4th 12th 5 0.5 0.2% direct yellow 199 13th 6th 1 0.5% direct blue 23 14th 4th • 1 ' 0.4% direct red 199 15th 7th 0.1 0.5% direct blue 199) 16 1 0.1% direct blue

17th

18 19

7 6

0.5) o, 5)

Acid yellow 5)

0.5% direct blue 199) acid yellow 5)

0.5 % direct yellow 0.5% direct yellow

yellow - ■ yellow yellow \ yellow - i blue - i orange - blue -; green - I. y red > red > black > blue > red -> blue ^ - green > red

green

yellow
yellow

Red

green
black

Direct yellow Direct blue Direct red Acid yellow

CI. 24890

CI. 74180

CI. 29160

egg. 47035

Table VII

E.g. Color formers in % of ex. 0.5 20th 1 0.1 21 1 0.5 22nd 4th 0.1 cn 23 4th 0.5 O
co 24 5 0.5 00 25th 0.5 cn 26th 6th 0.5 O 27 6th 0.5 co
00 28 6th 0.5 29 7th o, 5) 30th 7th o, 5) 1 31 5 1 32 6th 0.5 33 1

dye

Color change

0.1% direct blue 199) acid yellow 5)

0.2% direct yellow 4 0.07% direct red 23

0.5%. Direct blue 199

0.1% direct blue 199) acid yellow 5)

0.2% direct red 23

0.1% direct yellow 4 0.2% direct yellow 4 0.6% direct yellow 4

yellow

Red

green - ^ red yellow -> blue yellow -> gray-green colorless -> blue pink - ^ blue colorless -> red blue - ^ - red

green -> red red -> green gray-white -> black

yellow - ro
cn yellow - 1887 yellow - -> blue-green -> red -> red

Table VII (continued)

E.g. Color formers in % of ex. 0.2 34- 1 0.5 35 4th 0.5 cn 36 1 O 1 co
cn 37 5 -tr- 0.5 O) 38 7th 0.5)
0.4) O - 39 5 co 7th 0.5 OO 0.5)
0.1) -J 40 '7 0.1) 41 5 0.4) 6th 42 1 4th

dye

Color change

0.05 % direct blue 76 0.2% direct red 23

0.25% direct blue 199) acid yellow 5)

0.2 % direct blue 199) acid yellow 5)

0.2% direct yellow 4 1.5% direct red 23

0.2 % direct blue 199 0.5% direct yellow 4

0.5% direct yellow 4

green - orange green -

green -

yellow - red - i

blue yellow -

yellow -

»Red - ± blue

► blue-black

► blue

* ■ green black

* ■ green * - black

► black

Example 43

It was an aqueous mixture of 500 parts of a 4% aqueous starch, 2.5 parts of an acrylic latex and 0.033 parts of the sodium salt of a naphthalenesulfonic acid / formaldehyde condensation product manufactured. A solution of a coloring agent in 11.8 parts of 2-ethoxyethanol was added to this mixture added to form a stable dispersion.

The dispersion obtained was applied under on paper

Manufacturing conditions applied in a sizing press at 60 ° C. The amount of color former present in the dispersion was adjusted by successive additions of color former solution in 2-ethoxyethanol in order to obtain between 0.004% and 0.04 % color former by weight on the paper.

When the color former present in the paper was activated, there was a change from yellow to red, which was the result Intensity depended on the amount of color former present.

Preliminary tests were carried out in the absence of the acrylic latex. In these cases it was found that the dispersion was less was stable.

Example 44-

An ink was made using nitrocellulose as the base for the vehicle. The carrier became made by mixing the following ingredients together:

31 parts of nitrocellulose 120 parts of denatured ethyl alcohol 18 parts of 2-ethoxyethanol

Then a printing ink was prepared from the following components:

509846/0987

0.07 part of color former no. 25 of Table I 5.0 parts of the printing ink vehicle 4.0 parts of denatured ethyl alcohol 0.4 parts of triethanolamine

After complete dissolution, this printing ink contained 10 % nitrocellulose.

The triethanolamine was dissolved in the denatured ethyl alcohol prior to mixing with the other ingredients.

The printing ink was printed on the surface of a paper, no color reaction occurred and the printing ink only gave a yellow print.

Example 45

It was an activator solution of 50 parts maleic acid, 50 parts Water and 50 parts glycerine. 7 parts of this were then applied to an ink-free ink pad, and the printed paper made in Example 44 became stamped with the activator solution. It immediately resulted in an intense red color when the activator solution with the print came into contact.

Example 46

A printing ink was made from the following components:

0.07 part of color former No. 32 of Table I 5 * 0 parts of the printing ink vehicle of Example 44 4.0 parts denatured ethyl alcohol 2.0 parts butyl phthaloyl butyl glycolate 0.4 parts of triethanolamine.

The ink was coated onto the surface of a clay Paper as printed in Example 44.

509846/0987

There were five activator solutions according to the procedure of Example 45 using the following acids:

Maleic Acid Citric Acid Malic Acid Tartaric acid succinic acid

When it was applied to an ink-free stamp pad and stamped on the printed paper, it immediately became a very red color Color generated.

Example 47

A printing ink was prepared by dissolving the color former No. in Table I in linseed stand oil in an amount such that one 1% solution to get dissolved.

The printing ink was printed on the surface of an alkaline coated paper. It turned very red Coloration produced when the paper was stamped with the activator solution from Example 45.

5098A6 / 0987

Claims (12)

Claims 1. A security document, characterized, geke η η ζ eichnet, ~~ "that it comprises a backing, a first turned bring in the substrate or applied to the base substance, said first substance is to take part in a color-formation reaction in the layer and a second to the substrate applied substance, said second substance is to participate in a different color-forming reaction in a position, wherein in carrying out the verification of the security document by applying at least one Eeagens to the security document, this first substance and said second substance color by change the color formation reactions. 2. Security document according to claim 1, characterized in that that the first substance contains at least one color former and / or at least one dye or pigment. 3. Security document according to claim 2, characterized in that the dye or pigment is separated into the base is introduced by the color former. 4. Security document according to claim 1, characterized in that the first substance is introduced into the support during manufacture the document has been introduced. 5. Security document according to claim 1, characterized in that that the first substance has been completely introduced into the support by the support by a solution of the first Substance has been carried out. 509846/0987 6. Security document according to claim 1, characterized in that the first substance is applied to at least one surface of the Is printed on the backing. 7 security document according to claim 1, characterized in that that the second substance comprises at least one color former and / or at least one dye or pigment. 8. Security document according to claim 1, characterized in that the second substance is applied to at least one surface of the Is printed on the backing. 9 «Security document according to claim 1, characterized in that that more than one second substance is applied to the base. 10. Security document according to one of claims 1 to 6, characterized in that the first substance and the second substance comprise or consist of a color former, which is an azo compound with the following general formula I. is: N-N- where E ^, IL ^ ^and · ^ x each represent a hydrogen atom, a halogen atom. Alkyl, alkoxy, aryloxy, alkoxycarbonyl, dialkylaminocarbonyl, acylamino or acyl (alkyl) amino radical or the Eest where Iy. and Y ^ are each alkyl or aryl, 5 09846/0987 or where T. and Y ~ together represent an alkylene group, X ^ is a hydrogen atom or an alkyl radical, X _{2 is} an alkyl, cyanoalkyl or arylmethylene radical, or X ^ and X ₂ together represent an alkylene group, H-, a Is alkyl or aryl radical and η = 1 or 2, where it is in particular a compound of the following general formula II. N = N-N (II) where Z , and Z ₅ . each represent a hydrogen atom, an alkyl, substituted alkyl, alkoxy, halogen, nitro, acylamino, aminoacyl or alkoxy carbony Ire st, and each represent an alkyl or phenyl radical, or A ^. and A ₂ together with the nitrogen atom to which they are bonded form a heterocyclic ring system, and η = 1 or 2. 509846/0987 11. Security document according to claim 4, characterized in that the reagent is an organic acid in the form of maleic acid, Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tricarballylic acid, diglycolic acid, lactic acid, Malic acid, tartaric acid, citric acid, pyrophosphonic acid, Benzenesulfonic acid, naphthalene-2-sulfonic acid, 1-phenol-4-sulfonic acid, Polymaleic acid, copolymers and terpolymers of Maleic acid with ethyl acrylate and vinyl acetate, hydroxyethane diphosphonic acid or methylamino-N, N-dimethylene phosphonic acid provided that when the color former is a compound of Formula II, an azo coupler is also present. 12. Method for checking a security document, which is a document, a first introduced into the document or substance applied to the support, this first substance taking part in a color-forming reaction is capable, and at least one second substance applied to the substrate, wherein the second substance is capable of participating in a different color-forming reaction comprises, thereby characterized in that at least one reagent is applied to the security document and the color change of the the first and second substances is observed by the color forming reactions with the reagent. 509846/0987