DE19527100A1 - Water fast and brilliant print prepn. applied onto textiles or paper - by thermal ink jet printing using water soluble anionic azo dye and cationic polymer auxiliary agent to treat the printable substrate - Google Patents

Abstract

A method for the prepn. of water-fast and brilliant print on substrates contg. hydroxy or amide gps. comprises: (i) ink-jet printing the substrate with a dye contg. anionic water-soluble gp(s).; and (ii) applying a cationic polymer auxiliary agent onto the substrate before, during or after printing.

Description

The invention relates to a method for producing water-correct prints substrates containing hydroxyl or amide groups with cationic polymeric auxiliaries agents and dyes carrying anionic residues and by this process colored substrates.

From EP-A-528 644 it is already known that water-correct ink jet prints are produced can, if you use inks that are hydroxy in addition to the dye contain ethylated polyethyleneimine and an ammonium salt. The formation of the water-based imine-dye complex which forms on the paper is in the ink by a certain pH value and by special dye / imine Ammonium salt combination suppressed. The disadvantage here is that this principle is limited to specific dyes and the formation of poorly soluble Dye-imine complexes in the ink can cause nozzle clogging.

In EP-A-534 634, water-correct ink jet prints are obtained by: Impregnate substrates such as paper with a metal salt solution of multivalent metals and then treat the paper so treated with a dye solution Dye that carries at least one carboxy group, using the ink-jet method printed. However, these prints still have certain brilliance, in particular Disadvantages. To print both water-correct and brilliant prints on hydroxy or to obtain substrates containing amide groups has become a new process found, which is characterized in that the substrate with a Dye, which as a water-solubilizing group at least one anionic Rest carries, printed by means of the ink-jet method and on the substrate before or applies a polymeric cationic auxiliary after printing.

For example, a substrate containing hydroxyl or amide groups is preferred textile fabrics made of cotton, wool and / or polyamide or in particular other paper.  

Suitable cationic auxiliaries are, for example, in Textilveredlung 25 (1990) 2, page 54 ff (fastness-improving agents for direct dyes), G. Troemel et al., Wochenblatt für Papierfabrikation No. 2 (1989), p. 63 ff (wet strength agent) and in E. Arnold, G. Martin, Wochenblatt für Papierfabrikation 15 (1988) 617 ff (Dye fixer for paper dyes).

The cationic reaction products are cationic polymeric auxiliaries U1-U12 or mixtures thereof are preferred. These implementation products can be form as follows.

U1. Condensates of amines and dicyandiamide or amines and guanidines;
U2. Reaction products of the condensates from U1 with bifunctional alkylating agents and / or aldehydes, and / or compounds containing methylolamide;
U3. Condensation products of amines and monofunctional alkylating agents, which are optionally further reacted with monofunctional alkylating and / or acylating agents;
U4. Polyallylamines or polyallylammonium compounds obtained by polymerizing mono- and / or di- and / or triallylamine and / or -ammoniumverbindungen;
U5. Reaction products from polydiallylamines or Polydialkylammoniumver compounds of group U4. with bifunctional alkylating agents which may also contain reactive groups (such as chlorohydrins by reacting U4 with epichlorohydrin);
U6. Polyamide amines obtained by reacting amines with polycarboxylic acids or derivatives thereof;
U7. Reaction products of guanidines or dicyandiamide with aldehydes;
U8. Implementation products from U6. with bifunctional alkylating agents;
U9. Reaction products of polyols and polyisocyanates and their reaction products or quaternized secondary products with bifunctional alkylating agents and / or polycarboxylic acids or derivatives thereof
U10. Basic polyureas which are obtained by reacting urea with amines or by reacting polyisocyanates with amines and, if appropriate, by further reaction with bifunctional alkylating agents and / or aldehydes and / or methylolamide-containing compounds,
U11. Polyether amines and quaternary polyether ammonium compounds which are obtained by acid-catalyzed polycondensation of amino alcohols and, if appropriate, by further reaction with monofunctional alkylating and / or acylating agents,
U12. Polymers made from aziridine and / or substituted aziridines and their reaction products with bifunctional alkylating agents and / or polycarboxylic acids or derivatives thereof and / or monofunctional alkylating and / or acylating agents.

In a preferred embodiment, the amines used in the reaction products U1-U12 are aliphatic, aromatic or cyclic amines and polyamines such as ammonia, ethylenediamine, diethylenetriamine, triethylene tetramine, polyethylene polyamines, 1,1-dimethylpropanediamine, piperazine and also for condensates from di- or polyamines with optionally substituted ureas, provided that they still contain basic nitrogen atoms,
the bifunctional alkylating agents used for 1,2-dichloroethane, 1-bromo-3-chloropropane, epichlorohydrin, 1,3-dichloroethane, 1,4-dichlorobutene or dichloropropane,
the polycarboxylic acids used for succinic acid, butane tetracarboxylic acid, adipic acid, maleic acid or terephthalic acid and the half esters, esters and nitriles derived therefrom,
the monofunctional alkylating agents used for benzyl chloride, methyl chloride, alkyl halides, or dimethyl sulfate and the monofunctional acylating agents used for acetic anhydride, acetyl chloride or monofunctional carboxylic acids (which also react as acylating agents at elevated temperature), such as stearic acid,
the polyols used for glycerol, glycol, diethylene glycol, propanediol or for amino alcohols such as mono-, di- or triethanolamine, alkyldiethanolamines or oxyethylates of amines,
the polyisocyanates used for hexamethylene diisocyanate, isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI) or tris (isocyanatohexyl) triisocyanurate,
the guanidines used for optionally substituted guanidines and their salts,
the aldehydes used for aromatic or aliphatic aldehydes, such as formaldehyde, acetaldehyde, glyoxal, glyoxylic acid, glycol aldehyde, and for compounds from which aldehydes can be split off, such as N-methylolamides (e.g. urea-formaldehyde resins, which are used for the crease-resistant treatment of cotton be used).

Some particularly preferred polymeric cationic auxiliary types are, for example, those from the group:
U1, U3, U4, U7, U10, U11 and U12.

Examples of preferred cationic polymeric auxiliaries are those of DE-A-39 40 481, in particular example 1; DE-A-34 16 693, in particular Bei game 1; DE-A-27 56 431, polyamine 2; or to call from DE-A-23 51 754.

The cationic polymeric auxiliary is preferably applied to the substrate in the form of an aqueous solution. This aqueous solution generally has the following composition
1 to 20% by weight of a cationic polymeric auxiliary
0 to 30% by weight of one or more organic solvents
0 to 10% further additives and
40 to 98% water.

As further additives in aqueous solutions or emulsions of the cationic poly Other aids include ionic or non-ionic substances nen with which the viscosity and / or the surface tension in the for Application required areas can be set. For example can be called anionic, cationic or neutral surfactants.

The cationic polymeric aid can be applied to the sub in any manner be applied strat. Examples of this are given in EP-A-534 634. So can the cationic polymeric auxiliary, for example, with the help of one there described mechanical roller mechanism or by fine spraying, in particular, however, applied to the substrate using the ink jet method will.

For the greatest possible effect on water fastness on the one hand and on brilliance on the other on the other hand, preferably 0.1 mg to 100 mg of the cationic poly meren aids used per cm². The Ver use an amount of 0.5 to 10 mg of auxiliary solution per cm² of substrate exposed.

Any dye which can be used as the dye in the process according to the invention as a water-solubilizing group carries at least one anionic radical. Under anionic radical is understood in particular to be a sulfo or carboxy group. The dyes used according to the invention particularly preferably carry so many Sulfo and / or carboxy groups that their water solubility at 1 to 250 g / l Is 25 ° C. The dyes preferably do not carry any ammonium residues. Especially the process according to the invention using color is preferred substances that do not carry COOH groups. The dyes are in erfindungsge Processes preferably in the form of aqueous preparations, in particular Solutions used. These aqueous dye preparations generally contain nen one or more dyes of the type mentioned, if appropriate suitable organic solvents, including hydrotropic compounds as well as other aids and / or stabilizers. It is advantageous to use the aqueous Dye solutions in the course of dye synthesis itself, without intermediate insulation of the dye.

The aqueous dye solutions generally contain about 0.5 to 20% by weight of one or more dyes of the type mentioned, 80 to 99.5% by weight  Water and / or organic solvent and optionally other conventional solvents Components.

Preferred organic solvents are alcohols and their ethers or Esters, carboxamides, ureas, sulfoxides and sulfones, especially those with molecular weights <200. Particularly suitable solvents are, for example wise: methanol, ethanol, propanol; Ethylene, propylene, diethylene, thio diethylene and dipropylene glycol; Butanediol; β-hydroxypropionitrile, penta methylene glycol, ethylene glycol monoethyl and propyl ether, ethylene diglycol mono ethyl ether, triethylene glycol monobutyl ether, butyl polyglycol, formamide, tri ethylene glycol, 1,5-pentanediol, 1,3,6-hexanttriol, 2-hydroxyethyl acetate, 2 (2'-hydroxy) ethyl acetate, glycerol, glycol acetate, 1,2-dihydroxypropane, 1-methoxy-2-propanol, 2-methoxy-1-propanol, N, N-dimethylfomamide, pyrrolidone, N-methyl-caprolactam, ε-caprolactam, N-methyl-caprolactam, butyrolactone, Urea, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N, N'-dimethylol propylene urea dimethyl sulfoxide, dimethyl sulfone, sulfolane, isopropanol, Polyethylene glycol.

Ionic or non-ionic additives are other common additives in printing inks Substances in question with which the viscosity and / or surface tension in the for the application required areas can be set as at for example anionic, cationic or neutral surfactants such as dispersants and Viscosity regulators. The function of viscosity regulators can, for example be taken over by the organic solvents.

Aqueous dye preparations, in particular dye solutions, are preferred with the following composition:

• 0.5 to 20% by weight, in particular 1 to 10% by weight, of one or more Dyes of the type mentioned,
• - 50 to 99.5 wt .-%, in particular 60 to 93 wt .-% water
• 0 to 30% by weight, in particular 5 to 20% by weight, of one or more organic solvents,
• - 0 to 30 wt .-%, in particular 1 to 10 wt .-% viscosity and / or Additives affecting surface tension,

the sum of the ingredients mentioned being added to 100% by weight.  

The inks can be prepared by dissolving the dye salts in water or from the con condensation solutions, which may include desalination e.g. B. by pressure permeate tion and / or by adding one or more of the above mentioned organic solvents, if appropriate at elevated temperatures (preferably 30 to 100 ° C, especially 30 to 50 ° C) and with the addition of inorganic and organic bases are produced; if necessary usual ionic or non-ionic additives are also used be, e.g. B. those with which the viscosity lowers and / or the surfaces voltage can be increased.

Instead of the dye salts, the corresponding free acids can also be used in Combination with preferably equimolar or larger amounts of the corre sponding bases are used.

As inorganic bases such. B. lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate can be used.

As organic bases z. B. ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, 1- Amino-2-propanol, 2-amino-1-propanol, di-isopropanolamine, N-2-hydroxyethyl diisopropanolamine, tris-N, N, N- [2 ′ (2′-hydroxyethoxy) ethyl] amine or sodium serve methylate, lithium ethylate, potassium tert-butoxide.

The dyes, which have a lower solubility in water than 10 g / l at 25 ° C., are preferably used in the form of their aqueous dispersions. Preferred dispersants here are monomeric or polymeric surfactants or emulsifiers. Such aqueous dispersions preferably contain
1 to 10% by weight, in particular 1 to 8% by weight, of one or more dyes of the type mentioned,
1 to 10% by weight, in particular 1 to 8% by weight, of dispersant,
0 to 30% by weight, in particular 5 to 20% by weight, of organic solvent,
0 to 10% by weight, in particular 1 to 8% by weight, of further additives and
40 to 98% by weight of water, in particular 50 to 92% by weight of water,
where the sum of the ingredients mentioned adds up to 100%.

Under the ink jet method of the method according to the invention, a Understanding the ink jet recording method in which the ink drops on the Substrate are sprayed. The fine ink droplets can be distinguished by processes are generated. They are preferred according to the general known thermal jet, bubble jet, piezzo jet or valve ink jet process generated.

The ink droplets after the thermal jet are particularly preferred Process generated.

The dye is preferably in the process according to the invention in aq ger solution or dispersion according to one of the above-mentioned ink-jet methods that has preferably already been treated with the polymeric cationic auxiliary Substrate applied. The aid is particularly preferably applied and the dye using a multi-chamber inkjet cartridge. The Cartridge-like systems are described for example in EP-A-534 634. For the sequential or simultaneous application of tools and paint In EP-A-534 634 there are also numerous possibilities based on Illustrations presented. The techniques described there are also for that The method according to the invention can advantageously be used.

In a preferred embodiment, the polymeric cationic auxiliary medium and the dye applied to the substrate using the same ink jet method carry. This is preferably done so that only the surface of the substrate with the cationic polymeric auxiliaries that are also treated with the dye to be printed. The method according to the invention can also be used for input can be used for multi-color printing.

The black dyes are from the group

• C.I. Direct Black 19, 22, 51, 62, 113, 154, 171 and 168,
• C.I. Food Black 2 and
• C.I. Acid Black 24, 26, 52, 52: 1, 109, 155, 172, and 222

prefers.

The yellow dyes are from the group

• C.I. Acid Yellow 19, 23, 49, 79, 135, 141, 151, 169, 184, 230 and 242 and
• C.I. Direct Yellow 28, 50, 58, 84, 86, 132, 137, 153 and 163

advantageous.

The dyes are from the group as magenta dyes

• C.I. Acid Red 35, 106, 114, 127, 143, 143: 1, 145, 227, 249, 254, 265, 266, 274, 318, 337, 341 and 361,
• C.I. Recative Red 180 (hydrolyzed) and
• C.I. Direct Red 80, 81, 82, 83, 89, 95 and 212

preferred and as cyan dyes are the dyes from the group

• C.I. Acid Blue 9, 41, 62, 78, 80, 138, 140, 182, 185, 205, 220, 221, 225, 260, 264, 277: 1, 290, 324, 350 and
• C.I. Direct Blue 86, 87, 106, 189, 192, 193, 199, 229, 237, 290 and 291

advantageous.

In the following examples, the dyes and auxiliaries were same ink jet method applied to the substrate. This was a trade Usual ink-jet printer that uses the thermal jet process Ink drops created. Photocopy paper (pH of the surface 6.7) used.

The waterfastness of the prints obtained was determined using a full area pressure was stored in water for one hour and after drying the sun treated paper the proportion of the dye remaining on the paper was judged. A water fastness of 100% means that the entire Dye content remains on the paper and a water fastness of 0% that the all of the dye disappears from the paper. The results of water justice testing as well as the regulations for the production of the aids mentioned are in summarized in the table.

example 1

First, an auxiliary solution consisting of 90 parts of fully desalinated water water and 10 parts of a 20% aqueous solution of a dicyandiamide / ammo niak / formaldehyde condensates (Catiofast® FP, BASF; auxiliary from the group U7) printed and then the black dye in the form of a dye solution containing a dye mixture of the two dyes of the formula

wherein
n = 0 and 1, which are known from Rev. Prog. Coloration 24 (1994) 1, applied to the paper pretreated in this way. Water fastness 90%.

Example 2

The paper was first filled with the auxiliary solution consisting of 90 parts demineralized water and 10 parts of a 30% aqueous solution of a dicyan diamide / diethylenetriamine condensates (known from DE-A 39 40 481, Example 1, Auxiliaries from group U1) and then with a dye solution in the form of a Ink from 90 parts of fully demineralized water, 10 parts of diethylene glycol and 1 part Acid Blue 9 printed. Water fastness 60%.

Example 3

The paper was first filled with an auxiliary solution consisting of 80 parts demineralized water, 10 parts of 1,5-pentanediol and 10 parts of a 30% solution a dicyandiamide / diethylenetriamine condensate (known from DE-A 39 40 481, Example 1, auxiliaries from group U1) and then with a dye in the form an ink consisting of 90 parts deionized water, 10 parts 1,5-pentanediol and 1 Part of Acid Red 52 printed. Water fastness 40%.  

Example 4

The paper was first filled with an auxiliary solution consisting of 80 parts demineralized water, 10 parts of 1,5-pentanediol and 10 parts of a 30% solution a dicyandiamide / diethylenetriamine condensate (known from DE-A 39 40 481, Example 1, auxiliaries from group U1) and then with a dye in the form an ink consisting of 90 parts demineralized water, 10 parts 2-pyrrolidone and 1.5 parts C.I. Direct Red 082 printed. Water fastness 90%.

Example 5

An auxiliary solution consisting of 80 parts of fully demineralized water, 10 parts Diethylengykol and 10 parts of a 30% solution of a dicyandiamide / di ethylene triamine condensates (known from DE-A 39 40 481, Example 1, auxiliary of group U) was applied to paper. Then it was treated like this Paper with an ink made up of 88 parts deionized water, 10 parts 1.5- Pentanediol and 1 part Acid Yellow 79 and 0.2 part Direct Yellow 86 also printed. Water fastness 80%.

Example 6

An auxiliary solution consisting of 80 parts of fully demineralized water, 10 parts Diethylene glycol and 10 parts of a 30% solution of a dicyandiamide / di ethylene triamine condensates (known from DE-A 39 40 481, Example 1, auxiliary of group U) was applied to paper in the manner described. That so treated paper was inked with 86 parts deionized water, 1 part of i-propanol, 6 parts of triethylene glycol, 4 parts of 1,2,6-hexanetriol and 3 parts printed with Direct Yellow 86. Water fastness 80%.

Example 7

First, the paper was inked with 90 parts of fully desalinated Water, 10 parts 2-pyrrolidone and 1.5 parts Direct Red 082 printed and then the aid, consisting of 80 parts of fully demineralized water, 10 parts of 1.5 Pentanediol and 10 parts of a 30% solution of a dicyandiamide / diethylene triamine condensates (known from DE-A 39 40 481, Example 1, auxiliaries of Group U7). Water fastness 90%.  

The prints obtained according to Examples 1 to 7 have brilliant colors.

Other waterfast and brilliant prints were made using the in the Example 3 dye and the polymers mentioned below cationic auxiliaries according to the procedure described in Example 3 receive.

Comparative example

If you print paper with the black dye from Example 1, you get a black shade. However, the waterfastness of this print is only 40%.

If the paper to be printed is treated according to EP 534 634 with a 10% strength CaCl₂ solution before, so you get a water fastness of the pressure of 90%, however, the print bronzes very strongly and you only get a black brown.

In the pretreatment according to the invention with polymeric cationic auxiliaries you get a non-bronzing black shade and a very good one Water fastness of 90% (see example 1).

Claims (14)

1. A process for producing water-correct and brilliant prints on substrates containing hydroxyl or amide groups, characterized in that the substrate is carried with a dye of at least one anionic radical as a water-solubilizing group, printed by means of the ink-jet method and applied to the substrate, applying a polymeric cationic aid during or after printing. 2. The method according to claim 1, characterized in that the hydroxy or amide group-containing substrate from a textile fabric Cotton, wool and / or polyamide or in particular paper. 3. The method according to claim 1, characterized in that a cationic reaction product U1-U12 or mixtures thereof is used as the cationic polymeric auxiliary, the reaction products U1-U12 having the following meaning:
U1. Condensates of amines and dicyandiamide or amines and gua nidines;
U2. Reaction products of the condensates from U1 with bifunctional alkylating agents and / or aldehydes, and / or compounds containing methylolamide;
U3. Condensation products from amines and monofunctional alkylating agents, which are optionally further reacted with monofunctional alkylating and / or acylating agents;
U4. Polyallylamines or polyallylammonium compounds which are obtained by polymerizing mono- and / or di- and / or triallylamine and / or -ammonium compounds,
U5. Reaction products from polydiallylamines or polydialkylammonium compounds from the group U4. with bifunctional alkylation agents, which may also contain reactive groups;
U6. Polyamide amines obtained by reacting amines with polycarbonates or derivatives thereof;
U7. Reaction products of guanidines or dicyandiamide with aldehydes;
U8. Implementation products from U6. with bifunctional alkylating agents;
U9. Reaction products of polyols and polyisocyanates and their reaction products or quaternized secondary products with bifunctional alkylating agents and / or polycarboxylic acids or derivatives thereof;
U1O. Basic polyureas which are obtained by reacting urea with amines or by reacting polyisocyanates with amines and optionally by further reaction with bifunctional alkylating agents and / or aldehydes and / or methylolamide-containing compounds,
U11. Polyetheramines and quaternary polyetherammonium compounds which are obtained by acid-catalyzed polycondensation of amino alcohols and optionally further reaction with monofunctional alkylating and / or acylating agents,
U12. Polymers made from aziridine and / or substituted aziridines and their reaction products with bifunctional alkylating agents and / or polycarboxylic acids or derivatives thereof and / or mono-functional alkylating and / or acylating agents. 4. The method according to claim 1, characterized in that the cationic polymeric auxiliaries in the form of an aqueous solution on the substrate is applied. 5. The method according to claim 1, characterized in that the cationic polymeric aids are applied to the substrate before the substrate is printed with the dye.   6. The method according to claim 4, characterized in that the aqueous solution
1 to 20% by weight of a cationic polymeric auxiliary
0 to 30% by weight of one or more organic solvents
0 to 10 wt .-% of other additives and
40 to 98 wt% water
contains. 7. The method according to claim 1, characterized in that the dye in Form of an aqueous solution is used. 8. The method according to claim 7, characterized in that the aqueous Dye solution 1 to 20% by weight of dyes, 80 to 90% by weight of water and / or contain organic solvents. 9. The method according to claim 1, characterized in that the auxiliary and the dye is applied to the substrate using the same ink-jet method will wear. 10. The method according to claim 1, characterized in that dyes from the group as black dyes

• CI Direct Black 19,22,51,62, 113, 154, 171 and 168,
• CI Food Black 2 and
• CI Acid Black 24, 26, 52, 52: 1, 109, 155, 172 and 222,

as yellow dyes dyes from the group

• CI Acid Yellow 19, 23, 49, 79, 135, 141, 151, 169, 184, 230 and 242 and
• CI Direct Yellow 28, 50, 58, 84, 86, 132, 137, 153 and 163

as magenta dyes from the group

• CI Acid Red 35, 106, 114, 127, 143, 143: 1, 145, 227, 249, 254, 265, 266, 274, 318, 337, 341 and 361,
• CI Recative Red 180 (hydrolyzed) and
• CI Direct Red 80, 81, 82, 89, 95 and 212 and

as cyan dyes from the group

• CI Acid Blue 9, 41, 62, 78, 80, 138, 140, 182, 185, 205, 220, 221, 225, 260, 264, 277: 1, 290, 324, 350 and
• CI Direct Blue 86, 87, 106, 189, 192, 193, 199, 229, 237, 290 and 291

be used.