JPS6234959A - Production of halftone gravure printing ink - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides halftones using azo dyes.
tone) relates to a method for producing gravure printing ink.

Halftone gravure inks used for example for printing illustrated magazines and commercial catalogs are preferably 5-
It is a low viscosity liquid consisting of 10% pigment, 25-40% resin and solvent.
Encyclopedia der techn
ischenChmie), 4th edition, volume 10, page 196;
(see Verlag Hemy, Weinheim, 1973).

These printing inks dry by evaporation of the solvent, thereby leaving the resin and pigment on the printing carrier. It is important that the pigment remains as close to the surface of the print carrier as possible, since too deep penetration of the coating into the print body leads to a marked reduction in color strength. When printing thin uncoated papers, too deep penetration of the colorant may even result in penetration to the other side of the paper, resulting in loss of depth of both color and gloss, as well as a clean print on the other side. It becomes difficult. As a result of the use of special pigments in the production of halftone printing inks,
Although the pigment particles remain on or near the surface as caused by the filter action of the absorbent matrix, penetration can also occur here due to the low viscosity of the printing ink and the resulting rapid penetration. These difficulties are /\-
This is even more to be expected when soluble dyes are used instead of pigments in the production of photogravure printing inks. In this case, soluble dyes can penetrate particularly easily and deeply, since there is no filter paper action of the print carrier. This has meant that until now soluble colorants have found only very limited use in the noftone gravure printing process, for example as so-called toning dyes together with most pigments. That's why it hasn't been done. In particular, most soluble dyes will cause penetration and impression on thin and absorbent papers.

Surprisingly, compounds of the formula [where A1, A2 and A3 are hydrogen, /\logen, for example CI, Br or F, -CN, -No2. ct-C6
-alkyl, especially methyl and ethyl, cycloalkyl, especially hexyl and cyclopentyl, C1-C
l8-Alkoxy, especially methoxy and ethoxy, optionally substituted phenoxy, optionally substituted C1-〇I8-alkylsulfonyl, optionally substituted phenylsulfonyl, optionally I!
optionally substituted sulfamoyl, optionally substituted carbamoyl, optionally substituted phenylazo, C1-C1-alkoxycarbonyl,
-CF3, -3CN, C, -C,2-furkylmercapto, C, -C6-alkylcarbonyl, optionally substituted phenylcarbonyl or -OH, A4 and A5 are hydrogen, halogen, For example, CI, Br
or F, optionally substituted c, -C6-
Alkyl, especially methyl and ethyl, optionally substituted C,-C6-alkoxy, especially methoxy and ethoxy, -NH-O-CH2CH,OA, -NH-O-A8, -NH-5o2-A8 ,NH-O-
0-A9, -NH-O-A-COOH1 -NH-O-CH20Ae, Alo All l0A11 .

A8 represents CI C22-alkyl, C2-C22-alkenyl, C3-C7-cycloalkyl, in particular cyclopentyl and cyclohexyl, phenyl, naphthyl or phenyl-Ct-C4-alkyl, in which the aryl group mentioned above is for example Cm-C6 -alkyl, c, -C1
, -alkoxy, C1,Br, F, -No2 and cyclohexyl, A9 is ci C22-alkyl, C2-C22-alkenyl, C3-C7-cycloalkyl or phenyl-
c, -C4-alkyl, Alo, A'lo and All are hydrogen, CI C2
2-alkyl or C2C22-alkenyl, preferably dodecenyl, and A' and A'' are optionally substituted by c, -Ca-alkyl, especially methyl, halogen, such as chlorine or bromine, or -COOH A6 represents aryl, preferably optionally substituted phenyl, or A7 represents hydrogen or aliphatic represents a group group in which the groups A4 and A6 can also be joined to form a ring, preferably a 6-membered ring, such as a tetrahydroquinoline or benzomorpholine ring, and in which the groups A6 and A7 are -(CH2)n - group (n=4 or 5) or -(CH2) 20 (
It has now been found that dyes of the following are suitable for the production of semi-toned gravure printing inks.

Phenylsulfonyl, phenoxy, phenylcarbonyl and phenylazo groups A, , A2 and A3 are e.g.
1-C6-alkyl, Cm-C6-alkoxy, CI
, Br, F, -NO2 and cyclohexyl.

The ct-C1B-alkylsulfonyl groups A, , A2 and A3 may be substituted, for example, by c, -C6-alkoxy. Examples include c, -C6-alkoxy-c, -C6-alkylsulfonyl groups.

The sulfamoyl and carbamoyl groups A1, A2 and A3 can, for example, also be -0H1-〇N or the group -0-O-
A-COOI (, 1 or 2 CI − which may be substituted by Alo All A 1oA I 1 )
Optionally substituted with a CI 8-alkyl group.

C, -c,, -alkyl groups A4 and A5 are for example -C
Optionally substituted by OOH and c, -C6-alkoxycarbonyl. cl -cl-alkoxy group A
4 and A5 may be substituted, for example by C1-C4-alkoxy.

The phenyl group A6 is, for example, Ct-C6-alkyl, c, -
Optionally substituted by C6-alkoxy, cyclohexyl, CI, Br, F and -NO2.

The following groups are suitable groups A: The aliphatic groups A6 and A7 are preferably ci-C22-alkyl and C2C22- which may be optionally interrupted and/or substituted by zero non-adjacent atoms. It is an alkenyl group or a C3-C7-cycloalkyl group. Those in F are examples of suitable substituents in these alkyl and alkenyl groups: -0H1-
CN, -0-O-A-COOH1 -O-O-CH-CH-COOH1A IOAta -0CO-As, -0-Oo-A9, -COOA9 and JC and -OA, 2° where A, A8. A9. A. and aZ have the meanings indicated for formula 1 and Al1 represents C3-C7-cycloalkyl, in particular cyclopentyl and cyclohexyl, phenyl, naphthyl and phenyl-c,-c4-alkyl.

Preferred groups A6 and A7 are as follows: hydrogen, -
CI C2 substituted by CN or 10H
2-alkyl, C2C22-alkenyl, C3C7-cycloalkyl, -CH2-CH-A, 4', OA,.

mCH2CH2-C00A9, - (CH2CH2-0)mCH2-0), -(CH2
CH20) m-A45, where Ata represents Hl-CO-A-CO- or Alo A11 IoA11 and Ata is hydrogen, c, -CB-alkyl or mCH2-
0-As, Ata represents hydrogen or c, -O-alkyl, n represents l, 2 or 3, and m represents 1.2.3.4.5.6.7.8.9 or 10, and A8. AIo, A++ and A have the meanings indicated for Formula 1.

It is preferred to use compounds according to formula 1 below: 1°A.

, where A16 represents CI, Br or CN, X represents H,
CH3, C2H5, C6H12, tert-butyl, C, -C4-alkoxy, CI or Br, Y is -NO2, -CN, -CF3, CH-CI2
Compounds representing -alkylsulfonyl, and Y' represents -No2 or 10N.

2°, where AB7 represents hydrogen, chlorine, C,-C4-alkyl, especially methyl and ethyl, and c,-c4-alkoxy, especially methoxy and ethoxy, and AH8 represents -NHO CH2CH20A8, -NH -C
OAg, -NH-O-0-A9, -NHCOCH20Ae, -NH-Go-A-CO-AloA11A+oAl+, and A, AB, A9, Alo and Az have the meanings indicated for Equation 1. Compounds with

A6. A7. AI 6. With regard to AHt, AI B, X, Y and Y', it is therefore particularly preferred to use compounds of the formula having the meanings given above.

is A6 N is -N (C2H5) 2 , N (0387)
2, N (CH3)2, or.

The last-mentioned groups are added by reacting the corresponding OH compounds with dodecenylsuccinic anhydride.

Compounds of the formula 1 are known or can be prepared analogously to methods known from the literature (for example German patent specification 6).
55.950, European Patent Application 273.382, Swiss Patent Specification 567.067, German Published Specification 1.
544.388, German Publication No. 2,815,506
, German Published Specification 1,544,386. (see German Published Specification 2.129,590 and Italian Patent Specification 886.176).

The present invention also relates to the formula [wherein A5' represents AIOA11 IoA11 and A6' is optionally
t A represents a CI C22-alkyl or c2 C22-alkenyl group optionally substituted by IOA I 1 or in particular represents the group -CH2-CH-Ata OA' +a, where A'13 is -O- A-COOH1A lo A11 AtOA+1 and All A2. Aa, A4. A5. A6. A7, A, A
lo, A11 and ata have the meanings given above.] It also relates to novel dyes.

Half compounds of the formula 1 have a proportion by weight of hydrocarbon groups not directly bonded to the azo groups in the dye molecule of at least 20%, particularly preferably at least 25% and very particularly preferably at least 30%. It is suitably used in the production of tone gravure printing ink.

Let us illustrate the calculation of the selection of these compounds by means of two examples: In formulas α) and β), hydrocarbon groups that are not directly bonded to the azo group are marked.

In formula α) the weight proportion of these groups in the total weight of the molecule is 39.6% and in formula β) 23.
It is 8%.

l\-Ftone gravure printing inks prepared using dyes of formula I preferably have component classes A), B) and C.
A) about 2% to about 20% colorant, B) about 10% to about 40% resin, and C) about 80% by weight.)
Contains approximately 50% by weight solvent.

The colorant can also be a mixture of different dyes of formula I, and in particular of at least one dye of formula 1 and at least one pigment suitable for halftone gravure printing inks. . The last mentioned mixtures contain up to 90% by weight, preferably 50% by weight.
Contains pigments up to.

Pigments suitable for the preparation of mixtures of dyes and pigments of formula 1 are preferably red pigments, such as C,1, Pigment Red 2.53.57:l, 112.122.146 and 148. In addition, pigments with different shades can be used to produce special shades, such as C,1, Pigment Yellow 12.13.14.17.74 and 83, c, r, Pigment Orange 5 and 34, C,1, Pigment purple 19, C, 1,
Pigment Blue 15 and 27, C,1, Pigment Green 7 and 3
6, as well as C,1, pigment black 7, are also suitable. Dyes of formula 1 can also be used for toning the pigments mentioned above.

Examples of suitable resins are giltzite asphalt, rosin-modified resins, such as calcium, zinc and magnesium salts of resin acids and their modified products, resin esters, maleate resins, rosin-modified phenolic resins. hydrocarbon resins, ketone resins, chlorinated rubber, nitrocellulose, polyamide resins, shellac, vinyl resins, etc.

Suitable types can be found, for example, in Lackrohst Offtabe by Karsten.
llen) J, 7th edition, Kurt-RΦ Vincent Verlag.

Suitable solvents are aromatic and aliphatic hydrocarbons, such as gas oil fractions, C, -C8-aliphatic hydrocarbons, xylene and especially toluene.

It is also possible to use mixtures of aliphatic and aromatic hydrocarbons.

The present invention relates to the use of dyes of formula 1 in the preparation of halftone gravure printing inks, preferably based on toluene.

To prepare half')-n gravure printing inks, the dyes of the formula I, optionally mixed with pigments, are added in a customary manner to the printing ink mixture.

In the method according to the invention for producing halftone gravure printing inks, an inorganic additive having a BET specific surface area of at least 50 m'/g, preferably at least 100 m2/g and particularly preferably at least 200 m2/g can be added in addition to the dyes of formula I.

Additives that have proven suitable are in particular aluminum hydroxide, very especially silica. The additives preferably amount to 0.2-2% by weight relative to the weight of the printing ink.
of, particularly preferably 0.4-0.9% by weight.

These additives can further reduce the penetrating tendency of the dye and can produce results that are only obtainable when using pigments alone.

The finely divided silicas preferably used are mainly amorphous, cross-linked to varying degrees and finely divided silicas having the specific surface areas mentioned above. Silicas of this type are known, for example, from Ullmann's Encyclopedia der Technisschen Hemi, 4th edition, volume 21, pages 451-476. The silicas are obtained, for example, by precipitation from solution or by high-temperature processes and, besides the major silica, they can also contain other metal oxides and hydroxides, such as those of aluminum and titanium.

It is necessary that silica be dispersed in the gravure printing ink. This dispersion can be carried out in the finished gravure printing ink or in the concentrate. However, it is also possible first to prepare the dispersion in the solvent used for the gravure printing ink, which may optionally be relatively concentrated, and part or all of the resin added at this stage. The following are examples of suitable dispersion equipment: Nystara-1 high speed stirrer, dissolver, bead mill and ball mill or combinations of these equipment.

In addition to the silicas, it is also advantageous to add wetting agents and dispersants to these silicas. Particularly suitable dispersants are salts of strong organophilic acids with aliphatic amines and polyamines which may optionally contain hydroxyl groups.

The following are examples of organophilic strong acids: C1o C
20-Alkanesulfonic acids, alkylarylsulfonic acids, such as dodecylbenzenesulfonic acid or di-tert-butylnaphthalenesulfonic acid, or sulfuric acid monoesters or phosphoric acid monoesters or diesters of alkanols, or their combination with ethylene oxide. Reaction products. Examples of alkanols of this type are saturated or unsaturated linear or branched ca-
c22-Aliphatic alcohols, such as butanol, 2-
Ethylhexanol, dodecanol, tetradecyl, hexadecyl and octadecyl alcohols and oleyl alcohol and the reaction products of these alcohols with 1-20 moles of ethylene oxide or propylene oxide.

The following are examples of suitable aliphatic amines: ethylenediamine, 2H2N (CH2CH2NH)nH [where n=2-
6], propylene diamine, dipropylene diamine and beef tallow propylene diamine. Examples of suitable amines containing hydroxyl groups are those formed in the reaction of ammonia or CI C20-alkyl mono-, di- or polyamines with ethylene oxide or propylene oxide or with shrimp chlorohydrin. .

The following are examples of these: ethanolamine, jetanolamine and triethanolamine, tris-(2-(2- and droxyethoxy)-ethyl]-amine, bis-[2-(2-hydroxyethoxy) )-ethyl]-amine, bis-(2-hydroxyethyl)-methylamine, bis-(2-hydroxyethyl)-ethylamine, bis-(2-hydroxyethyl)-propylamine or bis-(2-hydroxyethyl) -butylamine, 2-(2-aminoethylamino)-ethanol, 2-
(hydroxyethyl)-bis-(2-hydroxypropyl)-amine, tris-(2-hydroxypropyl)-
amine, 3-[bis-(2-hydroxyethyl)-amino]-propylamine, pentahydroxyethyldiethylenetriamine and 2,3-dihydroxypropylamine: and oxidation of 2 moles with coconut oil amine, tallow amine, stearylamine and oleylamine Reaction products of ethylene or tallow propylene diamine and 3 moles of ethylene oxide.

These dispersants contain 10-200% by weight of silica.
preferably between 50 and 100% by weight.

Examples of other suitable finely dispersed additives are finely dispersed aluminum hydroxide or aluminum hydroxide gel;
They are substantially amorphous and are obtained from acidic aluminum salt solutions by precipitation with bases or by flame hydrolysis methods. Suitable aluminum hydroxides have a BET specific surface area of at least about 50 m'/g. They can be dispersed in the same manner as described above for silica, with the addition of the same dispersants. Mixtures of finely dispersed aluminum hydroxides and silicas can also be used according to the invention.

Penetration or penetration of the printing ink is assessed visually from the other side or with a colorimeter to assess the extent to which the print or coating of the printing ink on the printed material, such as printing paper, is visible or penetrated. It can be tested by

Penetration is particularly important in the case of attractively priced grades of paper which have paper form weights of less than 42 g/m2 and which are increasingly used.

Furthermore, the novel dyes according to the invention can also be used for surface coatings, dyeing other organic solvents and mineral oil products, since they are characterized by an unexpectedly high solubility in these media. This is because Examples of these individual substrates that can be dyed with the new dyes are esters, ketones, glycols, glycol ethers and alcohols such as ethyl acetate, butyl acetate,
Methoxyethyl acetate, acetone, methyl ethyl ketone,
Methyl glycol, methyl diglycol, butyl diglycol, ethanol, propatool, butanol, butyl phthalate and ethyl phthalate, or writing inks, fuel oils and diesel oils and common organic solvents.

In particular, the new dyes, optionally mixed with pigments, can also be used for the production of flexographic and packaging gravure printing inks. The novel dyes can also be used in this application in the formulations described above containing finely dispersed inorganic additives.

17.3 g (0.1 mol) of 2-chloro-4-nitroaniline were stirred overnight with a mixture of 40 ml of water and 35 ml of 1ON hydrochloric acid. Bring the mixture to 0°C by adding ice.
and diazotized with 7.0 g of an aqueous solution of sodium nitrite. The mixture was heated at O-5°C for 2
After stirring for an hour and keeping the excess nitrite constant, the excess nitrite was destroyed using sulfamic acid. Then 45.6 g of N-[3-(dipropylamine)-phenyl]-oleylamide in the hydrochloride form
ml of a solution in rice acetic acid was added to the mixture. Coupling was completed in 5 hours. The precipitate was filtered off with suction and washed thoroughly with water. The wet paste was added to 300 ml of toluene and the solution was washed with 200 ml of IN sodium carbonate solution. The organic phase was separated and the toluene was removed by distillation. The remaining residue (61.8 g) was dissolved in 60 g of toluene. This gave a 50% strength solution of the dye of formula.

10 g dye solution, 69.5 g toluene and 25.
5g of Arcinol K, a thinless hydrocarbon resin
Z71 was mixed. This gave a toluene gravure ink with a viscosity corresponding to a flow time of 23 seconds in a DIN 3 cup as specified in DIN 53,211. When this printing ink was used for printing gravure paper on a Tuner gravure manual proofing device, very deep bluish-red prints were obtained.

When these prints were evaluated, it was found that the printing inks already had very good penetration properties.

Only on very light papers was a somewhat worse penetration performance compared to a printing ink of the same viscosity made with pigments only.

Example 2 A printing ink was carried out consisting of 10 g of the dye solution according to Example 1, 70 g of toluene and 25 g of Arsinol KZ71 and also containing 0.8 g of a dispersion of Aerosil 380, a finely dispersed silica from Degussa. Produced in the same manner as in Example 1. The performance of printing ink is shown in Example 1.
The penetration performance was satisfactory even when printing on paper with low weight per unit area.Aerosil 300, Aerosil 200 or Wacker φ
Similar results were obtained when HDKT40, a finely dispersed silica manufactured by Hemy, was used in place of Aerosil 380.

The above silicas had BET specific surface areas of 300.200.400 and 380 m'/gv, respectively.

Printing inks having similar properties were obtained using dyes prepared in the same manner as in Examples 1 and 2 from the components listed in the table below.60.H.

Blue λ = a x 61 1 614 lm Blue blue color ↓ 1 37.9 g of diazotized 2-chloro-4-nitrotoluene is N,N-bis-(2-hydroxyethyl)-
The dye obtained by coupling with 3-methylaniline, 200 ml of toluene and 58.6 g of National Starch dodecenyl succinic anhydride (mixture) Fibran 68 was heated under reflux for 12 hours,
Then some of the toluene was removed by distillation. This gave 135 g of a dark solution of a mixture of dyes of the general formula in which the radicals R and R' represent dodecenylsuccinic acid half ester radicals.

Printing inks prepared analogously to Examples 1 and 2 produced red prints with properties very similar to those described in these Examples.

The dyes listed in the table below were reacted according to the method described in Example 17 with the anhydrides also indicated in the table. The printing inks prepared from the new esters obtained in this way were comparable in their properties to the printing inks prepared according to Examples 1 and 2).

CH9 C113 By CH3 Br C' If 3 Fipran Purple CH3 Printing inks with equally good compatibility could be prepared with the dyes of Table 3 below.

Table 6: , CI printing color tone CM NH-CO-(CH,), 6CH3CI
NH-CO-(CH,), -CH3C,H.

CM NH-8Ot(CH,), -CH3 bluish red CI NH-O -(CM,),,CH3N
H-O (CH,), CH=CH-(C) 1° decenyl ruby purple fzL"s purple greenish blue [CHtLCHs greenish blue greenish blue reddish blue H3 true color CM NEC0 (CH, ),,CH3CN N
HCO(CH,), CH=CH-(CCF3 NHC
O-(CH,), CH=CH-(blue blue Ht) y''Hs blue CH,), CH.

t CM CN　　　　(’Z CH3 ■ dodecenyl red red red Agn-

Claims (1)

[Claims] 1. Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, A_1, A_2 and A_3 are hydrogen, halogen, such as Cl, Br or F, -CN, -NO_2, C_1-C_6-alkyl, especially methyl and ethyl, cycloalkyl, especially cyclohexyl and cyclopentyl, C_1-C_1_8-alkoxy,
In particular, methoxy and ethoxy, optionally substituted phenoxy, optionally substituted C_1-
C_1_8-alkylsulfonyl, optionally substituted phenylsulfonyl, optionally substituted sulfamoyl, optionally substituted carbamoyl, optionally substituted phenylazo,
C_1-C_1_8-alkoxycarbonyl, -CF_
3, -SCN, C_1-C_1_2-alkylmercapto, C_1-C_6-alkylcarbonyl, optionally substituted phenylcarbonyl or -OH, A_4 and A_5 are hydrogen, halogen, e.g. Cl,
Br or F, optionally substituted C_1-
C_6-alkyl, especially methyl and ethyl, optionally substituted C_1-C_6-alkoxy, especially methoxy and ethoxy, -NH-CO-CH_2CH_2OA_8, -NH-C
O-A_8, -NH-SO_2-A_8, NH-CO-
O-A_9, -NH-CO-A-COOH, -NH-CO-CH_2OA_8, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Indicates that A_8 is C_1-C_2_2-alkyl , C_2-C_
2_2-alkenyl, C_3-C_7-cycloalkyl, in particular cyclopentyl and cyclohexyl, phenyl, naphthyl or phenyl-C_1-C_4-alkyl, where the aryl group mentioned above is for example C_1-C_
6-alkyl, C_1-C_6-alkoxy, Cl, B
Optionally substituted by r, F, -NO_2 and cyclohexyl, A_9 is C_1-C_2_2-alkyl, C_2-C_
2_2-alkenyl, C_3-C_7-cycloalkyl or phenyl-C_1-C_4-alkyl, A_1_0, A'_1_0 and A_1_1 are hydrogen,
C_1-C_2_2-alkyl or C_2-C_2_
2-alkenyl, preferably dodecenyl, a is ▲a formula, a chemical formula, a table, etc.▼ or ▲a
There are chemical formulas, tables, etc.▼ where A' and A'' are optionally C_1-C_4-alkyl,
Carbocyclic 5 optionally substituted especially by methyl, halogen, such as chlorine or bromine, or -COOH
or the remaining members of a six-membered ring, A_6 represents aryl, preferably optionally substituted phenyl, or A_7, and A_7 represents hydrogen or an aliphatic group, where the groups A_4 and A_6 can also be linked to form a ring, preferably a 6-membered ring, such as a tetrahydroquinoline or benzomorpholine ring, and the groups A_6 and A_7 are -(CH
_2)_n- group (n=4 or 5) or -(CH_
2) _2-O-(CH_2)_2- may be cyclized with a group] A method for producing a halftone gravure printing ink, characterized by using the following dyes. 2, C_1-C_2_2-alkyl and C_2-C_2_, in which A_6 and A_7 may be optionally interrupted and/or substituted by non-adjacent O atoms;
2. Process according to claim 1, characterized in that dyes of the formula I are used which represent a 2-alkenyl group or a C_3-C_7-cycloalkyl group. 3, A_6 and A_7 are each arbitrarily non-adjacent O
C_1-C_2_2- which may be interrupted by atoms
Represents alkyl and C_2-C_2_2-alkenyl groups, and these groups are -OH, -CN, -O-CO-A-COOH, -OCO-A_8, -O-COO-A_9, -COOA
_9 and -OA_1_2, where A_1_2 is C_3-C_7-cycloalkyl,
Especially cyclopentyl and cyclohexyl, phenyl,
2. Process according to claim 1, characterized in that dyes of the formula I are used which represent naphthyl and phenyl-C_1-C_4-alkyl. 4. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A_1_6 is Cl , Br or CN, X is H, C
H_3, C_2H_5, C_6H_1_2, -C(CH
_3) _3, C_1-C_4-alkoxy, Cl or Br, Y is -NO_2, -CN, -CF_3, C_1-C_1
_2-alkylsulfonyl, and Y' is -NO
_2 or -CN] The method according to claim 1, characterized in that the dyes are used. 5. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A_1_7 is hydrogen, chlorine, C_1-C_4-alkyl,
especially methyl and ethyl, and C_1-C_4-alkoxy, especially methoxy and ethoxy, and A_1_8 is -NH-CO-CH_2CH_2-OA_8, -NH-
CO-A_8, -NH-CO-A_9, -NH-CO-A-COOH, -NH-COCH_2-OA_8, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, The method according to claim 1, characterized in that dyes of the following are used. 6. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. Method. 7. Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (III) [In the formula, A_1, A_2 and A_3 are hydrogen, halogen, such as Cl, Br or F, -CN, -NO_2, C_1-C_6-alkyl, Especially methyl and ethyl, cycloalkyl, especially cyclohexyl and cyclopentyl, C_1-C_6-alkoxy, especially methoxy and ethoxy, optionally substituted phenoxy, optionally substituted C_1-C_
6-alkylsulfonyl, optionally substituted phenylsulfonyl, optionally substituted sulfamoyl, optionally substituted carbamoyl, optionally substituted phenylazo, C_1-
C_6-alkoxycarbonyl, -CF_3, -SCN, C_1-C_1_2-alkylmercapto,
C_1-C_6-alkylcarbonyl, optionally substituted phenylcarbonyl or -OH, A_4 is hydrogen, halogen, e.g. Cl, Br or F
, optionally substituted C_1-C_6-alkyl, especially methyl and ethyl, optionally substituted C_1-C_6-alkoxy, especially methoxy and ethoxy, -NH-CO-CH_2CH_2OA_8, -NH
-CO-A_8, NH-CO-O-A_9, -NH-C
O-A-COOH, -NH-SO_2-A_8, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, A'5 indicates ▲Mathematical formulas, chemical formulas, tables, etc. There is ▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where A_8 is C_1-C_2_1-alkyl, C_2-C_
2_1-alkenyl, C_3-C_7-cycloalkyl, especially cyclopentyl and cyclohexyl, phenyl, naphthyl or phenyl-C_1-C_4-alkyl, A_9 is C_1-C_2_2-alkyl, C_2-C_
2_2-alkenyl, C_3-C_7-cycloalkyl or phenyl-C_1-C_4-alkyl, A_1_0 and A_1_1 are hydrogen, C_1-C_2
_2-alkyl or C_2-C_2_2-alkenyl, preferably dodecenyl, where A_1_1 is other than H if A_1_0=H and A_1_1 if A_1_1=H
＿0 is other than H and indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and A' and A'' are optionally C_1-C_4-alkyl,
Carbocyclic 5 optionally substituted especially by methyl, halogen, such as chlorine or bromine, or -COOH
or the remaining members of a six-membered ring, A_6 represents aryl, preferably optionally substituted phenyl, or A_7 represents hydrogen or an aliphatic group, where the groups A_4 and A_6 may also be linked to form a ring, preferably a 6-membered ring, such as a tetrahydroquinoline or benzomorpholine ring, and the group A
_6 and A_7 are -(CH_2)_n- group (n=4 or 5) or -(CH_2)_2-O-(CH_2
)_2-group may be cyclized, and A'_5 may represent ▲a numerical formula, a chemical formula, a table, etc.▼, or] dyes. 8. Formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (IV) [In the formula, A_1, A_2 and A_3 are hydrogen, halogen, such as Cl, Br or F, -CN, -NO_2, C_1-C_6-alkyl, Especially methyl and ethyl, cycloalkyl, especially cyclohexyl and cyclopentyl, C_1-C_6-alkoxy, especially methoxy and ethoxy, optionally substituted phenoxy, optionally substituted C_1-C_
6-alkylsulfonyl, optionally substituted phenylsulfonyl, optionally substituted sulfamoyl, optionally substituted carbamoyl, optionally substituted phenylazo, C_1-
C_6-alkoxycarbonyl, -CF_3, -SCN, C_1-C_1_2-alkylmercapto,
C_1-C_6-alkylcarbonyl, optionally substituted phenylcarbonyl or -OH, A_4 and A_5 are hydrogen, halogen, e.g. Cl,
Br or F, optionally substituted C_1-
C_6-alkyl, especially methyl and ethyl, optionally substituted C_1-C_6-alkoxy, especially methoxy and ethoxy, -NH-CO-CH_2CH_2OA_8, -NH-C
O-A_8, NH-CO-O-A_9, -NH-CO-
A-COOH, -NH-SO_2A_8, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, A_8 is C_1-C_2_1-alkyl, C_2-C_
2_1-alkenyl, C_3-C_7-cycloalkyl, especially cyclopentyl and cyclohexyl, phenyl, naphthyl or phenyl-C_1-C_4-alkyl, A_9 is C_1-C_2_2-alkyl, C_2-C_
2_2-alkenyl, C_3-C_7-cycloalkyl or phenyl-C_1-C_4-alkyl, A_1_0 and A_1_1 are hydrogen, C_1-C_2
_2-alkyl or C_2-C_2_2-alkenyl, preferably dodecenyl, where A_1_1 is other than H if A_1_0=H and A_1_1 if A_1_1=H
＿0 is other than H, A is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲Mathematical formula,
There are chemical formulas, tables, etc.▼ where A' and A'' are optionally C_1-C_4-alkyl,
Carbocyclic 5 optionally substituted especially by methyl, halogen, such as chlorine or bromine, or -COOH
or the remaining member of a 6-membered ring, A_7 represents hydrogen or an aliphatic group, and A_6' is -O-CO-A-COOH, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲Numerical formulas, represents a C_1-C_2_2-alkyl or C_2-C_2_2-alkenyl group substituted by ▼ or specifically represents a group ▲ represents a mathematical formula, table, etc. ▼, where A_1_3' is - CO-A-COOH, ▲ formula,
There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ] Dyes. 9. Process for producing halftone gravure printing inks according to claims 1 to 8, characterized in that azo dye/pigment mixtures are used. 10. A method according to claims 1 to 9 for producing a toluene-based halftone gravure ink.