JPS6234960A - 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 relates to a method for making halftone gravure printing inks using pyridone azo dyes, and to novel pyridone azo dyes.

Halftone gravure printing inks used for printing pictorial magazines and commercial catalogs are preferably low viscosity liquids consisting of 5-10% pigment, 25-40% resin, and solvent [see Ullmann's Eng. Cyclopedie Dare ◎ Technissien Hemi (U11mann!
＋ Eneyklopaedieder technique
lschen Chemie), 4th edition, Vol.
emia, We'inhe1m), 1979]. These gravure printing inks dry by evaporation of the solvent, so that resin and pigment remain on the printing carrier. In this case it is important that the pigment remains on the surface of the print carrier as much as possible, since if the colorant penetrates too deeply into the print carrier, the apparent intensity of the color will be reduced. When printing on thin, uncoated paper, the result of too deep penetration of the colorant is that the color bleeds through to the reverse side of the paper, which reduces both color depth and gloss. damage, and even makes it difficult to print cleanly on a good surface. If special pigments are used in the production of halftone gravure printing inks, the pigment particles remain on or near the surface as a result of the filtration action of the absorbent substrate, but due to the low viscosity of the printing ink and the resulting rapid Strike-through also occurs in this case due to penetration. These difficulties are expected to be exacerbated when soluble dyes are used in place of pigments in the production of 1-ftone gravure printing inks. Since the filtration action of the print carrier is absent in this case, the soluble dye penetrates particularly rapidly and deeply. This is because soluble colorants have hitherto only been used in limited ways in halftone gravure printing, for example in so-called toning.
ing) This is the reason why it has only been found to be used as a dye in combination with an overwhelming proportion of pigments.

It has now surprisingly been discovered that certain pyridone azo dyes are suitable for the production of halftone gravure printing inks.

One group of these pyridone azo dyes is prepared by reacting pyridone azo dyes having 1 to 4 hydroxyl groups or 1 to 4 carboxyl groups with dihydroxy or polyhydroxy compounds or with dicarboxylic acids or polycarboxylic acids/polycarboxylic acids. Both can be prepared by creating an ester-like linkage between two identical or different birylene azo dyes.

Pyridone azo dyes having 1 to 4 hydroxyl groups have the formula % [wherein D represents the group of the diazo component, T1 represents alkyl, aryl or -COOT, and T! represents H, -ON, -COOT, or -CONH-T@(OH)n, and Ts is an aliphatic or aliphatic compound in which one or more oxygen atoms may be present.
7 represents an atic group, T represents hydrogen or alkyl, T, F! represents an aliphatic or arariphatic group in which one or more oxygen atoms may be present, and m and n represent 0.122.3 or 4, provided that the sum of man is 122.5 or 4; Corresponds to [Ruru].

D is preferably optionally substituted C1-Ctt alkyl,
C-Ctt alkenyl, cyclohexyl, cyclopentyl, cyclohexenyl, halogeno such as Ct, Br or Hz C's-Co alkoxy, optionally substituted phenoxy, -CN, -0F,.

-NO, optionally substituted C1-Cta alkylsulfonyl 2't substituents belonging to the system comprising optionally substituted *benzylsulfonyl, optionally substituted phenoxysulfonyl, optionally substituted carbamoyl and optionally substituted sulfamoyl Represents a phenyl group which may contain 1 to 4.

C! ~CI! The alkyl group in alkyl and cl-cts alkylsulfonyl is, for example, -OH.

Substituted with 01-C6 alkoxy or -〇N. The phenyl group in phenoxy, phenylsulfonyl, phenoxysulfonyl and benzylsulfonyl may be substituted, for example with C3-C4 alkyl or 710rn, such as Ct and Br.

The carbamoyl group is preferably C1-0111-alkyl, C! which may be substituted, for example by -OH. ~C1, alkenyl, aryloxyalkyl, C9~C1l aral; xyalkyl, C1~Croaralkyl, C4~CSS
Acytetraxyalkyl, C6-C14 alkoxycarbonyloxyalkyl, C6-Ctt alkylaminocal has two identical or anisotropic substituents belonging to the system comprising nyloxyalkyl and 04-C dialkylaminoalkyl ; The corresponding diazo component is described in German Patent Publication No. 3.
No. 111,648.

The sulfamoyl group is preferably C1-C18 alkyl or 01-CI! optionally substituted with 0 and optionally substituted with hydroxy or phenoxy! It has one or two substituents belonging to the system comprising alkyl or Cτ to Ctt alkyl: the corresponding diazo component is disclosed in Yorotsunohira Patent No. 1a567.

The following may be mentioned as examples of diazo components: aniline, Q-1nl- and p-)luidine, O-ethylaniline, p-ethylaniline, 2,3-dimethylaniline,
3.4-dimethylaniline, 2.4-dimethylaniline, 2.5-dimethylaniline, O-isopropylaniline, p-isopropylaniline, 2.4゜5-trimethylaniline-2,5,5-)dimethylaniline, 2-Methyl-5-isopropylaniline, 4-tert-butylaniline, 4-aec-butylaniline, aniline substituted with straight chain or branched Cs*Hta-alkyl at Q+ or p-position, 4-cyclohexylaniline , 4-cyclohexyl-2-methylaniline, 4-(1-cyclohexen-1-yl)-aniline, p-13- and p-
10 Luaniline, 2e3-1264-12.5- and 3
．． 4-dichloroaniline, 5-10-2-methylaniline, 4-chloro-2-butylaniline, 3-chloro-
2-methylaniline, 2-μ-5-methylaniline)
7. A-10-5-metalani I) 7. S-chloro-
4-Methylaniline, 2-chloro-3,4-dimethylaniline, 5-chloro-2,4-dimethylaniline, 4-
Chlor-2,5-dimethylaniline, o-13- and Up
= Nitroaniline, 2-! Chloro-4-nitroaniline, 2-nitro-4-chloroaniline, 2-methyl-
4-2) 1:+7='), 4-methyl-2-2-4troaniline, 294-dimethyl-5-nitroaniline, 2.5-dimethyl-4-nidotetraaniline, 4-improvir-2- 5-tetraaniline, 4-tert-butyl-2-nitroaniline, 4-\chlorohexyl-2-nido-paniline, 0-13- and p-methoxyaniline, 2
-Ethoxy- and 4-ethoxyaniline/, 2-phenoxyaniline, 2-(2-methylphenoxygen)-aniline, 5-riP-2-methoxyaniline, 5-chloro-2
-phenoxy-aniline, 5-dichloro-2-(4-chlorophenoxy)-aniline, 4,5-dichloro-2-methoxyaniline, 2-methoxy-5-nitroaniline,
2-Methoxy-4-nitroaniline, 5-14-4-
Methoxyaniline, 4-ethoxy-3-nitroaniline, 3-methoxy-4-methylaniline, 4-methoxy-
2-methylanili/, 2-methoxy-5-methylaniline, 2-ethoxy-5-methylaniline, 4-chloro-
2-methoxy-5-methylaniline, 4-chloro-2,
5-dimethoxyaniline, 2.5-dimethoxy-4-nitroaniline, 2-(phenylsulfonyl)-aniline, 2-(methylsulfonyl)-4-nitroaniline, 2
-methoxy-5-(phenylsulfonyl)-7niline
5-(4-ndylsulfonyl)-2-methoxyaniline,
5-(ethylsulfonyl)-2-methoxyaniline, or when m in formula I is >0, i.e. the diazo component is 1
When it has ~4 hydroxyl groups, DFi prefers "! or hydroxy-01~C,,, flukoxy, -'No
! , -CNN F% C1% Br or C1~C
[where T6 and T, #i denote an aliphatic group optionally having one or more intervening oxygen atoms, and T is hydrogen or one or more The above represents an aliphatic or acylphatic group which may have an intervening oxygen atom] represents a phenyl group substituted with a group of 1 or 2
may contain additional substituents.

Alkyl (T1 and T4) is preferably C1-C.

Represents alkyl, especially methyl and ethyl.

When the weight is 0, TI and T1 are preferably 01-C■alkyl, C2-C, alkenyl, C,-C-1 cycloalkyl, benzyl, phenethyl, C1-C,, flukoxyalkyl, phenoxy-〇, ~CWt alkyl or phenoxy-〇, ~018 represents alkoxyalkyl.

Examples of suitable groups T or T are methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, inbutyl, n-pentyl, isopentyl, -CHlC(CHa
)ssn-to'P syl, cyclohexyl, n-;ttrif
k, 2-ethyl-hexyl, decyl, dodecyl, tukurumityl, stearyl or oleyl; or -C) T,C
H,OCH -CHICH,QC,H-CH1CH
gCH10(CHJsCHs, -CbirdCHz CHl
OCHl CH(CHt) s CHs, C, Hl -CH2CH2CH20(CHt)+ ICHm, -C
H, CH, OCH, CH10CRs.

-CHsCHtCH2OCHxCHtO(CHt)
s CI (represents s).

When n is >0, Ta and T are preferably 1L1 to 6
C represents an alkyl group in which O atoms may be present, and the following are examples of corresponding hydroxyalkyl groups: -CH, CH, OH, -CH, CH, CH, OH.

-CHICH(OH)CHs, -CHtCH(O
H) CHICHI, -CHtCHlCH(OH)CHs
, -CHICH*CHtCH*OH%-CH,CH,
QC quick C horse OH.

-CH*CHt (OCH*CHt) pOH(p=
1-5), -CHtCH,CH錞OCH いCH,O
H.

-CHtCHtCHt (0CHtCH*) q O
H (q=1-3), -CH,CH,CHHO2CH
, ), OH.

-CH, CBICH 0 (CHl, OH.

-CHt CHsCHtOCHtCHlIc H(CH
s) CHt CHs OH%-C-CH(OH)C
Pyridone azo dyes having 1 to 4 carboxyl groups preferably have the formula (COOH)n [wherein m, n and T1 have the meanings given for formula (2) and T2' indicates H, -CN or -COOT4', provided that T
4 has the meaning shown in formula ①, T represents an aliphatic or arariphatic group in which one or more oxygen atoms may be present, and p/ represents a group of a diazo component] corresponds to

When n=o, T. is preferably 01 to Ct! Alkyl, C! ~C! Elephant alkenyl, C1-C, cycloalkyl, benzyl, phenethyl, C1-C1, alkoxyalkyl, phenoxy-01-C22 alkyl or phenoxy-C! ~CtS represents alkoxyalkyl.

Examples of suitable radicals T9 are methyl, ethyl, n-glovir, inglovir, allyl, n-butyl, isobutyl, n-pentyl, impentyl, -CH,C(OH,), , n
-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, decyl, dodecyl, palmityl, stearyl, oleyl, -cH! cI(, ocI(,, -CH,
CI(IOC!H,.

-CH2CHICH! O(CHt)scHs, -C
H2CHICHtOCH2CH (CHri acHs, C
,H.

-CHt CH2CH2O(CHt) 1 t CH
s, -CH, CH, OCH, C horse OCH,, -CH2C
Hz CHt OCHz CHe O(CHz ) a
CI(s).

If n is >0, T9 preferably represents a C1-ctt alkyl group. The following are the corresponding groups -T, (COOH
)n examples are CH, C0OH, -CH, CH2C0OH.

-CH(CHa)COOHs -(CHs)icOO
Hs-(CHJ16COOH,-(CHri1l-COO
H%HOOCCH Snow-CHCoOH.

DI preferably has the meaning mentioned for D. When m in formula (2) is >0, that is, when 1 to 4 cals in the diazo component have xyl groups, the xyl groups may be bonded to the phenyl ring directly or through an intermediate.

The following are examples of diazo components having directly attached carboxyl groups: 2-13- or 4-aminobenzoic acid;
4-chloro-14-methoxy- or 4-methyl-3-aminobenzoic acid, 3-aminophthalic acid or 4-aminophthalic acid, 5-aminoisophthalic acid and 2-aminoterephthalic acid.

An example of a suitable intermediate tool is C! ~C6 alkylidene or -〇-
(C,~C6-alkylidene) groups; the following are examples of corresponding diazo components: 2-13- or 4-aminophenoxy acids, 2''''= '- or 4-aminophenoxypropion acid, 2-13- or 4-aminophenyl acetic acid and alkyl 01-0, halodane, e.g. C1, Br5/, substituted with one or two substituents belonging to the system comprising Fl-CN or -NO1 derivatives of the above-mentioned acids.

Suitable dicarboxylic or polycarginic acids for reaction with dyes of formula I are oxalic acid or % [where GI represents an aliphatic or aromatic hydrocarbon group having 1 to 51 carbon atoms; and a represents 2.3 or 4] and further a carganic acid of the formula CG']-(OCHtCHz-COOH)a' f
V [in the formula, G# is preferably saturated and has 2 to 20 carbon atoms and 1 to 9 carbon atoms in the carbon chain]
represents a hydrocarbon group which may contain an intervening atom, and has an ILI of 2.3.4 or 5].

I can do it.

The following are examples of carbic acids: maleic acid,
fumaric acid, itaconic acid, succinic acid, adipic acid and preferably higher dicarboxylic acids such as sulfuric acid, azelaic acid, sepacic acid, dodecanedioic acid, dodecenylsuccinic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid,
isophthalic acid, terephthalic acid, hexahydrophthalic acid,
Tetrahydrophthalic acid, 4-methylhexahydrophthalic acid, trimesic acid and pyromellitic acid.

The following is an example of carnic acid of formula HOOCCH
2CHtCCHx CH20CHl CI%COOI(
%HOOCCH,CH,OCR,CH2CH,OCH,
C.H., Coon.

HOOCCHl CHz O-CHl-CH-OCHt
CH Yicoon.

CH.

HOOCCHl CH2O-CHl -CH-0-C)
(20HICOOHs■ CH, -CH.

HOOCCHtCHl O-CHl -CHl -CH
-0-CHt C mountain coon~0H.

HOOCCHICHIO-(CH number-0-CHtCH
ICOOH%? H HOOCCH, CH, O-CHt-C-CH, -0-C
H, CH, COOH.

CH.

HOOCCHl CH2O-(CHt)so CHtC
HtCOOH%CHs CHa HOOCCH,CH,OCH,CH,OCH,CH,O
CH, CH, COOH.

HOOCCH,CH,0CH2CH,OCH,CH,O
CH, CH! OCH, CH, COOH.

] Page Touma H, OCH, CH, OCH, CI (, QC Horse C
H, OCH, CI (Snow OCH, CH Goose C term.

For the reaction with dyes of the formula (1), it is very particularly preferred to use dimer or trimer acids which can be prepared by low-volume polymerization of fatty acids.

Dihydroxy or polyhydroxy compounds which are particularly suitable for reaction with dyes of the formula (1) have the formula % formula % [wherein G11 represents an aliphatic hydrocarbon group having from 2 to 54 carbon atoms and al i1'', 2 .3.4 or 5].

The following are examples of compounds of formula V! 122-1123
- and 1゜4-butanediol, neopentyl glycol, 126-hexanediol, 2゜5-hexadiol, 3-methyl-1,5-bentanediol, 2-methyl-2-propyl-1,3-propanediol , octanediol (e.g. 1 cup mixture), trimethyl-1,
6-hexanediol (e.g. mixture), 1212-octadecanediol, dalisequar, 12121-trimethylolethane, 1,121-)limethylolpropane, ethylene glycol, propylene glycol, 12
4-Cyclohexanediol, 124-cyclohexane dimetatool, 2,2-bis-(4-hydroxycyclohexyl)-propane and hibis-hydroxymethyl-tricyclodecane (@TCD-diol").

The reaction products of compounds of formula v with ethylene oxide or propyleneoxy y can also be used.

Other suitable hydroxy compounds are diglycols or polyglycols having 3 to 20 ethylene oxide units;
Diglopylene or polypropylene glycol having 3 to 20 propylene oxide units, and copolymers of ethylene oxide and propylene oxide, and also 1° 4-bis-(2-hydroxyethoxy)-benzene, 4° 4I-bis -(2-hydroxyethoxy)-diphenylsulfone, 2,2-bis-(4-(2-hydroxyethoxy)-phenyl)-pronocon, and 125-
12.6-12.7- and 1,7-bis-(2-hydroxyethoxy)-naphthalene.

When esterifying pyridone azo dyes of the formula (1) containing hydroxyl groups, it is further possible to add dihydroxy or polyhydroxy compounds, e.g. It is appropriate to increase the amount to a certain extent. Reactions of this type lead to an elongation of the molecular chain, so that the technical properties of the product in use, such as solubility and strikethrough properties, can be improved.

A similar method can be followed when esterifying a pyridone azo dye of formula (1) in which the cal contains a xyl group with a dihydroxy or polyhydroxy compound. In this case, dicarboxylic acids or polycarboxylic acids of the type mentioned above are added.

If an excess of carboxy or aliphatic hydroxyl groups is present in the already linked pyridone azo dye, these groups may have been esterified with the previously mentioned diols or polyols or dicarboxylic acids or polycarboxylic acids, resulting in Pyridone azo dyes can optionally obtain additional linkages. The excess carboxyl or hydroxyl groups of the pyridone azo dye, which already contains ester-like linkages, can be replaced by monofunctional alcohols or monofunctional carboxylic acids such as saturated or unsaturated
1 G'=C! ! Aliphatic alcohol, Coo-0
It may be further esterified by wt fatty acids or reaction products of fatty alcohols, such as those also used as emulsifiers and dispersants, with ethyleneoxy P or propylene oxide.

In all the esterification reactions mentioned, compounds in which the cal contains both xyl groups and aliphatic hydroxy groups may be added. Although these do not serve as linking members, they can lengthen the molecular chain and thus improve solubility, for example. Examples of such hydroxylic acids are glycolic acid, lactic acid, s-hydroxypropanoic acid, 6-hydroxycaproic acid, ricinoleic acid, hydroxycaproic acid, 4-(2-hydroxyethoxy)-benzoic acid or, if appropriate, Lactones, low weight polymers or polymers of these compounds.

The mentioned esterification reaction may of course be carried out before the reaction with each component.

During the esterification reaction, the components containing esterifiable hydroxyl and carboxyl groups can be used in equal amounts in the simplest case. However, it is also possible to use one or more components in excess. This is advantageous for some reactions.

It is thus possible, for example, to promote esterification by this means. Under certain circumstances, it is also possible for esterification to occur to the extent possible with respect to one of the components. This is particularly important if, for example, the pyridone azo dyes used, which contain hydroxyl or carxyl groups, are themselves hardly soluble and are only converted into modified soluble compounds as a result of esterification. Components used in excess can also cause chain termination and thus limit the molecular weight of the compound. This is important if compounds with fairly high molecular weights, ie possibly very high viscosities, are formed in the esterification of equivalents of compounds containing carboxyl or hydroxyl groups.

Esterification itself is a conventional method, for example, as described by Houban-Weyl, Methoden der.
Organic Hemi (Methodender)
(Georg ThimeV
erlag * 8 tuttgart), 1952.

Thus, for example, the components may be heated in a suitable solvent in the presence of an acid catalyst and the resulting water removed at the azeotropic point. The following are examples of suitable acid catalysts: sulfuric acid, hydrochloric acid, chlorosulfonic acid, phosphoric acid, methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid and dodecylbenzenesulfonic acid, and 7
Talene-1-sulfonic acid and naphthalene-2-sulfonic acid, and acid type exchange resin.

Esters can also be produced by transesterification. In this case, the starting materials are lower fatty acids and lower alcohols.
For esters of components containing hydroxyl and hycarboxyl groups, the transesterification reaction is carried out in the presence of a catalyst according to known methods. At this time, lower fatty acids and lower aliphatic alcohols are simultaneously removed from the equilibrium by distillation.

It is also possible to prepare esters from activated derivatives of carboxylic acids, for example starting from carboxylic acid chlorides and anhydrides. Particularly suitable derivatives for this purpose are, for example, maleic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, tetrahyphthalic anhydride and Ydecenylsuccinic acid. The use of these anhydrides is particularly advantageous if the starting material is a pyridone azo dye containing hardly soluble hydroxyl groups.

The pyridone azo dye can first be reacted with one of the mentioned anhydrides to produce a product of improved solubility which can generally be more easily esterified.

Further linked pyridone azo dyes which may be used according to the invention have the formula % in one of its tautomeric forms: in which the formula n has the meaning given for formulas 1 and 2 and L represents an optionally substituted phenylene group such as m-phenylene or p-phenylene or a group of formula, provided that rings A' and B' are May be optionally substituted and QVi-0-1-8-1-80,-, -C-1I OH3 0"So R110 P heavy OR11 -8Q, -0-Q, =O-8o, or -0- 0 5
-QIl-8O, -0-, where R1 and R11 are water or, for example, -OH or -CN
C8-〇6alkyl or C1~ which may be substituted with
C2-cycloalkyl, and also R12 and 1Rtt
may be taken together to form a -(CH*)t-* bridge, where Q is one or more non-adjacent 0 atoms or -N- groups intervening in the carbon chain. R1 represents an optionally substituted hydrocarbon group 1 RSS represents hydrogen or 01-C, alkyl which may be substituted with, for example, -〇 H″r:@, and this group is preferably C
1-C3° alkanes, Cs++C, derived from cycloalkanes, preferably cyclohexane, phenyl-C1-C6 alkanes or naphthyl-C1-C6 alkanes, benzene or naphthalene, Ql and Qs represent aromatic groups, and nI is 122 ．．
3.4.5 or 6].

OR1, R ■ O R, OR Ai 1 CH3I suitable group Q! is an optionally substituted phenylene, an optionally substituted naphthalene, or an optionally substituted group of the formula.

A preferred group Qs is an optionally substituted phenylene or an optionally substituted 7talene group.

The following may be mentioned as examples of LQl: Other suitable compound groups which can be used according to the invention, the formula [where DI and DI represent radicals of the diazo component, T, '
and T, 'Vi alkyl, aryl or -COT, #, T4t is hydrogen or alkyl, Ml is one or more non-adjacent O atoms or -N- groups intervening in the carbon chain. represents an optionally substituted 1m hydrocarbon group, R13 is hydrogen or C optionally substituted with -OH, for example;
1-C4 alkyl, and r, r'% I and 8'
corresponds to 0) 1 or 2].

The preferred meanings of D, and correspond to the preferred meanings of D above.

The following are also mentioned as suitable diazo components: diazo components containing the radicals H, N-X, -, for example diazo components containing carbamoyl substituents, such as -CNH-(CHt)aN(CHa)t, -C-NH-
(CHt)sN(CtHs)t, -CNH-(CHt)
sN(CHlCHtOH)t%-8O1-NH-(C
Hl)mN(CHa)z, -so鵞-NH-(CHl)
sN (CtH++) t, 1↓-SO-NH-(CHt)sN(CHtel(tOH)t, 2■ and
If 1 contains a -COOH group, di, t- or ti
Polyols or radicals can be esterified with phosphoric or polycarboxylic acids, thereby increasing the degree of linkage and improving solubility.

Essentially, the esterification reaction is a formula! and (2) can be carried out in the same manner as the esterification already mentioned above.

In particular, the dyes ① and ③, since they are already linked, are monofunctional alcohols or monofunctional carbic acids such as saturated or unsaturated CI. ~C! aliphatic alcohol,
Cl O””C*! It may also be esterified by reaction products of fatty acids or fatty alcohols with ethylene oxide or propylene oxide.

Other suitable groups of dyes that can be used according to the invention are of the formula:
alkyl, optionally substituted 012-C22 alkenyl, -L, -0-L,, -L, -0-C-L,, -ca,
CHlO(CHIeHlo) tLf, -C
HtCH! O(CH,CH,O) i CL,'.

-CHzCHtCH20(CHIGHtO)tL7, -
CH! Oh! CH20 (ca, cH, O) t-C
-L? or -LsCOOL.

Indicates that L is C! ~CWt alkylene, L. is C elephant ~C
T! 7) v-? /L/ Mataij: C! ~C
Indicates Ikutomi alkenyl, L is hydrogen, Cl-Cff1 alkyl, C2-C! I
represents alkenyl or optionally substituted phenyl, R8 represents C1-Ctt alkylene, L, 'IdCt
~Ctt7/'ki/', C*~Ctt7 represents kenyl or optionally substituted phenyl, L is hydrogen C~C■
Alkyl or C! ~CWt represents alkenyl, 1t represents 0.122.3.4 or 5, Lf is hydrogen, halodane, such as F, C1 or 46-Br, C1~Cat alkyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, Aralkyl, % phenyl-C1-C4 alkyl and naphthyl-01-C alkyl, -CFa, "Not,"
CN%C0-C4 alkoxy, 01-C, alkoxycarbonyl, mono-C1-Cm furkylcarbamoyl, di-C1-C11 alkylcarbamoyl, mono-01
~C8 alkylsulfazoyl and diC, ~Ci alkylsulfamoyl, L is hydrogen, halogen, such as F, Ct or Br,
-CN, C1-C4 alkyl, 01-C4 alkoxy or 01-C,alkoxycarbonyl, and L4 represents hydrogen and C1-C4 alkyl].

Ctt～C! ! Alkyl and C12~C! The 2-alkenyl group may be substituted, for example, by -0H or 01-Ct2 alkoxy or C1-Ct2 alkenyloxy.

In formula (■), carbon number is preferably at least 12
, particularly preferably at least 18.

The dyes of the formula (1) are known and can be prepared analogously to methods known from the bb or literature (see e.g. Gokoku Kokai No. 2.214207, Kokukoku Kokai No. 111,
No. 648 and Gokoku Published Patent No. 8012.865).

One useful property of dyes of formula (1) is generally within the desired range for three or four color printing.

The present invention relates to novel dyes which can be prepared by reacting dyes of formula (1) with dicarboxylic acids or polycarboxylic acids to form ester-like linkages between at least two identical or different dyes of formula (1). Also related.

The present invention also relates to novel dyes which can be prepared by reacting dyes of formula (1) with dihydroxy or polyhydroxy compounds to form ester-like linkages between at least two identical or different dyes of formula (2). related.

Furthermore, the present invention provides the formula % formula %) [wherein (Pyt3 and CP yt ] have the meanings indicated for formula The present invention relates to novel dyes in which the cyclohexyclene group may be substituted with, for example, C1-C4 alkyl, and the phenylene group may be further substituted with -No and Ct.

The preparation of the dyes of the formulas ■, ■, ■, ■, ■, and ■ is carried out according to or analogously to methods known from the literature (see, for example, Kyokoku Unexamined Patent No. 2 216.207, Kyokoku Unexamined Patent No. 5). , No. 111,648, Strong Country Publication Patent No. 3
,012. Lug No. 2,152.55
/i and U.S. Pat. No. 4,474,318).

If the pyridone azo dyes mentioned above also contain aliphatic amino groups, the dyes can be converted into salts with suitable acids in order to increase solubility. The following are possible suitable acids: saturated or unsaturated 01-CHI fatty acids, resin acids such as abietic acid or its reaction products with maleic acid or fumaric acid, and dimer or tri-monofatty acids, C
,. ~C3° Phosphoric acid monoesters or diesters of alkanesulfonic acids, dodecylbenzenesulfonic acids and aliphatic alcohols.

The above-mentioned pyridone azo dyes which also contain free calitic acid groups can likewise be converted into salts with amines.

The following are examples of suitable amines: dicyclohexylamine, saturated or unsaturated Cs o -C22 aliphatic or dialiphatic alkylamine, aliphatic alkylpropylene diamine, abiethylamine, or alkylene amines of these amines. Reaction products with oxides such as ethylene oxide and propylene oxide.

In the production of halftone gravure printing inks, the proportion by weight in the dye molecule of hydrocarbon groups not directly bonded to azo groups is at least 20%, preferably at least 25%.
% and particularly preferably at least 50 %"t'# of formula 1
It is preferred to use % I[, M, ■, ■ and ■ or their esterified products.

The calculations leading to the selection of these compounds are illustrated using two examples: In the J w Q 53 series α and β, hydrocarbon groups that are not directly bonded to the azo group are marked.

In the formula α, the weight proportion of these substituents in the total weight of the molecule is 21.4%, and in the case of the formula β it is 32.2%.

Halftone gravure printing inks prepared using pyridone azo dyes preferably contain components A), B) and C.
A) from about 2 to about 20% by weight of a colorant, B) from about 10 to about 40% by weight of a resin, and C) from about 80 to about 50% by weight of a solvent, and further additives if appropriate. Contains.

The coloring agent is a mixture of some of the above-mentioned 2-ridone azo dyes,
mixtures of at least one of these pyridone azo dyes with other dyes suitable for halftone gravure printing, and in particular of at least one of the above-mentioned pyridone azo dyes and at least one pigment suitable for halftone gravure printing inks. It may be a mixture. The last mentioned mixture is 90
It may contain up to % by weight, preferably up to 50% by weight, of pigment. Mixtures of pyridone azo dyes with one another are often obtained simply by using, during the preparation, natural products or components produced from natural products in the form of mixtures according to the invention, or components in the form of mixtures of stereoisomers. However, it is possible to increase the proportion in the mixture by mixing the final product or by using a mixture of components during manufacture, such as a mixture of pyridone azo dyes, such as those produced by a mixed coupling reaction. You can also do it.

Pigments suitable for the preparation of mixtures of the mentioned pyridone azo dyes with pigments are preferably yellow pigments, such as CII pigments Yellow 12.13.14.17.74 and 83. Pigments with further different hues, e.g. TBA CII Orange 5
and 34: CI pigment shoes” 2.53.57:1211
2.122.146 and 148: CII pigment violet 19; CII pigment blue 15 and 27: CI pigment green 7 and! , 6, and CI Pigment Black 7 are also suitable for producing special hues. Pyridone azo dyes can also be used to color correct the mentioned pigments.

Examples of suitable resins are calcium resinates, zinc resinates, phenol-modified colophony resins, colored gums, calcium salts of dimerized colophony, and synthetic hydrocarbon resins.

Suitable solvents are preferably petroleum ethers, especially light petroleum ether fractions, xylene and particularly preferably toluene.

The invention thus relates to the production of halftone gravure printing inks, preferably based on toluene.

For the production of halftone gravure printing inks, the pyridone azo dyes are incorporated into the printing ink mixture in a customary manner, if appropriate as a mixture with pigments.

In the process according to the invention for the production of halftone gravure printing inks, a finely dispersed ink having a BET specific surface area of at least 50 m"/f%, preferably at least 1000 m"/f and particularly preferably at least 200 m"/l is used. Inorganic additives can advantageously be added to the pyridone azo dyes.

In particular aluminum hydroxide and very especially silica have been found to be suitable as additives.

The additives are preferably used in amounts of a2 to 2 per weight of printing ink.
% by weight, particularly preferably in an amount of 04 to α9% by weight.

As a result of these additives, the tendency of dyes to bleed through can be further reduced, providing results that could only be achieved using pigments alone.

The finely dispersed silicas preferably used are mainly finely divided silicas which are amorphous and crosslinked to varying degrees and have the specific surface areas mentioned above. Examples of this type of silica include
It is known from Hemi-1 Vol. 4L, Vol. 21, pp. 451-476.

Silica can be obtained, for example, by precipitation from solution or by pyrogenic processes; and it is mainly composed of silica but also contains other metal oxides and hydroxides, such as oxides of aluminum and titanium, and water. It may contain an oxide.

It is necessary to disperse silica in the gravure printing ink. This dispersion can be carried out in the final gravure printing ink or in a concentrate.

However, it is also possible to first prepare the dispersion in the solvent used for the gravure printing ink, if appropriate at a high concentration, and to add some or all of the resin at this stage. The following are examples of suitable dispersion equipment: stirrers, high speed stirrers, dissolvers, bead mills and gale mills and combinations of these equipment.

In addition to silica, 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 optionally contain hydroxy groups.

The following are examples of strong organophilic acids: cto""at
. alkanesulfonic acid, alkylarylsulfonic acid,
? Lt is dodecylbenzenesulfonic acid or di-tert
-butylnaphthalenesulfonic acid and sulfuric acid monoesters or phosphorous monoesters or diesters of alkanols, or their reaction products with ethylene oxide or propylene oxide.

Examples of alkanols of this type are saturated or unsaturated, straight-chain or branched 04-CI aliphatic alcohols such as butanol, 2-ethylhexanol, dodecanol, tetradecyl-hexadecyl and octadecyl alcohol, and oleyl alcohol, and also these alcohols. Of, 1~
It is the reaction product of 20 moles of ethylene oxide and propylene oxide.

The following are examples of suitable aliphatic amines: ethylenediamine, amines of formula H,N (CH,CH,NH) nH, where n==2-6, propylene diamine, dipropylene cyakine and tallow. fatty propylene diamine. HiF
Examples of suitable amines containing loxyl groups are those obtained in the reaction of ammonia or C1-CtO alkyl mono-, di- or poly-amines with ethyleneoxy F or propylene oxide or epichlorohydrin.

The following are examples of these: ethanolamine, diethanolamino, triethanolamine, tris-[2
-(2-hydroxyethylcy)-ethyl]-amine, bis-(2-hydroxyethyl)-methylamine, -ethylamine, -zolopylamine or -butylamine, 2-
(2-7minoethylamine)-ethanol, 2-(hydroxyethyl)-bis-(2-hydroxypropyl)-
Asan, tris-(2-hydroxypropyl)-amino, 3-[bis-(2-hydroxyethyl)-amino]-
Reaction of globylamine, intahydroxyethyldiethylenetriamine and 2,3-dihydroxypropylamine; and of coconut acid, tallow fat amine, stearylamine and oleylamine with 2 moles of ethylene oxide or of tallow fat propylene diamine with 3 moles of ethylene oxide. product.

These dispersants are 10 to 200% by weight based on silica,
It is preferably added in an amount of 50-100% by weight.

Examples of other suitable microdispersed additives are microdispersed aluminum hydroxide or x-ray, which is mostly amorphous and prepared, for example, from acidic aluminum salt solutions with bases or by flame hydrolysis. It is aluminum hydroxide glue.

Suitable aluminum hydroxide has a diameter of about 50m”/
It has a specific surface area of ng'r of f. They can be dispersed in the same manner and with the addition of the same fractionation agents as described above for silica.

Mixtures of finely dispersed aluminum hydroxide and silica can also be used according to the invention.

Penetration and/or bleed-through of printing ink is visible to the naked eye from the back side.
Alternatively, it can be tested colorimetrically by evaluating the see-through or bleed-through of a printing or coating of a printing ink on a printing material, such as a printing paper.

The throughput is 42t/m! This is particularly important in the case of attractively priced paper grades that have paper weights of 50% or less and are increasingly being used.

Furthermore, the novel dyes according to the invention can be used for surface coating,
It can be used to dye other organic solvents and mineral oil products. This is because they are characterized by an unexpectedly high solubility in this medium.

Examples of individual substances that can be dyed with the new pyridone azo 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, pronol, butanol,
Printing or writing inks based on butyl phthalate and ethyl 7-thalate, fuel oils and diesel oils, and common organic solvents.

In particular, the novel dyes may be used, if appropriate in mixtures with pigments.
It can also be used in the production of flexographic printing and packaging gravure printing inks.

The novel dyes of the invention can also be used in the above-mentioned preparations, containing finely dispersed inorganic additives.

Example 1 57.1 f (CL 1 mol) of a dye of formula 1% (1 mol of CL) obtained by diazotization and coupling according to a conventional method, Pribol (
pripol) 1010, i.e.: x, = )1-t(
A commercially available dimer fatty acid 3129F having an acid number of about 195, 200 F of luene and 1 F of methanesulfonic acid were heated under reflux for 7 hours, during which time the water produced by esterification was separated in a water separator. did. During the last 2 hours, the entire amount of toluene was slowly distilled off. As a result, the temperature rose to about 130°C. At this time, the unesterified dye could no longer be detected by thin layer chromatography. This solution was diluted with 50% of toluene and a small amount of undissolved residue was suctioned off and rinsed with a small amount of toluene. This resulted in a bright yellow solution 230f.

This solution 182, arsinol (A13ynol) Kz
71, a commercially available hydrocarbon resin from Synres, 50 Titoluene solution 51f and Toluene 561
were mixed. The Dashibia printing ink thus obtained had a viscosity corresponding to a flow time of 23 seconds in a DIN accent No. 3 cup as specified in DIN 53,211. Using this printing ink, Durner
The gravure paper was printed on a Dacivia printing manual testing device, resulting in a very deep yellow print.

dye solution 212 df, ) 49.9 f luene and Erkazlt 899, i.e. Laekharzvr@rke Robert
Similar results were achieved using printing inks consisting of calcium resinates 2 & 5F (Kraemsr).

Stream side 2 Dye solution 18f according to Example 1, Arcinol Kz71
o 50% solution 50 t, ) luene l 9 e and also Aerosil 380, i.e. about 5F30
597 dispersion in toluene of commercially available microdispersed silica (manufacturer: D*gusga) having a specific surface area of m''/fOBET 1
A printing ink consisting of 6f was produced in the same manner as in Example 1. As a result, a printing ink having the same viscosity and properties as in Example 1 was obtained. The backing properties were satisfactory even in the case of printing papers with very low weight per unit area.

Aerosil 300 [commercially available microdispersed silica with a BET specific surface area of approximately 500 m2/l (manufacturer: Degutsa)
], Nishisil 200 [commercially available microdispersed silica (manufacturer: Degutsa) with a BET specific surface area of about 200 mt/y] or HDKT40 [Walaka Hemi (Wa
Similar results were obtained when Aerosil 3800 series silica (Microdispersed Silica manufactured by Oker Chemie) was used.

Example 3 The method in Example 1 was followed except that Bilipol 1040 (commercially available trima fatty acid manufactured by Unikema) 3 and 1F were used as a substitute for the dimeric fatty acid. As a result, a solution was obtained which essentially contained as a dissolved component the pyridone azo dye of the formula shown in Example 1 bonded five times through the trimer fatty acid.

Printing inks prepared from this in the same manner as in Examples 1 and 2 showed similarly good properties.

Example 4 Pyridone azo dye 57.1f (1
1 mol), toluene 200- and 4-methylhexahydrophthalic anhydride 514F ([L5 mol) under reflux.
heated for an hour. During this time everything dissolved. methanesulfonic acid 1 and diglopylene glycol m compound s
2.2y (α24 mol) was added, heating was continued under reflux, and water produced by esterification was separated using a water separator. After about 1 hour, enough toluene was distilled off until the temperature reached about 130°C and heating was continued for an additional 8 hours. A further step (as in Example 1) comprises a pyridone azo dye of the formula shown in Example 1 linked through an oligomeric ester formed from di,4-methylhexahydrophthalic anhydride and diglopyrendalicol. Solution 265f was obtained. Additionally, oligomeric esters formed from 4-methylhexahyto47talic acid and dipropylene glycol were also likely present. The printing ink produced in the same manner as in Example 1 exhibited good strike-through strength compared to the printing ink of Example 1. A printing ink prepared analogously to Example 2 (by using microdispersed silica) gave results comparable to the printing ink according to Example 2.

Example 1 from pyridone azo dyes of general formula A shown in Table 1
Connected pyridone azo dyes were prepared by esterification of carboxylic acid, carboxylic anhydride and alcohol in the indicated amounts as shown in Table 2 in a similar manner to the method shown in Table 2. Other esterification products of pyridone azo dyes shown in can be expressed by the following formula:
R,=-CHtCH! OCH,CH,0HXXD
iR,=-CIH! A pyridone azo dye of OH, CH, OH was prepared as a starting material.

Table 2 The amount of carboxylic acid or carboxylic acid anhydride used per mole of dye is shown in Column C. The amount of alcohol used per mole of dye is also shown in column A.

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Printing inks were produced from the dyes of Examples 5 to 80 in the same manner as in Examples 1 to 4. In each case, the amount of resin eDI
The viscosity was adjusted by varying the flow time from a No. 3 N cup to correspond to 23 seconds. This printing ink gave yellow to orange deep-colored prints whose strike-through properties corresponded to those of the printing inks according to Examples 1 to 4.

Example 81 2,2-his-(4-aminophenyl)-propane 1
123F, 100° of water and 28° of 1N hydrochloric acid were stirred briefly and the mixture was cooled to 0° C. by addition of ice. Diazotization was carried out by adding dropwise an aqueous solution of 7 tons of sodium nitrite, and after 15 hours, excess nitrous acid was decomposed with sulfamic acid. The diazotized mixture was clarified and 5
- Commercial wetting agent based on cyano-2-hydroxy-4-methyl-1-oleyl-rid-5-one 42f and sodium dioctyl sulfosuccinate (aerosol 0T) 3
F+7), a solution in 350° of water and 14° of 1ON sodium hydroxide solution was added dropwise over about 1 hour at 0-5°C. After 10 hours at room temperature, the mixture was heated to 50° C. to complete the coupling. The yellow dye obtained was filtered off with suction F, washed with water and dried under vacuum at 50°C.

As a result, a yellow substance 55f of the formula was obtained.

When 6 parts of this dye and 31 parts of Elcatit 899 are dissolved in 63 parts of toluene, a gravure printing ink is obtained which gives a deep natural yellow print on the paper and exhibits very favorable strike-through properties. 6 parts of dye, 50 parts of 89 cp and 63 parts of toluene
A similar printing ink obtained from Part 1 and also containing a dispersion of Part α7 of Aerosol 380 likewise gave deep prints and showed a further reduced tendency to strike through.

Example 82 4-Methyl-2-nitroaniline 15.2rQ5N The mixture was stirred with 70% of hydrochloric acid and diazotized in a conventional manner. The diazotized mixture was clarified and a solution of 421 of 5-cyano-2-hydroxy-4-methyl-1-oleyl-pyrid-6-one in 200 g of toluene, 70 g of water, 62 g of succinic acid, and 1ON sodium hydroxide solution was added. Add dropwise to the mixture consisting of 8 g. The temperature was then kept between 0 and 10 DEG C. by the addition of ice and the pH was kept at a value of 5.5 by the dropwise addition of sodium hydroxide. Coupling was complete after 15 minutes. The mixture was heated to 60°C and the toluene phase was separated. After drying with sodium sulfate and clarification,
Part of the toluene was distilled off. As a result, a solution 130f containing dyestuff 561 of the formula was obtained.

A toluene-based gravure printing ink prepared from this according to Example 1 gave a deep yellow print, but Example 1
The printing ink showed some poor bleed-through characteristics.

On the other hand, the printing ink produced in the same manner as on the actual flow side 2 exhibited excellent cross-removal properties even on paper having a light weight per unit area.

Dyes were prepared analogously to the method described in Example 82 from the components shown in Table 3, and printing inks were prepared from these dyes. This showed the same tendency of properties as the printing ink according to Example 82.

Table 3 Oreil Physical data for manufacturing examples 5a-61445 7B-75455 76,77440 79,80440 O.C.

Claims (1)

[Claims] 1. Formula ▲ Numerical formula, chemical formula, table, etc.▼ I [In the formula, D represents a group of a diazo component, T_1 represents alkyl, aryl or -COOT_4, T_2 represents H, -CN , -COOT_4 or -CONH-T_5(OH)_n, T_3 represents an aliphatic or araliphatic group in which one or more oxygen atoms may be present, T_4 represents hydrogen or alkyl, T_5 represents an aliphatic or arariphatic group which may contain one or more oxygen atoms, and m and n represent 0, 1, 2, 3 or 4, provided that the sum of m+n is 1, 2 , 3 or 4] with a dicarboxylic or polycarboxylic acid to form an ester-like linkage between at least two identical or different pyridone azo dyes. 2. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ II [In the formula, m, n and T_1 have the meanings indicated for formula I described in claim 1, and T_2' is H, -CN or -COOT_4, where T_4 has the meaning given in formula I, T_■ represents an aliphatic or araliphatic group optionally having one or more intervening oxygen atoms, and D ' represents a radical of the diazo component] A dye prepared by reacting a pyridone azo dye of the formula with a dihydroxy or polyhydroxy compound to form an ester-like linkage between at least two identical or different pyridone azo dyes. 3. A method for producing halftone gravure printing ink using the dye according to claims 1 and 2. 4. Formula [P_y___1]-N=N-L-N=N-[P_y___
2] VI [In the formula, [P_y___1] and [P_y___2
] corresponds in one of its tautomeric forms to the formulas ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where T_1, T_2, T_3, T_2', T
_9 and n have the meanings indicated for formulas I and II;
and L represents an optionally substituted phenylene group such as m-phenylene or p-phenylene, or a group of the formula ▲numerical formula, chemical formula, table, etc.▼, provided that rings A' and B' may optionally be substituted, and is -O-, -S-, -SO_2-, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, -CH_2-, -CH_2CH_2
-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O(CH_2)_n'-O-
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc.▼ -SO_2-O-Q_2-O-SO_2 or -O-O_
2S-Q_3-SO_2-O-, and R_1_0
and R_1_1 is hydrogen or C_1 to C_6 alkyl or C_6 which may be substituted with, for example, -OH or -CN.
3~C_7-cycloalkyl, and R_1_0 and R_1_1 together represent -(CH_2)_1_~_
Q_1 may form a 4-bridge, and Q_1 is one or more non-adjacent O atoms in the carbon chain or an optionally substituted carbon that may contain a mathematical formula, chemical formula, table, etc. represents a hydrogen group, R_1_2 represents hydrogen or C_1-C_4 alkyl which may be substituted with e.g.
~C_6 alkane or naphthyl - derived from C_1 to C_6 alkane, benzene or naphthalene, Q_2 and Q_3 represent an aromatic group, and n' is 1,
2, 3, 4, 5 or 6] A method for producing a halftone gravure printing ink using a pyridone azo dye. 5.Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼VII [In the formula, D_1 and D_2 represent the groups of the diazo component, and T
_1′ and T_1″ are alkyl, aryl or -COT
_4', T_4' represents hydrogen or alkyl, M_1 is an optionally substituted hydrocarbon group in which one or more non-adjacent O atoms or -N- groups may be present in the carbon chain; , R_1_3 represents hydrogen or C_1-C_4 alkyl optionally substituted with, for example, -OH, and r, r', s
and s' represents 0, 1, or 2] A method for producing a halftone gravure printing ink using a pyridone azo dye. 6. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼VIII [In the formula, L_1 is optionally substituted C_1_2 ~ C_2_
2 alkyl, optionally substituted C_1_2~C_2_2 alkenyl, -L_5-O-L_6, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼, -CH_2CH_2O(CH_2CH_2O)_tL_
7, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_2CH_2CH_2O (CH_2CH_2O)
_tL_7, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -L_8COOL_9, L_5 represents C_2~C_1_2 alkylene, L_8
is C_2-C_2_2 alkyl or C_2-C_2_2
Indicates alkenyl, L_7 is hydrogen, C_1-C_2_2 alkyl, C_2-
C_2_2 alkenyl or optionally substituted phenyl, L_8 represents C_1-C_1_2 alkylene, L_7
' is C_1-C_2_2 alkyl, C_2-C_2_2
Indicates alkenyl or optionally substituted phenyl, L_9
Hydrogen, C_1-C_2_2 alkyl or C_2-C_2
_2 represents alkenyl, t represents 0, 1, 2, 3, 4 or 5, L_2 represents hydrogen, halogen, such as F, Cl or Br, C
_1-C_2_2 alkyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, aralkyl, especially phenyl-C_1-C_4 alkyl and naphthyl-C_1-C_4
Alkyl, -CF_3, -NO_2, -CN, C_1~
C_4 alkoxy, C_1-C_4 alkoxycarbonyl, mono-C_1-C_8 alkylcarbamoyl, di-
C_1~C_8 alkylcarbamoyl, mono-C_1~
C_8 alkylsulfamoyl and di-C_1 to C_8
represents alkylsulfamoyl, L■ is hydrogen, halogen, such as F, Cl or Br, -C
A process for producing a halftone gravure printing ink using a pyridone azo dye of N, C_1-C_4 alkyl, C_1-C_4 alkoxy or C_1-C_4 alkoxycarbonyl, and L_4 represents hydrogen and C_1-C_4 alkyl. 7. Formula [P_y__1]-N=N-L'-N=N-[P_y_
_2] IX [wherein, [P_y___1] and [P_y___2]
] has the meaning indicated for formula VI, and L' has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ where the phenylene, cyclopentylene and cyclohexylene groups may be substituted with, for example, C_1 to C_4 alkyl, and the phenylene group may be further substituted with -NO_2 and Cl] dyes . 8. Use of a dye in which the weight proportion of hydrocarbon groups not directly bonded to the azo group in the dye molecule is at least 20%, preferably at least 25%, particularly preferably at least 30% Halftone/
Manufacturing method of gravure printing ink. 9. A method for producing a halftone gravure printing ink according to claims 1 to 8, using a pyridone azo dye/pyridine mixture. 10. Process according to claims 1 to 9 for the production of halftone gravure printing inks based on toluene.