CH637152A5 - Diazo compounds, preparation thereof, and use thereof as pigments - Google Patents

Description

The present invention relates to new valuable disazo compounds of the formula I.

X X

is where R4 is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, lower carboalkoxy or nitro;

wherein X and Y are hydrogen, chlorine and / or bromine atoms, methyl, ethyl, methoxy and / or ethoxy groups and K are identical or different residues of enolizable ketomethyl compounds of the formulas II to VI which do not contain any water-solubilizing groups, mean,

-CH-CO-NH-Ar

COR

where R is methyl or phenyl and Ar is a radical of the formula IIa a

(HD,

where R5 is phenyl, tolyl or chlorophenyl and R6 is methyl, lower carboalkoxy, carbonamido or lower alkanoylarnino:

R

R

R-

(Ila)

in which R1, R2 and R3, which are the same or different, denote hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, lower alkanoylarnino, benzoylamino or nitro,

where R3 is hydrogen when X and Y are hydrogen 35, or Ar is a radical of the formulas IIb, IIc, Ild, Ile or Ilf

(IIb)

(IIc)

45

50

55

(Hd)

(Ile)

or

(VI)

where Z represents oxygen, sulfur or = NH.

Here and below, the expression “lower” means alkyl and alkoxy radicals with 1 to 4 carbon atoms, alkanoyl radicals with (in total) 2 to 5 carbon atoms and carboalkoxy alkoxy radicals with 1 to 4 carbon atoms.

Examples of possible residues Ar of the formula IIa are:

Phenyl, o-, m-, p-tolyl, o-, m-, p-methoxyphenyl, o-, m-, p-ethoxyphenyl, o-, m-, p-chlorophenyl, o-, m-, p- Bromophenyl,

0-, m-, p-nitrophenyl, 2,4-dimethylphenyl, 2,5-dimethoxyphenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,4,5-trichlorophenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2-chloro-5-methylphenyl, 3-chloro-2-methylphenyl, 4-chloro-2-methylphenyl, 2-methoxy-5-chlorophenyl, 2,5-dimethoxy-4-chlorophenyl, 2,4-dimethoxy-5-chlorophenyl, 2-methoxy-4-chloro-5-methylphenyl, 4-acetylaminophenyl or 4-benzoylaminophenyl.

Ar in the formula IIb are in particular benzimidazol-2-one-5-yl, 7-chloro-benzimidazol-2-one-5-yl and 7-methyl-benzimidazol-2-one-5-yl Consider.

Examples of pyrazolone radicals of the formula III are the radicals of l-phenyl-3-methylpyrazolon- (5), l- (4'-TolyI) -3-methyl-pyrazolon- (5), l-phenyl-3-carbomethoxypyrazolon- ( 5),

1- (4'-Tolyl) -3-carboethoxypyrazolone- (5) or l-phenyl-3-acetylaminopyrazolone- (5) in question.

The invention further relates to a process for the preparation of the disazo compounds of the formula I, the di-azo component of the formula VII

65

(vii)

637 152

4th

wherein X and Y have the meaning given for formula I, bisdiazotized by methods known per se and combining one equivalent of the bisdiazonium compound thus obtained with 2 equivalents of the coupling components K-H in a customary manner, for example in an aqueous medium. A single coupling component or a mixture of several coupling components can be used here. The invention further relates to the use of the disazo compounds of the formula I as pigments outside the textile industry. The di-azo components of the formula VII can be prepared by known processes, for example by condensation of the appropriately substituted 4-acylaminobenzoic acid, 4-nitrobenzoic acid or of methyl or ethyl 4-nitrobenzoate with hydrazine or its salts in the presence of a condensing agent, such as sulfuric acid, phosphoric acid or polyphosphoric acid and subsequent hydrolysis of the acylamino compound or reduction of the dinitro compound obtained by known processes, such as, for example, iron dust reduction or catalytic hydrogenation.

The diamines of the formula VII can be bisdiazotized, for example, with alkali metal nitrites and a mineral acid, but also with nitrosylsulfuric acid. It can be useful here, as well as in the subsequent coupling, to use an addition of surface-active agents, such as, for example, nonionic, anionic or cationic dispersants.

Diazotization and coupling can also be carried out in the presence of suitable organic solvents, such as, for example, glacial acetic acid, lower alkanols, dioxane, formamide, dimethylformamide, dimethyl sulfoxide, pyridine or N-methylpyrrolidone. To achieve the full color strength and a particularly favorable crystal structure, it is often advisable to heat the coupling mixture for some time, for example to boil it or to keep it under pressure at temperatures above 100 ° C., optionally in the presence of an organic solvent such as ethanol, o-dichlorobenzene, Dimethylformamide, N-methyl-pyrrolidone or in the presence of resin soap. Particularly pure and strongly colored pigments are obtained with the products according to the invention if, after coupling, the moist presscake or the dried powders are subjected to a thermal aftertreatment with organic solvents, such as alcohols, for example lower alkanols, pyridine, glacial acetic acid, dimethylformamide, N-methylpyrrolidone, Dimethyl sulfoxide,

subject to aromatic solvents, such as chlorobenzene, dichlorobenzene or nitrobenzene, or a grinding of the pigments with the addition of grinding aids.

The pigments can also be prepared in the presence of a carrier material, for example heavy spar.

The new pigments are water-insoluble and insoluble in the usual organic solvents and are suitable for the production of printing inks, colored lacquers and dispersion paints, for coloring rubber, and natural or io synthetic resins.

The pigments can also be used for other areas of application, e.g. in finely divided form for dyeing rayon made of viscose or cellulose ethers or esters, polyamides, polyurethanes, polyglycol terephthalate or polyacrylonitriles in the 15 spinning mass or for dyeing paper.

The pigments can be processed well in the media mentioned. The dyeings have clear shades, very good color strength and light fastness and are resistant to the effects of heat and the influence of chemicals, especially solvents.

In the following examples, percentages are by weight unless otherwise stated.

example 1

25 16.6 g of 2,5-bis- [4'-amino-3'-chlorophenyl- (l ')] - l, 3,4-oxadiazole are in 100 ml of glacial acetic acid and 25 ml of 31% Hydrochloric acid stirred for several hours. The suspension is then cooled to 0 ° C. with ice and diluted to about 300 ml with water. Diazo-30 is rapidly used with 13.5 ml of 40% sodium nitrite solution. The mixture is stirred for an hour with a slight excess of nitrite and then clarified over a layer of diatomaceous earth.

18.6 g of N-acetoacetyl-aniline are dissolved in 600 ml of water and 15 ml of 33% sodium hydroxide solution. 2 g of an emulsifier made from ethylated, hydrogenated tallow fatty alcohol are added. 20 ml of glacial acetic acid are added dropwise at 15 ° C. 35. The diazo solution, which had previously been freed from excess nitrite with a little amidosulfonic acid, is added dropwise to the suspension thus obtained at 20-25 ° C. over the course of an hour. The pH is kept at 5.5 40 by simultaneous addition of dilute sodium hydroxide solution. After the coupling has ended, the mixture is heated to 95 ° C. for 30 minutes. The product is isolated, washed salt-free with water, dried and pulverized.

37 g of a greenish yellow pigment of the formula with excellent lightfastness and high color strength are obtained. Example 2

12.6 g of 2,5-bis- [4'-aminophenyl- (1 3,4-oxadiazole) are stirred in 100 ml of glacial acetic acid and 25 ml of 3 l% hydrochloric acid overnight. The next morning with ice and water the temperature is set to 0 ° C. and the volume to 300 ml, diazotized with 13.2 ml of 40% sodium nitrite solution, stirring is continued for 30 minutes and clarified over a layer of diatomaceous earth.

21.8 g of N-acetoacetyl-4-methoxy-aniline are dissolved in 600 ml of water with 15 ml of 33% sodium hydroxide solution. 2 g of an emulsifier made from ethylated, hydrogenated tallow fatty alcohol are added. At 15 ° C, the coupling component is precipitated with 20 ml of 60 glacial acetic acid. 0.5 g of amidosulfonic acid is added and the diazonium salt solution is added dropwise at 20 ° C. over the course of an hour. The pH value is kept at 5.5 by simultaneous addition of dilute sodium hydroxide solution. After the coupling has ended, the pigment suspension is heated to 95 ° C. for 30 minutes. The solid is suction filtered, washed, dried and pulverized at 65 70 ° C. 34.5 g of a greenish-yellow pigment with the structural formula are obtained

5

637 152

Hg CO- ^ Qym-CO-ÇH-NiiN- ^ Q ^

i °

CE,

-N "

-N = N-ÇH-C0-NH- ^ Qy0CEj

CO I

CE,

This pigment is characterized by high color strength, color purity and good light and migration fastness.

0 CE,

(^ Q ^ -NHCO-ÇH-N = N- ^ Q ^ -: Cl

CO t

CH3

The pigment powder is stirred in dimethyl sulfoxide for 1 Vi hours at 150-160 ° C. After cooling to 70 ° C., the pigment is filtered off, washed with methanol, dried and pulverized. A slightly greenish yellow pigment is obtained with excellent lightfastness and very good color strength.

Example 4

16.1 g of 2,5-bis- [4'-amino-2'-chlorophenyl- (1 ')] - !, 3,4-oxadiazole are in 100 ml of glacial acetic acid and 50 ml of 3 l% Hydrochloric acid stirred overnight. By adding ice the temperature is set to 0 ° C the next morning. It is diazotized with 13.2 ml of 40% sodium nitrite solution and stirred for an hour with light example 3

Instead of N-acetoacetyl-aniline in Example 1, 24.3 g of N-acetoacetyl-2-methoxy-aniline are used. According to the process described in Example 1, 39 g of a yellow pigment of the formula are obtained

OCE,

N = N-CH-CONII— (Q)

CO I

CE,

excess nitrite. A clear diazonium salt solution is obtained.

21.6 g of N-acetoacetyl-2,4-dimethyl-aniline are suspended in 600 ml of water and dissolved in 20 ml of 33% sodium hydroxide solution. 15 ml of glacial acetic acid and 0.5 g of amidosulphonic acid are added at 15 ° C. The diazonium salt solution is added dropwise to the suspension obtained at 20 ° C. over the course of one hour. The pH is kept at 5.0 by simultaneous addition of dilute sodium hydroxide solution. After coupling is complete, the pigment suspension is heated to 90 ° C. for 15 minutes. The pigment is then filtered off, washed free of salt, dried and pulverized. Yield: 38 g. 20 g of this pigment powder with the structural formula

25th

30th

✓CHg

H3 c ~ NH-CO-CII-N = N -

CO I

CE,

C ^

0 / - ^ - n ^ - ^ n-co-NH - ^ - cu,

CO t

CE,

are stirred in 250 ml of dimethylformamide at 110 ° C for 20 minutes. The solid is filtered off with suction at 70 ° C., washed with ethanol, dried and pulverized. 19 g of a yellow pigment with high color strength and good light fastness are obtained.

Example 5

16.1 g of 2,5-bis- [4'-amino-2'-chlorophenyl- (l ')] -1,3,4-oxadiazole are dissolved in 50 ml of 3% hydrochloric acid and 45 ml Water stirred overnight. The next morning, the mixture is cooled to 0 ° C. with ice and diazotized with 13.2 ml of 40% sodium nitrite solution. The mixture is stirred for an hour with a slight excess of nitrite and then clarified over a layer of diatomaceous earth. The Fil-50 step is made up to 400 ml with water and 1 g of an emulsifier made from ethylated, hydrogenated tallow fatty alcohol is added.

20 g of 3-methyl-1- (4'-tolyl) -pyrazolone- (5) are dissolved in 200 ml of water with 11 ml of 33% sodium hydroxide solution. This solution 55 is added dropwise to the diazonium salt solution at 10-20 ° C within 1 hour. After the coupling has ended, the mixture is heated to 95 ° C. for 30 minutes. The solid is then suction filtered at 70 ° C., washed free of salt, dried and pulverized. 35 g of a reddish yellow pigment of the following structural formula are obtained:

®3 C ~ (0) ~ N ^^ yN-N-

"CH3

/ = *

637 152

This pigment is particularly characterized by its excellent color strength.

Example 6

The diazonium salt solution is prepared according to Example 1, but four times the amount of 31% hydrochloric acid is used in the salt formation.

24.4 g of 5-acetoacetylamino-benzimidazolone are dissolved in 440 ml of water and 28.4 ml of 33% sodium hydroxide solution. For the clear

20 ml of glacial acetic acid are added dropwise at 15 ° C. to the solution of the coupling component. The diazo solution is added dropwise to the suspension thus obtained at a temperature of 20 ° C. in the course of 80 minutes. The pH is kept at 5.0 by simultaneous addition of 5 dilute sodium hydroxide solution. After the coupling has ended, the mixture is heated to 95 ° C. for 30 minutes. The pigment is suctioned off at 70 ° C., washed salt-free with water, dried and pulverized. 45 g of pigment with the following structural formula are obtained:

0 -

H

^^ = N-ÇH-C0NH-CqEK-

co

I.

CHg u

■ = 0

20 g of the pigment thus obtained are heated in 400 ml of dimethyl sulfoxide at 180 ° C. for 40 minutes. The mixture is allowed to cool to 70 ° C., the solid is filtered off with suction and the filter cake is washed with methanol. After drying and pulverizing, 17 g of a reddish yellow pigment are present. This pigment is characterized by very good color strength, excellent resistance to solvents and migration, and excellent lightfastness.

Example 7

7.9 g of 2,5-bis- [4'-amino-2'-methylphenyl- (1 ')] -1,3,4-oxadiazole are dissolved in 150 ml of glacial acetic acid and 15 ml of 3% Hydrochloric acid mixed overnight. Then it is brought to 10 ° C. with ice and bis-diazotized by the rapid addition of 10 ml of 5N sodium nitrite solution. You leave 30 minutes with a little nitrite excess. stir the shot. 14.3 g of aceto-acetyl-2,5-dimethoxy-4-chloro-aniline is added to 80 ml of water. Then you dissolve with 6 ml

33% sodium hydroxide solution and clarifies with a little activated carbon and diatomaceous earth. The clarified solution is allowed to run to a mixture of 5 ml of glacial acetic acid and 1 g of a 10% aqueous solution of a stearyl alcohol oxyethylated with 25 20 ethylene oxide in 100 ml of ice water.

The diazonium salt solution described above is run on the suspension prepared in this way at room temperature after the excess nitrite has been eliminated with a little amidosulfonic acid solution, while the pH is kept at 5.5 at the same time with 6% sodium hydroxide solution. When the addition is complete, the mixture is heated to 95 ° C. and kept at this temperature for 30 minutes. The greenish-yellow pigment is filtered off, washed with water until salt-free and dried at 65.degree.

35 If the crude pigment is treated with 50 ml of dimethylformamide at 100 ° C for 30 minutes, 17.4 g of the strong yellow pigment of the formula are obtained after suction, washing and drying

OCH

o ^ Oj—

OCBg

^ CO HNOC-èH-M

CO

qyL \

^ N-IH-conh— / O VOI

OCEg

Further examples, which were produced in accordance with the examples described, are summarized in the following table:

K-N = N

N — N -

X

Y

K-H

Color (letterpress)

60 x

Y

K-H

Color (letterpress)

H

H

N-Acetoacetyl-aniline greenish yellow

H

H

N-acetoacetyl-2-methoxyani-

greenish-yellow

H

H

N-AcetoacetyI-2-methylaniline yellow

lin

H

H

N-acetoacetyl-4-methylaniline yellow

65 H.

H

N-Acetoacetyl-2-chloroaniline reddish yellow

H

H

N-acetoacetyl-2,4-dimethyl

yellow

H

H

N-Acetoacetyl-4-chloroaniline reddish yellow

aniline

H

H

N-acetoacetyl-2,5-dichloroani-

reddish-yellow

7 637152

X

Y

K-H

Color (letterpress)

X

Y

K-H

Color (letterpress)

H

H

N-acetoacetyl-2-methyl-4-

reddish-yellow

OCHJ H

N-Acetoacety 1-4-chloro-an ili n reddish yellow

chloraniline

5

och3 h

5-acetoacetylamino-benz

reddish-yellow

H

H

N-acetoacetyl-2-methoxy-5-

reddish-yellow

imidazolone

chloraniline

OCHj H

3-methyl-l- (4'-tolyl) pyrazo-

yellowish-orange

H

H

5-acetoacetylamino-benzimi-

yellow

lon- (5)

dazolon

OC2H5H

N-acetoacetyl-4-methoxy-ani-

reddish-yellow

H

H

5-acetoacetylamino-7-methyl

reddish-yellow

10th

lin

benzimidazolone

H

OCH3

N-Acetoacetyl-4-methyl-aniline reddish yellow

H

H

5-acetoacetylamino-7-chloro

reddish-yellow

H

OCH3

N-acetoacetyl-4-methoxy-ani-

reddish-yellow

benzimidazolone

lin

H

H

1 -phenyl-3-methylpyrazo-

reddish-yellow

H

OCH3

N-acetoacetyl-2,5-dichloro-ani-

orange

lon- (5)

15

lin

H

H

1 - (4 '-Tolyl) -3-methylpyrazo-

reddish-yellow

H

OCH3

N-acetoacetyl-4-chloro-2,5-

reddish-yellow

lon- (5)

dimethoxy aniline

H

H

Barbituric acid yellowish orange

H

OCH3 3-methyl-l-phenyl-pyrazo-

yellowish-orange

Cl

H

N-Acetoacetyl-2-methyl-aniline greenish yellow

lon- (5)

Cl

H

N-Acetoacetyl-4-methyl-aniline greenish yellow

20th

Cl

C1

N-Acetoacetyl-aniline greenish yellow

Cl

H

N-acetoacetyl-2,4-dimethyl

greenish-yellow

Cl

Cl

N-acetoacetyl-2,4-dimethyl

greenish-yellow

aniline

aniline

Cl

H

N-acetoacetyl-4-methoxy-ani-

11 n yellow

Cl

Cl

N-acetoacetyl-2-methoxy-ani-

lin greenish yellow

Cl

H

1111

N-Acetoacetyl-2-chloro-aniline greenish yellow

25th

Cl

Cl

1111

N-acetoacetyl-4-chloro-2,5-

reddish-yellow

Cl

H

N-acetoacetyl-4-chloro-aniline yellow

dimethoxy aniline

Cl

H

N-acetoacetyl-2,5-dichloro-ani-

greenish-yellow

Cl

Cl

5-acetoacetylamino-benz

reddish-yellow

lin

imidazolone

Cl

H

N-acetoacetyl-4-chloro-2-me-

greenish-yellow

Cl

Cl

3-methyl-1-phenyl-pyrazo-

yellowish-orange

ethyl aniline

30th

lon- (5)

Cl

H

N-acetoacetyl-5-chloro-2-me-

yellow

Br

H

N-acetoacetyl-4-methoxy-ani-

yellow

thoxy aniline

lin

Cl

H

N-acetoacetyl-4-chloro-2,5-

reddish-yellow

Br

H

3-methyl-1 - (4'-tolyl) pyrazo-

orange

dimethoxy aniline

lon- (5)

Cl

H

5-acetoacetylamino-7-chloro

reddish-yellow

35

CHj

H

N-acetoacetyl-2,4-dimethyl

greenish-yellow

benzimidazolone

aniline

Cl

H

3-methyl-1-phenyl-pyrazo-

reddish-yellow

ch3

H

N-acetoacetyl-4-methoxy-ani-

greenish-yellow

lon- (5)

lin

Cl

H

3-methyl-l- (4'-tolyl) pyrazo-

reddish-yellow

CHj

H

N-acetoacetyl-4-chloro-2,5-

reddish-yellow

lon- (5)

40

dimethoxy aniline

Cl

H

Barbituric acid yellow

CH3

H

5-acetoacetylamino-benz

reddish-yellow

H

Cl

N-Acetoacetyl-aniline greenish yellow

imidazolone

H

Cl

N-Acetoacetyl-2-methylaniline greenish yellow

ch3

H

3-methyl-1-phenyl-pyrazo-

yellowish-orange

H

Cl

N-Acetoacetyl-4-methylaniline greenish yellow

lon- (5)

H

Cl

N-acetoacetyl-2-methoxyani-

lin greenish yellow

45

CzH5

H

N-acetoacetyl-2-methoxy-ani-

lin greenish yellow

H

Cl

1111

N-acetoacetyl-4-methoxyani-

greenish-yellow

H

CH3

1111

5-acetoacetylamino-benz

reddish-yellow

lin

imidazolone

H

Cl

N-Acetoacetyl-2-chloroaniline greenish yellow

H

CHs.

N-acetoacetyl-2,4-dimethyl

greenish-yellow

H

Cl

N-acetoacetyl-4-chloroaniline greenish yellow cn

aniline

H

Cl

N-acetoacetyl-2,5-dichloroani-

reddish-yellow

H

CH3

N-Acetoacetyl-aniline greenish yellow

lin

H

CH3

N-acetoacetyl-2-methoxy-ani-

greenish-yellow

H

Cl

N-acetoacetyl-4-chloro-2-me-

greenish-yellow

lin

thylaniline

H

CHj

3-methyl-l- (4'-tolyl) pyrazo-

yellowish-o range

H

Cl

N-acetoacetyl-5-chloro-2-me-

reddish-yellow

55

lon- (5)

thoxyaniline

Cl

CH3

N-acetoacetyl-4-chloro-2,5-

reddish-yellow

H

Cl

N-acetoacetyl-4-chloro-2,5-

reddish-yellow

dimethoxy aniline

dimethoxyaniline

H

Cl

6-N-acetoacetylamino-tetra-

reddish-yellow

H

Cl

5-acetoacetylaminobenz

reddish-yellow

hydroquinoxaline-2,3-dione

H

imidazolone

60

H

Cl

6-N-acetoacetylamino-tetra-

reddish-yellow

Cl

5-acetoacetylamino-7-chloro

reddish-yellow

hydro-quinazoline-2,4-dione

benzimidazolone

Cl

H

N-acetoacetylaminohthal

yellow

H

Cl

3-methyl-1-phenyl-pyrazo-

reddish-yellow

imid

lon- (5)

Cl

H

6-N-acetoacetylaminotetra-

brownish-yellow

OCHs H

N-acetoacetyl-2,4-dimethyl

reddish-yellow

hydrophthalazin-2,3-dione

aniline

03

Cl

H

2,6-dihydroxy-4-methyl-5-

brown

O O X

H

N-acetoacetyl-2-methoxy-ani-

yellow

cyanopyridine

lin

Cl

H

2,4-dihydroxyquinoline brown

Claims (4)

637 152 2nd PATENT CLAIMS 1. Compounds of Formula I X is where R4 is hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, lower carboalkoxy or nitro; N-K (I), .o (HD, where R3 is phenyl, tolyl or chlorophenyl and R6 is methyl, lower where X and Y are hydrogen, chlorine and / or bromine atoms, res carboalkoxy, carbonamido or lower alkanoylarnino Are methyl, ethyl, methoxy and / or ethoxy groups and K; the same or different residues of enolizable ketomethyl compounds of the formulas 11 to VI which do not contain any water-solubilizing groups, -CH-CO-NH-Ar I. COR • (II), where R is methyl or phenyl and Ar is a radical of the formula IIa R1 3acN _ / v (IV), <V) OH HO 0. / H R R- (Ha) 30th -D- y ~ \ is in which R1, R2 and R3, which are the same or different, Are hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, lower alkanoylarnino, benzoylamino or nitro, 35 where R3 is hydrogen if X and Y are hydrogen, or arein the rest of the formulas IIb, Ile, Ild, Ile or Ilf 2. Process for the preparation of the compounds of formula I according to claim 1, characterized in that or (VI), where Z represents oxygen, sulfur or = NH. one equivalent of that obtained by bisdiazotizing the diamine of formula VII (IIb) (IIc) (Ild) (Hey) or (VII) The bisdiazonium compound obtained, in which X and Y have the meanings given in claim 1, couples with two equivalents of one or more compounds of the formula K-H, where K is the one given in claim 1 55 meaning. 3. Use of the compounds according to claim 1 as pigments outside the textile industry. 4. Use according to claim 3 of the compounds according to claim 1 for dyeing rubber and natural 60 or synthetic resins, for printing on non-textile substrates, for dyeing rayon made of viscose or cellulose ethers or esters, polyamides, polyurethanes, polyglycol terephthalate or polyacrylonitriles in the dope or for dyeing paper. 65 5. Use according to claim 3 of the compounds according to claim 1 for the production of printing inks, lacquers and emulsion paints. (Ilf) 3rd 637 152