JPS60156759A - Water-soluble disazo compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [X is nitro, or amino; A is group shown by the formula II, or III (R1 is H, methoxy, methyl, OH, nitro; R2 is H, methyl, methoxy, acetylamino, etc.; R3 is H, methoxy, or ethoxy; n is 0, or 1); Y is (methyl)amino, acetylamino, N-methyl-N-acetylamino(substituted) phenylamino, etc.; with the proviso that Y is bonded to 6-7 position of naphthalene nucleus, when X is nitro, cases where R1 is methoxy, ethoxy, R2 is H, methyl, methoxy, etc. and Y is (methyl)amino, phenylamino, etc. are omitted], and its copper complex compound. EXAMPLE:A compound shown by the formula IV. USE:For preparing polarizing film. Having improved sublimation resistance and heat stability. PREPARATION:A compound shown by the formula V is diazotized, and coupled with a compound shown by the formula VI, etc. to give a monoazo compound shown by the formula VII. This compound is further diazotized, and coupled with a compound shown by the formula VII, to give a compound shown by the formula I (X is nitro).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to water-soluble disazo compounds. More specifically, as a free acid, use the formula (T) [In the formula (I), X is a nitro group or an amino group, and A is the formula (a) or (b) - □ represents a hydrogen atom, a methoxy group, an ethoxy group, a methyl group, or a hydroxyl group; L represents a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, an acetylamino group, or one ureido group; ' Ratt.

a hydrogen atom, a methoxy group, or an ethoxy group, n represents 0 or old, respectively)iway, z'"Y is an amino group, a methylamino group, an acetylamino group, an N-methyl-N-acetylamino group, β - A phenylamino group optionally substituted with 1 or 2 of a hydroxyethylamino group, a phenyl-nuclear cannitro group, an amino group, a hydroxyl group, a methyl group, a sulfonic acid group, or a carboxyl group, or a ben: each represents a secondary amino group However, Y is assumed to be bonded to the 6 or 7 position of the naphthalene nucleus, and when X is a nitrogen group, R1 in formula (a) is a methoxy group, an ethoxy group, and R2 is a hydrogen atom, a methyl group, methoxy group, ethoxy group and Y are amino group, methylamino group, β-hydroxyethylamino group, phenylamino group, carboxyphenylamino group, sulfophenylamino group.] Copper □ complex salt flower compound with water-soluble disazo compound or
Regarding.

□ Although it is difficult to use the disazo compound of the present invention for dyeing cellulose fibers, it is mainly used for producing polarizing films. Conventionally, one color agent and groove in the polarizing film □ production group were
The object of the present invention is to provide a compound for producing a polarizing film having excellent sublimation resistance and thermal stability.

The water-soluble disazo compound of the present invention is generally produced as follows. That is, a compound represented by the formula (I) as a free acid is diazotized by a conventional method to form a compound of the formula (I]
(In formula (Illra), R1 and R2 have the same meanings as above.) or as a free acid, formula (mb) (In formula (Ilb), R3 and n have the same meanings as above.) Coupled with a compound represented by y as a free acid, formula (IV) 5- (In formula (IV), .1 represents the same meaning as above.)
A monoazo compound represented by 03S,' (in 2M, Y represents the same meaning as above, and the group Y is at the 6- or 7'-position.) method, and the free acid is obtained by formula (VI) (2′ (■) and Y represent the same meanings as above,
A water-soluble disazo compound is prepared, in which the group Y' is bonded to the 6' or 7-position.

Further, the compound represented by formula (VI) is treated with copper sulfate or the like to produce the respective copper complex salt compound. In addition, the compound represented by the formula (II) is reduced with sodium sulfide, etc., and the compound is converted into a free acid as shown in the formula (■).

6- (In the formula (■1), A and Y represent the same meanings as above, and the group Y is bonded to the 6th or 7th position) is produced, and Further, if necessary, it is treated with copper sulfate or the like to produce a copper complex salt compound of the compound of formula (1).

Compounds represented by formula (1) are usually produced as IJium salts, but they can also be produced as free acids or as potassium salts, lithium salts, ammonium salts, alkyl amines, and ethanolamine salts. I can do it.

Specific examples of the compound represented by formula (11Ta) include p-cresidine, 2,5-dimethoxyaniline, 2
．． 5-jethoxyaniline, aniline, p-gysylidine, m-)luidine, N-acetyl-m-phenylenediamine, 5-acetylamino-2-methoxyaniline, 5
-ureidoamino-2-methoxyaniline, N-ureidoamino-m-phenylenediamine, etc., and the formula (
Specific examples of the compound represented by IITI) include monoph-2-ethoxy-1-naratylamine-6-sulfphonic acid, 2-methoxy-1-diathylamine-6-sulfonic acid, and 2-ethoxy-1-naphthylamine. , α-naphthylamine, 2-methoxy-1-naphthylamine, 1-
Naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid, etc. are mentioned, and a specific example of the compound represented by 2M is 1-hydroxy-6-aminonaphthalene-3-sulfonic acid (hereinafter referred to as J Acid and abbreviation -t)N-
Phenyl, ■ acid, N-methyl J acid, N-acetyl J acid,
N-methyl-N-acetyl J acid, N-benzoyl J acid,
N-(3- or 4-carboxyphenyl)J acid, N-
(3- or 4-sulfophenyl) J acid, N-(4-7
minnow-3-sulfophenyl)J acid, N-(4-hydroxy-3-carboxyphenyl)J acid, N-(4-nitrobenzoyl)J acid, N-(4-aminobenzoyl)J acid, N-(4-aminobenzoyl)J acid, -amino-3-methylbenzoyl)Je, N
-Cβ-hydroxyethyl) J acid, N-(3 or 4-carboxybenzoyl) J acid, N-(3- or 4-sulfobenzoyl) J acid, N-(4-amino-3-sulfobenzoyl) J acid , N-(4-hydroxy-3-carboxybenzoyl) J acid, N-(4-nitrophenyl) J acid,
1-Hydroxy-7-aminonaphthalene-3-sulfonic acid (hereinafter abbreviated as γ acid), N-methyl γ acid, N-7 cetyl γ acid, N-methyl-N-acetyl γ acid, N-phenyl γ acid
acid, N-(3- or 4-carboxyphenyl)γ#N
-<3- or 4-sulfophenyl γ acid), N-(4-
Amino-3-sulfophenyl)γ acid, N-(β-hydroxyethyl)r#N-(p-methylphenyl)γ acid, N
-benzoyl gamma acid, N-(3- or 4-carboxybenzoyl) gamma acid, N-(3- or 4-sulfobenzoyl)
γ acid, N-(4-amino-3-sulfobenzoyl) γ acid, N-(49-monomethylbenzoyl) γ acid, N-(4-nitrobenzoyl) acid, N-(4-nitrophenyl) Examples include gamma acids.

The compound of the present invention is also useful for dyeing cellulose substrates such as cotton, cotton, viscose, rayon, paper, and harutz using ordinary dyeing methods, and is therefore useful for dyeing these substrates. It is valuable as a coloring agent for producing polarizing films with polarizing properties.

Conventionally, polarizing films that use iodine as a polarizing element (coloring agent) have been widely used because of their high polarization rate and their ability to absorb light in the entire visible light range, but they lack robustness and are susceptible to heat. Another disadvantage is that when exposed to light for a long time, the color fades or sublimes, resulting in a significant decrease in effectiveness.

When a disazo compound of formula (r) or a copper complex salt compound with the formula (r) is used as a polarizing element (coloring agent), these drawbacks can be overcome, and a polarizing film with a high polarization rate and excellent fastness can be obtained, and it is possible to obtain a polarizing film with a high polarization rate and excellent fastness. The previously limited applications of polarizing films can be greatly expanded.

Materials for manufacturing polarizing films include synthetic or recycled positive polymers with hydroxyl groups such as polyvinyl alcohol and cellophane, polyamide resins such as Nyloy, or resins such as copolymers of polyvinyl alcohol and vinyl acetate. type is used.

A polarizing film is produced by dyeing or coloring these materials with a disazo compound of formula (T) or a copper complex salt thereof using a conventional method, and subjecting them to stretching treatment as required.

Next, the present invention will be explained in more detail with reference to Examples. In these examples parts are by weight and percentages are by weight. In the examples, sulfonic acid groups and carboxyl groups are expressed in free form.

Example 1 57.7 parts of sodium 4-nitro-4-aminostilbene-2,2'-disulfonate was diazotized by a conventional method, and 20.9 parts of 2,5-dimethoxyaniline was added to an aqueous hydrochloric acid solution. Add the dissolved material, neutralize with sodium acetate, and couple. After the reaction was completed, the mixture was precipitated with hydrochloric acid, filtered, and dried to obtain 77.8 parts of a monoazo compound (the following formula).

11- Dissolve 77.8 parts of this monoazo compound in 1700 parts of water together with 11.7 parts of caustic soda, and dissolve 10.3 parts of sodium nitrite in this solution. Separately, an aqueous hydrochloric acid solution is prepared with 160 parts of water and 75 parts of 35% hydrochloric acid, and a mixed solution of the above-mentioned monoazo compound, sodium hydroxide, and sodium nitrite is added dropwise to diazotize the solution at 15 to 20°C. When diazotization is completed, sulfamic acid is added to eliminate excess nitrite ions. The above diazonium salt was added to a solution of 48.0 parts of N-(3-carboxy-4-hydro-xyphenyl) J acid dissolved in 1000 parts of a 10% soda ash aqueous solution, and
Coupling at °C. - The precipitate formed after stirring at night was separated in a furnace and dried to obtain 110.6 parts of a water-soluble disazo compound represented by the following formula.

The maximum absorption wavelength (λmax) of polyvinyl alcohol 12-coal film dyed with this disazo compound is 610.
nm and exhibited a deep blue color. This dyed film was stretched to obtain a dyed film with excellent polarizing properties.

Example 2゜In Example 1, 2-ethoxynaphthyl 7mine-6-sulfone-36.5 was used instead of 2.5-dimethoxyaniline.
Example 1 except that 30.6 parts of gamma acid was used instead of N-(3-carboxy-4-hydroxyphenyl)J acid. In the same manner as above, 93.4 parts of a water-soluble disazo compound represented by the following formula was obtained.

The maximum absorption wavelength (λmax) of the polyvinyl alcohol film dyed with this disazo compound is 627 nm, and it exhibits a deep blue color. This dyed film was subjected to stretching treatment to obtain a dyed film with excellent polarization properties.

13-Example 3-718゜Formula (VI) was prepared in the same manner as in Example 1゜2 using the compounds shown in the following table as the compounds represented by formula (IIIa) or formula (IITb) and 2M. The corresponding water-soluble disazo compound was prepared. In the table, the hue and λmax are
Are both polyvinyl alcohol films dyed? It is.

14- Example 19゜101.7 parts of the disazo compound produced in Example 1 were added to 3 parts of water.
000 parts of Cu 5o4-5 H20 dissolved in 20%
Add 137.5 parts of aqueous solution, 50 parts of N-methyl-N-ethanolamine, and 39.2 parts of 25% aqueous ammonia,
The reaction was carried out at ℃ for 4.5 hours. Adjust the pH of the reaction solution to 9.0 with a small amount of hydrochloric acid, add 3.0% salt to the reaction solution,
The produced precipitate was dried from house to house to obtain 90 parts of a copper complex compound represented by the following formula.

The maximum absorption wavelength (λmax) of the polyvinyl allure film dyed with this disazo compound was 557 nm, and it exhibited a green-blue color.

Examples 20 to 23 Example 1 was carried out using the compounds shown in the following table as the compounds represented by formula (■8) or formula (I]Tb) and 2M.
．． A disazo compound corresponding to formula (VII) was produced in the same manner as in Example 19, and then copper complex salts were produced in the same manner as in Example 19.

The hue and λmax in the table are for those dyed on polyvinyl alcohol film.

Example 24, 19.1 parts of a disazo compound represented by the following formula was added to 100 parts of water.
3.1 parts of sodium sulfide was added, and the mixture was reacted at 40°C for 2 hours.

After the reaction was completed, 5% of common salt was added to the reaction solution for salting out, and the solution was separated and dried to obtain 17.6 parts of a water-soluble disazo compound represented by the following formula.

The maximum absorption wavelength (λmax) of the polyvinyl alcohol film dyed with this disazo compound is 622 nm1
7- and exhibited a green-blue color.

Examples 25 to 37 Using the compounds shown in the following table as the compounds represented by the formula 0TTa) or the formula (ITTb) and the formula
) was prepared, and then the nitro group was reduced to an amino group in the same manner as in Example 24.

The hue, λmax, is for polyvinyl alcohol films dyed with these compounds.

18- Example 38゜5.6 parts of the disazo compound produced in Example 24 was added to 20 parts of water.
Dissolve in 0 parts and heat to 95°C. In this, CuSO
201.68 parts of 4-5H, 25% y-4-a water 2.
20 parts of an aqueous solution containing 4 parts of N-methyl-N-ethanolamine and 5 parts of N-methyl-N-ethanolamine are added and reacted at 95°C for 3 hours. After the reaction was completed, 10% common salt was added to the reaction solution for salting out, and the resulting precipitate was separated and dried to obtain 4.5 parts of a water-soluble disazo compound represented by the following formula.

The maximum absorption wavelength (λmax) of the polyvinyl alcohol film dyed with this disazo compound was 650 nm, and it exhibited a green-blue color.

Examples 39-49゜The compounds shown in the following table were used as the □ compounds represented by the formula (IHa) or (rlTb) and the formula (VlTb).
) and synthesize a water-soluble disazo compound corresponding to
A compound corresponding to formula (■) was prepared by using the same method as in Example 24, and this was further converted into a copper complex salt by the same method as in Example 3'8. The hue, λmax, is for polyvinylalconyl films dyed with these compounds. □ □.

Example 50 Next 5'''': 21 parts of the compound represented by 11
11 Dissolved in 1000 parts, added 1'3 parts of ethylenediaminetetraacetic acid disodium salt (dihydrite) and allowed to react at 35°C. After the end of the market,
Salt out by adding 7% common salt to the volume of the aqueous solution. The produced precipitate was separated and dried to obtain 1.7 parts of a water-soluble disazo compound represented by the following formula.

The maximum absorption wavelength (λ~...) of polyvinyl aluminum 4-'m dyed with a conotic solution is 616'n
m and reddish. J patent applicant with blue color Nippon Kayaku Co., Ltd. 22-

Claims (1)

[Claims] [In the formula m, X is a nitro group or an amine group, and A is a formula (
a) or formula (b) (in formula (a) or (b), Rn is a hydrogen atom, methoxy group, ethoxy group, methyl group, or hydroxyl group; R2 is a hydrogen atom, methyl group, methoxy group, ethoxy group, acetylamino group or ureido group, R3 represents a hydrogen atom, methoxy group or ethoxy group, n represents O or 1, respectively). It represents wo. Y is an amino group, a methylamino group, an acetylamino group, an N-methyl-N-acetylamino group, a β-hydroxyethylamino group, a phenyl nucleus is a nitro group, an amino group, a hydroxyl group, a methyl group, a sulfonic acid group, a carboxyl group. It represents a phenylamino group or a benzoylamino group which may be substituted with one or two groups. However, Y is assumed to be bonded to the 6 or 7 position of the naphthalene nucleus, and when X is a nitro group, R1 in formula (a) is a methoxy group or an ethoxy group, and R2 is a hydrogen atom, a methyl group, or a methoxy group. , except when the ethoxy group and Y are an amino group, a methylamino group, a β-hydroxyethylamino group, a phenylamino group, a carboxyphenylamino group, or a sulfophenylamino group. ] A water-soluble disazo compound or a copper complex salt compound thereof.