JPH04117369A - Triazine-based compound, dye and method for dyeing - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (A is -OPO3H2, -NHCH2 CH2OPO3H2, etc., provided that either of A may be H, OH, halogen, lower alkyl, etc.; R<1> is H or substitutive lower alkyl; D is azo dye residue, anthraquinone-based dye residue or pyrazolone-based dye residue; m is 1 or 2). USE:A dye, effective in dyeing leather treated with metallic tanning agents, especially chromium, aluminum, zirconium, titanium, etc., and excellent in color fastness. PREPARATION:A compound expressed by formula II (D' is dye or dye intermediate) or formula III (Y is -NHCH2CH2OH, etc.) is reacted with phosphorus oxychloride in the presence of a tertiary amine (e.g. pyridine) and then hydrolyzed to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel triazine compound, a dye containing the triazine compound as an active ingredient, and a method for dyeing leather using the dye.

Conventional technology and its challenges Conventionally used leather dyes mainly rely on hydrogen bonds, van der Waals bonds, and van der Waals bonds between dye molecules and leather proteins.
Dyeing is achieved through physical bonds such as hydrophobic bonds. However, due to the weak binding strength of these bonds, sufficient color fastness cannot be obtained for leather, resulting in discoloration, dye migration, and
It has problems such as discoloration.

Reactive dyes for textiles are also used as leather dyes. This dye molecule has a coloring part and a part that reacts with and binds to the object to be dyed. The coloring part mainly consists of an acidic dye, and the binding part consists of a group having active hydrogen that is reactive with fibers. A typical example of the above group is a chlorotriazine group having one or two chlorine atoms, and some of these groups can be formed by substitution reaction with cellulose fibers, protein fibers, nylon, modified vinylon, etc. under strong alkaline and high temperature conditions. Strongly covalently bonded. Fibers dyed with reactive dyes characterized by such a dyeing mechanism have excellent color fastness. However, since leather has low heat resistance and alkali resistance, dyeing conditions are limited, and even if leather is dyed using the above-mentioned reactive dyes, the effects cannot be expressed satisfactorily.

Means for Solving the Problems In view of the current state of leather dyeing technology as described above, the present invention provides a dye that can be dyed well under normal leather dyeing conditions and that can obtain dyed leather products with excellent color fastness. It was designed to provide the following.

That is, the present invention provides general formula (1) [wherein A is a group -0PO3H2, a group -N HCR2CR20P Os R2 or a group -NH
0oPo3H2, provided that either one of A is a hydrogen atom, a hydroxyl group, a halogen atom, a lower alkyl group, a lower alkoxy group, a sulfonyl group, a group -NHR2, a group -N (
R2) 2, (wherein R2 represents a lower alkyl group, and B represents a sulfonyl group, a carboxyl group, a halogen atom, a lower alkyl group, or a lower alkoxy group). R1 represents a hydrogen atom, or a lower alkyl group which may be substituted with a lower alkoxy group or a hydroxyl group. D is 1
Indicates a valent or divalent azo dye residue or anthraquinone dye residue. m represents 1 or 2. The present invention relates to a triazine compound represented by the following, a dye containing the triazine compound as an active ingredient, and a method for dyeing leather using the dye.

The present inventor previously discovered that a compound having a phosphoric acid group is effective as a dye in leather dyeing (Japanese Patent Application No. 63-57661). As a result of further research, the present inventor found that it is effective to utilize a triazine group in introducing the above-mentioned phosphoric acid group into the dye. That is, the triazine group has high reactivity with functional groups such as amino groups of dyes or dye intermediates, and is easily bonded thereto. Moreover, the bondability with phosphoric acid groups is also good. Therefore, by introducing a phosphate group via a triazine group, the range of applicable dye residues is expanded. Furthermore, the use of a triazine group has the advantage that the color tone of the dye residue can be maintained as it is even after the introduction of sulfuric acid.

The novel triazine compound of the present invention represented by the above general formula (1) is useful as a leather dye, and has a reactive moiety that binds to leather via a triazine group and a coloring moiety.

The reactive moiety that binds to the leather contains a phosphate group.

The phosphoric acid group reacts with the agent to form a complex compound with metals such as chromium, aluminum, zirconium, titanium, etc. present on the surface of the leather that has been dyed in advance. In other words, seven metal agents have a toughening effect on leather by binding to proteins in the leather or participating in cross-linking between proteins. Some do. The upper side, which is bonded to this carboxyl group, is very strongly bonded to the phosphoric acid group through a complex bond. This significantly improves color fastness.

In addition, the phosphoric acid group improves the water solubility of the dye, facilitates handling of the dye in the dyeing process, and effectively suppresses uneven dyeing.

On the other hand, for the coloring part, it is possible to apply a wide range of dye residues used for boat fishing, but since leather is usually dyed in an acidic region, azo dye residues, anthraquinone dye residues, etc. Acidic dye residues such as groups and pyrazolone dye residues are preferred. The color tones of these dyed residues do not change due to the above-mentioned complex bond formation, and dyes with various tones can be easily produced.

The compound represented by the general formula (1) of the present invention can be produced, for example, by the following reaction scheme-1.

In Reaction Scheme-1, A, D and R1 are the same as above, D' is a dye or a dye intermediate, X is a halogen atom, and Y is a group -NHCH2CH20H or a group -N Hi
o Indicates H.

2-Mainguchi a) Synthesis of compound (3) Compound (3) is obtained by reacting the dye or dye intermediate represented by general formula (2) with a triazine halide.

(1) Synthesis of compound (4) Compound (4) can be obtained by hydrolyzing compound (3).

C) Synthesis of compound (5) Compound (5) can be obtained by reacting compound (3) with an amino alcohol such as ethanolamine or hydroxyaniline.

2) Synthesis of compound (1) Compound (4) obtained by the above steps (a) to (c)
or (5) in the presence of a tertiary amine such as pyridine, triethylamine, etc.
13), followed by hydrolysis, and the dye intermediate is diazotized in a conventional manner and then coupled to obtain a dye, or
Alternatively, it can be obtained by reacting with stun pentoxide (P205) or polyphosphoric acid, followed by diazotization and coupling.

Diazotization and coupling reactions may be carried out under normal conditions.

When using the compound of the present invention as a dye, the compound can be used alone or by blending various additives used in the art according to conventional methods.

The compounds of the present invention are particularly effective for dyeing leather treated with metals such as chromium, aluminum, zirconium, and titanium. The amount used in dyeing is not particularly limited, but is usually about 1 to 10% of the weight of shaving leather.

Dyeing of leather with the dye of the present invention can be carried out according to known leather/leather dyeing methods. For example, bast leather that has been shaved to a certain thickness is neutralized in water using sodium formate, sodium bicarbonate, etc. while rotating in a drum, dye is added and permeated into the leather, and then formic acid, etc. The dye may be bonded in an acidic aqueous solution using . pH of the above acidic aqueous solution
is usually about 2 to 8, and the temperature is about room temperature to about 60°C. The leather dyed in this way is then fattened and
It is dried and finished to become finished leather.

Effects of the Invention According to the present invention, the following excellent effects can be achieved.

(1) When the compound of the present invention is used as a dye, it can be dyed under the usual leather dyeing conditions and according to the same recipe as conventional acid dyes, and the dyed product obtained is
It has excellent color fastness such as rubbing fastness, cleaning resistance, and light fastness compared to those using conventional dyes.

(2) The compound of the present invention has excellent water resistance and solubility compared to conventional leather dyes.

(3) During synthesis, the compound of the present invention maintains the color tone of the raw material dye, and the color tone also changes due to the formation of a complex compound due to the combination of the phosphoric acid group and the metal washing agent during dyeing. It does not change. Therefore, dyes of required colors can be easily prepared.

EXAMPLES Hereinafter, examples will be shown to further clarify the characteristics of the present invention.

Example 1 2.4.6-Dolichlor 1 in 100 g of ice water at 0-5°C
．． 3.5) Add 30.8 g of riazine and 67 g of acetone, then add 44.3 g of 6-amino-4-hydroxy-2-naphthalenesulfonic acid (γ acid) and 13.3 g of 30% aqueous sodium hydroxide solution, and reduce the temperature to 0. The temperature was maintained at ~5°C and stirred for 1 hour. followed by 20.3 g of ethanolamine and 30
% caustic soda aqueous solution was added thereto, and the mixture was stirred at 0 to 5°C for 1 hour. After that, keep the pH at 7-8 and raise the temperature to 120℃.
Acetone was distilled off by gradually raising the temperature over time. It was dried under reduced pressure and pulverized to obtain a triazine compound of γ acid.

Next, 40 g of pyridine was added to 64 g of phosphorus oxychloride, and the total amount of the γ-acid triazine compound obtained above was added to
Added at 306C. Furthermore, add about 200 g of pyridine,
Stirred at 0-60°C. After stirring, add water to pH 6~
7. Hydrolysis was carried out at 30°C for 5 hours. After hydrolysis, the aqueous solution was dehydrated under reduced pressure, dried and ground at 120° C. to obtain 197 g of a pale orange powder of a phosphorylated triazine compound.

Next, add 9.3 g of aniline to 30 formulas of concentrated hydrochloric acid and 1 oomc of water.
The solution was dissolved in a mixed solution with 5°C, cooled to below 5°C, and 7g of sodium nitrite was added to diazotize. This diazotized product was added with stirring to an ice-water solution of caustic soda in which 35.2 g of the above phosphorylated triazine compound had been dissolved, and the solution was allowed to stand for 24 hours for salting out to obtain 41 g of the dye of the present invention having the following structure.

[physicality]

Color tone: red Phosphorus content: 8.6% Melting point: 2300°C or higher Example 2 Add 30.8 g of 2.4.6-dolichloro1.3.5 triazine and acetone to 100 g of ice water at 0 to 5°C. 67, 69 g of 4-amino-5-hydroquine-2,7-naphthalenesulfonic acid (H acid) and 13.3 g of 30% caustic sorta aqueous solution were added, and the temperature was maintained at 0 to 5°C.
Stir for hours. After that, keep the pH at 7-8 and keep at 120°C.
The temperature was gradually raised over a period of 5 hours, and the acetone was distilled off. The product was dehydrated under reduced pressure, dried, and pulverized to obtain a triazine compound of H acid.

Next, 40 g of pyridine was added to 51.2 g of phosphorus oxychloride, and the total amount of the triazine compound of H acid obtained above was added to 2
Added at 0-30°C. Furthermore, add about 200g of pyridine,
Stir at 50-60°C.

After stirring, water was added and hydrolysis was carried out at pH 6 to 7.30°C for 5 hours. After hydrolysis, the aqueous solution was dehydrated under reduced pressure and
The mixture was dried and ground at °C to obtain 208 g of a reddish-brown powder of a phosphorylated triazine compound.

Next, the obtained phosphorylated triazine compound g and 13.8 g of p-nitroaniline were dissolved in a mixed solution of 30 times of concentrated hydrochloric acid and 100 times of water, and then 7 g of sodium nitrite was added to diazotize the mixture. This diazotized product was added with stirring to an ice-water solution in a caustic sorter in which 40 g of the above phosphorylated triazine compound had been dissolved, and the solution was left to stand for 24 hours for salting out to obtain 52 g of the dye of the present invention having the following structure.

[physicality]

Color tone: striated phosphorus content near, 6% Melting point = 300°C or higher Example 3 Add 30.8 g of 2,4.6-dolichloro1,3.5-triazine and 67 g of acetone to 100 g of ice water at 0 to 5°C. Further, 44.3 g of 6-amino-4-hydroxy-2-naphthalenesulfonic acid (gamma acid) and 13.3 g of 30% aqueous sodium hydroxide solution were added, and the mixture was stirred for 1 hour while maintaining the temperature at 0 to 5°C. Thereafter, the pH was maintained at 7 to 8, and the temperature was gradually raised to 120° C. over 5 hours to distill off acetone.

It was dried under reduced pressure and pulverized to obtain a triazine compound of γ acid.

Following the reaction with phosphorus oxychloride, Example 1 and In the same manner, a dye of the present invention having the following structure was obtained.

(Color: A: Red) Example 4 A dye of the present invention having the following structure was obtained in the same manner as in Example 1 except that p-hydroxyaniline was used instead of ethanolamine.

(color tone: red) Examples 5-53 The dyes of the present invention shown in Tables 1 and 2 were obtained.

In addition, the meanings of 21 to Z3 in Tables 1 and 2 are as follows, and except for changing the raw materials and blending ratio (molar ratio) as appropriate, those of A2 or Zl are as in Example 1, Z2 was synthesized in the same manner as in Example 2 or 3, and Z3 was synthesized in the same manner as in Example 4.

Zl Knee NHCH2CH20PO3H2Z2 Knee 0
PO3H2 In addition, Examples 5 to 26 show that 2.4.6-dolichloro1. 3. In place of 5-triazine, a triazine derivative in which one chlorine atom of the triazine was substituted with a group indicated by AI in Table 1 was used.

Color fastness test [Test dye] Example 1. 2. 35. 36. 37. 54. Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 [Dyeing Method] Chrome Co. cowhide was dyed in a boat fishing drum for leather dyeing according to the following steps. In the following, "%" indicates the percentage by weight based on the amount of shaving leather used.

200% water 10 min spin 1.5% sodium formate 1.5% sodium bicarbonate 150% water 60 min spin 200% water 3% dye 150% warm water (50°C) 60 min spin 0.5% formic acid
60 minute rotation 200% water 10 minute rotation 10% dye 150% warm water (50℃) 1% formic acid 60 minute rotation 30 minute rotation 200% water 10 minute rotation [Test method] Test the leather dyed as above. ! 4, the following three tests were conducted.

0 Rubbing fastness: Same as JIS K 6547i.

0 sweat Test: Same as JIS L 08481.

0 Dry cleaning test: According to JIS L 0860.

The test results are shown in Table 3.

Vermilion table

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A represents the group -OPO_3H_2, the group -NHCH_2CH_2OPO_3H_2, or the group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, either one of A is a hydrogen atom, hydroxyl group, halogen atom, lower alkyl group, lower alkoxy group, sulfonyl group, group -
NHR^2, Group -N(R^2)_2, Group▲There are mathematical formulas, chemical formulas, tables, etc.▼, Group▲There are mathematical formulas, chemical formulas, tables, etc.▼, Group▲There are mathematical formulas, chemical formulas, tables, etc.▼, or Even if the group is a mathematical formula, chemical formula, table, etc. (in the formula, R^2 represents a lower alkyl group, and B represents a sulfonyl group, carboxyl group, halogen atom, lower alkyl group, or lower alkoxy group). good. R^1 represents a hydrogen atom, or a lower alkyl group which may be substituted with a lower alkoxy group or a hydroxyl group. D is monovalent or divalent
This indicates an azo dye residue, an anthraquinone dye residue, or a pyrazolone dye residue. m indicates 1 or 2. ] A triazine compound represented by (2) A dye characterized by containing the compound according to claim (1) as an active ingredient. (3) A method for dyeing leather, which comprises using the dye according to claim (2) in dyeing tanned leather using a tanning agent selected from chromium, aluminum, zirconium, and titanium. (4) Leather dyed by the method according to claim (3) above.