JPH0826237B2 - Pyrimidine compound and method for dyeing or printing fiber material using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel pyrimidine compound in the field of dyeing or printing a fiber material as a reactive dye.

2. Description of the Related Art Dyeing or printing of a fiber material using a fiber-reactive pyrimidine compound is known, for example, in JP-A-60-58470 and is widely practiced.

Problems to be Solved by the Invention Due to recent changes in technical and economic conditions in the demand industry, existing fiber-reactive pyrimidine compounds are not always able to meet all the needs of the demand industry. For example, looking at the dyeing performance, which is one of the basic required performances of dyes, many unsatisfactory points have been found.

Means for Solving the Problems In order to find a novel pyrimidine compound having performance capable of responding to the sophistication of needs as described above, the inventors of the present invention connect the type and number of the fiber-reactive groups and connect them. As a result of diligent studies on the type of linking group and the linking site, a compound having specific performance was found by optimally combining specific ones, and the present invention was completed.

That is, the present invention has the following general formula (I) [Wherein D is a dye residue, A is hydrogen, chloro, bromo, methyl, nitro, cyano, carboxy or sulfo, R ₁ and R ₂
And R ₃ are each independently hydrogen or optionally substituted alkyl, B ₁ and B ₂ are independently phenylene or naphthylene optionally substituted, Y ₁ and Y ₂ are independently each other-
CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali) or vinyl. ] A pyrimidine compound represented by the following and a method for dyeing or printing a fiber material using the same.

Among the compounds of the present invention, the compounds represented by the following general formulas (II) and (III) are particularly preferable.

[In the formula, D, R ₁ , R ₂ , R ₃ , B ₁ , B ₂ , Y ₁ and Y ₂ have the above meanings. ] [In the formula, R ₄ is hydrogen, methyl or ethyl, and D has the above-mentioned meaning. When R ₁ , R ₂ and R ₃ are independently optionally substituted alkyl, such a group is described in, for example, JP-A-59-122549.
The groups indicated in the publication are applicable, preferably methyl or ethyl. Among them, it is particularly preferable that R ₃ is hydrogen and at least one of R _{1 and} R ₂ is hydrogen.

In the case of phenylene or naphthylene which may be independently substituted with each other, B ₁ and B ₂ correspond to the groups known in the same publication, among them, unsubstituted phenylene or methyl, methoxy, ethyl. , Ethoxy, chloro, bromo,
Phenylene substituted with 1 or 2 groups selected from the group consisting of nitro, sulfo and carboxy, or 1
Naphthylene, which may be substituted with one sulfo, is preferable, and among them, the number of groups substituting phenylene or naphthylene is preferably 1 or less.

When Y ₁ or Y ₂ is —CH ₂ CH ₂ L, what is known as a group capable of leaving by the action of an alkali corresponds to this, and examples thereof include sulfate, thiosulfate, acetoxy and Examples include chloro. Preferred Y ₁ and Y ₂ are
Both are cases of β-sulfatoethyl, in which vinyl may be partially mixed.

The dye residue represented by D is preferably an anionic dye residue, and is an alloy or non-metal-containing azo type, anthraquinone type, metal-containing phthalocyanine type or formazan type,
There are residues of dioxazine-based or stilbene-based dyes, and for example, the dye residues described in JP-A-60-173060 are applicable.

Among them, particularly preferable D is, for example, the following formulas (A) to (L): [In the formula, R ₅ is a lower alkyl group or a phenyl group which may be substituted with a chlorine atom or a nitro group. ] [In the formula, R ₆ is an amino group, a lower alkyl group or a phenyl group, and R ₇ is a hydrogen atom, a lower alkyl or a lower alkoxy group. ] [In the formula, Me is Cu, Ni or Co, preferably Cu. ] [In the Formula, W is _C2-6 alkylene, Is. ] [In the formula, Me is Cu, Ni, Co1 / 2 or Cr1 / 2, and particularly preferably Cu, CO1 / 2 or Cr1 / 2. ] [In the formula, Pc is a copper or nickel-phthalocyanine nucleus, preferably a copper phthalocyanine nucleus, and 1 ≦ a ≦
2, 0 ≦ b ≦ 2, 1 ≦ c ≦ 2 and a + b + c ≦ 4, B is —NHCH ₂ CH ₂ NH—, Is. ] [In the formula, R ₈ and R ₉ are each independently a sulfonic acid group or a lower alkoxy group. ] [Wherein V is a hydroxy group, vinyl or β-sulfatoethyl group, and T is a C ₂ -C ₆ alkylene or Represents ], And in some cases, the formula (A),
In (B), (D), (E), (G), (I) and (K), a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group or a carvone is added to the phenyl group or naphthyl group on the diazo component side. The acid group may be additionally substituted.

The present invention represented by the general formula (I) includes, for example, the following formula (I
V) [In the formula, D and R ₃ have the above-mentioned meanings. ] The dye represented by the following formula (V) [In the formula, Z ₁ , Z ₂ and Z ₃ are each independently chloro, bromo or fluoro, and A has the above-mentioned meaning. ] The halogenopyrimidine represented by the following formula (VI) [In the formula, R ₁ , B ₁ and Y ₁ have the above-mentioned meanings. ] And an amino compound represented by the following formula are condensed in any order by a conventional method to obtain a monohalogenpyrimidine compound, followed by the following formula (VII) [In the formula, R ₂ , B ₂ and Y ₂ have the above-mentioned meanings. ] The compound of the present invention can be produced by condensation with the amino compound represented by the formula at 40 to 100 ° C while adjusting the pH to 2 to 6.

Examples of the halogen pyrimidine represented by the formula (V) include 2,4,6-trifluoropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine and 2,4-difluoro-5,6-
Dichloropyrimidine, 2,4,6-trifluoro-5-methylpyrimidine, 2,4,6-trifluoro-5-nitropyrimidine, 2,4,5,6-tetrafluoropyrimidine, 2,4,6-
Trifluoro-5-bromopyrimidine, 2,4-difluoro-5-bromo-6-chloropyrimidine, 2,4-difluoro-5-nitro-6-chloropyrimidine, 2,4-difluoro-6-chloropyrimidine, 2 , 4,6-Trichloropyrimidine, 2,4,5,6-tetrachloropyrimidine, 2,4,6-
Trichloro-5-carboxypyrimidine, 2,4,6-trichloro-5-cyanopyrimidine, 2,4,6-trichloro-
5-sulfopyrimidine etc. are mentioned. Especially 2,4,
6-trifluoro-5-chloropyrimidine is preferred.

The compound of the present invention may exist in a free acid form, but is preferably an alkali metal salt or an alkaline earth metal salt, and examples thereof include sodium salt and potassium salt.

The compound of the present invention has a fiber reaction and can be used for dyeing or printing a hydroxy group-containing or carbonamide group-containing material. The material is preferably used in the form of a fibrous material or of a blended material thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulosic fiber materials or regenerated products thereof and polyvinyl alcohol. Cellulosic fiber materials are cotton, as well as other vegetable fibers such as linen,
Hemp, jute and ramie fibers are preferred. Regenerated cellulosic fibers are, for example, viscose staples and filament viscose.

Carbonamide group-containing materials are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers such as wool and other animal hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-
It is 4.

The compound of the present invention can be dyed or printed on the above-mentioned material, particularly on the above-mentioned fiber material by a method depending on physical and chemical properties.

For example, in the case of exhaust dyeing on a cellulose fiber, in the presence of an acid binder such as sodium carbonate, sodium phosphate tribasic, and caustic soda, a neutral salt, such as Glauber's salt or salt, is optionally added, and if desired, a solubilizing agent is added. Agent, penetrating agent, or leveling agent in combination, and is carried out at a relatively low temperature. Neutral salts which promote the exhaustion of the dye can be added only after the original dyeing temperature has been reached or before, optionally in portions.

When dyeing cellulose fibers according to the buzzing method,
After padding at room temperature or elevated temperature and drying, it can be fixed by steaming or dry heat.

When printing on cellulose fibers, in one phase, for example with a printing paste containing baking soda or other acid binder, then by steaming at 100-160 ° C, or in three phases, for example medium. It can be carried out by printing with a neutral or weakly acidic printing paste, passing it through a hot electrolyte-containing alkaline bath, or over-padding with an alkaline electrolyte-containing padding solution, and steaming or dry heat treatment.

In the printing paste, a sizing or emulsifying agent such as sodium alginate or starch ether is optionally used,
For example, it is used in combination with a usual printing aid and / or a dispersant such as urea.

Suitable acid binders for fixing the compounds of the present invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali upon heating. In particular, alkali metal hydroxides and alkali metal salts of weak or medium-strength inorganic or organic acids are mentioned, of which soda salts and potassium salts are particularly preferable. Examples of such an acid binder include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, sodium dibasic or tribasic phosphate, sodium silicate, sodium trichloroacetate and the like.

Dyeing of synthetic and natural polyamide and polyurethane fibers should be carried out by first exhausting from an acidic or weakly acidic dyeing bath under the control of a pH value, and then changing it to a neutral, and possibly alkaline, pH value for fixing. Can be done by Dyeing is usually carried out at a temperature of 60 to 120 ° C., but in order to achieve level dyeing, a common leveling agent such as a condensation product of cyanuric chloride and 3 times moles of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, an addition product of stearylamine and ethylene oxide can be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing on fiber materials. Particularly suitable for dyeing cellulose fiber materials, excellent fastness to sunlight, fastness to sweat and formalin, excellent fastness to wetness, for example, fastness to washing, fastness to peroxidative washing, fastness to chlorine, fastness to bleaching chlorine. , Fastness to sweat, fastness to acid hydrolysis and alkali resistance, and good fastness to rubbing and iron. Also extremely excellent pilling-up property, level dyeing property and wash-off property, good solubility and high exhaustion, point having dyeability, dyeing temperature, alkali agent, inorganic salt addition amount,
It is characterized in that it is hardly affected by fluctuations in the dyebath ratio and a dyed product of stable quality can be obtained.

Further, the compound of the present invention shows excellent build-up property and excellent alkali stability in cold batch up dyeing, and almost no difference in concentration and hue difference between fixation at low temperature and fixation at 25 ° C. It has the property of being less susceptible to hydrolysis by agents.

The present invention is described in detail below with reference to examples. In the examples, parts and% mean parts by weight and% by weight, respectively.

Example 1 1-Amino-8-hydroxy-7- (o-sulfophenylazo) -3,6-naphthalenedisulfonic acid (50.4 parts) in water (7)
It is dissolved in 00 parts, and 16.85 parts of 2,4,6-trifluoro-5-chloropyrimidine are added dropwise thereto at 10 ° C. At this time, the pH is adjusted to 8.5 to 9.5 using 5N aqueous sodium hydroxide solution, and the first condensation is completed at the same temperature and the same pH value.

Then, 28.1 parts of 1-aminobenzene-4-β-sulfatoethyl sulfone is added to complete the second condensation at 30 to 40 ° C. and pH 5 to 6.

Then, 28.1 parts of 1-aminobenzene-3-β-sulfatoethyl sulfone is added to complete the third condensation at 60 to 80 ° C. and pH 4 to 5. Then salt out with sodium chloride, overseparate, dry and in the form of the free acid: A pyrimidine compound represented by

Examples 2 to 81 1-Amino-8-hydroxy-7- (o-sulfophenylazo) -3,6-naphthalenedisulfonic acid, 2,4,6-trifluoro-5-chloropyrimidine used in Example 1 , 1-aminobenzene-4-β-sulfatoethylsulfone and 1-aminobenzene-3-β-sulfatoethylsulfone, in the following table, column A (compound of formula (IV)), column B (formula) Compound (V), column C (compound of formula (VI)) and column D (compound of formula (VII)) were synthesized in the same manner as in Example 1 to obtain corresponding pyrimidine compounds, The dyeing was performed to obtain a dyed product having a color tone shown in column E.

Dyeing Example 1 0.3 of each of the triazine compounds obtained in Examples 1-31
Parts are dissolved in 200 parts of water, 10 parts of Glauber's salt are added, 10 parts of cotton are added, and the temperature is raised to 60 ° C. Then, after 20 minutes, sodium carbonate 4
Parts and add, and dye at the same temperature for 1 hour. After dyeing, wash with water,
Each was subjected to soaping to obtain a dyed product excellent in dyeing performance and various fastnesses. Even when the dyeing temperature, the bath ratio and the addition amount of the inorganic salt were slightly changed, a dyed product with good reproducibility and stable quality was obtained.

Dyeing example 2 Color paste composition 5 parts each of the pyrimidine compounds obtained in Examples 1-31 5 parts urea 5 parts sodium alginate (5%) original paste 50 parts hot water 25 parts baking soda 2 parts balance 13 parts Colors with the above composition The paste is printed on mercerized cotton broad cloth, and after intermediate drying, steaming is performed at 100 ° C for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying.

In this way, a printed article having excellent dyeing performance and various fastnesses was obtained.

Dyeing Example 3 25 parts of each of the pyrimidine compounds obtained in Examples 1 to 31 are dissolved in hot water and cooled to 25 ° C. Immediately after adding 5.5 parts of 32.5% caustic soda aqueous solution and 150 parts of 50 degree Baume water glass, and further adding water to bring the total amount to 1,000 parts at 25 ° C., use this solution as a padding solution to wind up a cotton fabric. Seal with polyethylene film and store in a room at 20 ℃.

The cotton fabric padded in the same manner and rolled up and sealed with a polyethylene film is stored in a room at 5 ° C. After leaving each padding cloth for 20 hours, the dyed product is washed with cold water and then hot water, soaped in boiling detergent, further washed with cold water and dried to finish.

When the hue difference and the density difference between the dyed product left at 20 ° C. for 20 hours and the dyed product left at 5 ° C. for 20 hours were examined, almost no difference was observed. In addition, a dyed product having good build-up properties was obtained by cold batch-up dyeing.

Claims (8)

[Claims] 1. The following general formula (I): [Wherein D is a dye residue, A is hydrogen, chloro, bromo, methyl, nitro, cyano, carboxy or sulfo, R ₁ and R ₂
And R ₃ are each independently hydrogen or optionally substituted alkyl, B ₁ and B ₂ are independently phenylene or naphthylene optionally substituted, Y ₁ and Y ₂ are independently each other-
CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali) or vinyl. ] The pyrimidine compound shown by these. 2. A dye residue represented by D is a residue of an anionic dye containing or not containing azo, anthraquinone, containing phthalocyanine or formazan, dioxazine or stilbene. The pyrimidine compound according to claim 1. 3. The pyrimidine compound according to claim 1 or 2, wherein R ₁ , R ₂ and R ₃ are each independently hydrogen, methyl or ethyl. 4. B ₁ and B ₂ independently of each other are phenylene optionally substituted with 1 or 2 groups selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, carboxy and sulfo. A naphthylene which is or is optionally substituted with one sulfo.
Item 4. The pyrimidine compound according to any one of Items 3 to 3. 5. The pyrimidine compound according to any one of claims 1 to 4, wherein Y ₁ and Y ₂ are simultaneously β-sulfatoethyl. 6. The following general formula (II) [Wherein D, R ₁ , R ₂ , R ₃ , B ₁ , B ₂ , Y ₁ and Y ₂ have the meaning defined in the first claim. ] The pyrimidine compound in any one of Claim 1-5 shown by these. 7. The following general formula (III) in the form of a free radical. [In the formula, R ₄ is hydrogen, methyl or ethyl, and D has the meaning defined in claim 1. ] The pyrimidine compound of Claim 1, 2 or 6 shown by these. 8. The following general formula (I) [Wherein D is a dye residue, A is hydrogen, chloro, bromo, methyl, nitro, cyano, carboxy or sulfo, R ₁ and R ₂
And R ₃ are each independently hydrogen or optionally substituted alkyl, B ₁ and B ₂ are independently phenylene or naphthylene optionally substituted, Y ₁ and Y ₂ are independently each other-
CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali) or vinyl. ] The method of dyeing or printing the textile material characterized by using the pyrimidine compound shown by these.