CN1060196C

CN1060196C - Activated black dye

Info

Publication number: CN1060196C
Application number: CN95110249A
Authority: CN
Inventors: 吴祖望; 王桂娟; 林莉
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 1995-05-18
Filing date: 1995-05-18
Publication date: 2001-01-03
Anticipated expiration: 2015-05-18
Also published as: CN1136057A

Abstract

The present invention relates to easily carved black reactive dye for dyeing silk fabric, which is represented by a formula disclosed in the specification. After the silk fabric is dyed, the silk fabric has the advantages of blackness, high washing resistance, sweat resistance, water resistance, wet treatment fastness, light fastness, etc. The easily carved black reactive dye for dyeing silk fabric has the general formula structure, wherein R1 is equal to H, -SO3Na and -COOH; R2 is equal to H, -CH3, -C2H5, -OCH3, -OC2H5 and -ClR3; R4 is equal to H and -SO3Na; Y is equal to -SO2CH2CH2OSO3Na or -SO2CH2CH2-*-CH2CH2SO3<->-SO2CH is equal to CH2.

Description

Activated black dye

The present invention relates to the black and active dye that a class silk dyeing is used.

The dyestuff of application quantity maximum is a black dyes in the silk printing and dyeing, the kind of using at most in the past is that C.I. directly deceives 38, this dyestuff pitch black degree on silk is good, but its structure is owing to contain p-diaminodiphenyl pastern bone frame, and p-diaminodiphenyl has carcinogenic toxicity and forbidden by the countries in the world explicit order.In addition, fastness such as directly black 38 anti-ly soap, sweat stain are poor, and discharge is also undesirable, discharge printing place is not white, and easily yellowing, under the discharge printing technology of optimizing, carving is spent the whiteness (call in the following text and carve whiteness) at line place in vain and generally has only 48～50 whiteness units with the black silk fabric of this dyeing.The another kind of pitch black degree that often uses in silk printing and dyeing dyestuff preferably is the complexing metal dyestuff, and as reactive black 43, pitch black degree and wet colour fastness can meet the demands behind the silk though dye, and carve whiteness and have only 38 whiteness units, are unsuitable for discharge printing.Ri Kaiping 2-202956 and Chinese patent CN891032117 be based on the C.I. reactive black 5, pieces together mutually with the dyestuff of another or two chloride triazinyls, improved the pitch black degree when dyestuff dyes on cotton fibre.Its on silk pitch black degree still can, but the carving whiteness also have only 44 whiteness units.

The objective of the invention is to develop the black and active dye that a class silk is used, have that pitch black degree is soaped well, anti-concurrently, perspiration resistance and fastness to water and light fastness be good, with its dye black silk fabric during as the discharge printing background color, decorative pattern place carving whiteness excellence, and in synthetic, do not use and dye the aromatic amine that the former decomposition of greig does not produce carcinogenic toxicity.

Design of the present invention considers that in structure design the easy silk fabric black and active dye of the silk of no carcinogenic toxicity is to be pieced together to mix by 2～3 component dyestuffs to form, and the component dyestuff has following formula:

In the formula: R ₁=H ,-SO ₃Na or-COOH;

R ₂=H ,-CH ₃,-C ₂H ₅,-OCH ₃,-OC ₂H ₅Or-Cl;

1. be anti-ly soaping of guaranteeing printed silk behind dyed silk piece fabric and the discharge printing thereof, perspiration resistance and water-fast wet colour fastness such as soak, employing can with the reactive dyestuffs of protein fibre such as silk with covalent bonds.

2. adopting with black-and-blue dyestuff is main component, pieces together with the orange or red dyestuff and mixes, and absorbs in the hope of having than isostatic in 400～700nm visible region.

3. black is pieced together in the union dyeing material, and black-and-blue disazo dyes is main component, and its highest absorbing wavelength should be in more than the 620nm as far as possible, to guarantee to piece together mixed back pitch black degree.Should be with 1-amino-8-hydroxyl-3,6 naphthalene disulfonic acids (hereinafter to be referred as H-acid) are a disazo dyes of coupling component, under common dyeing condition, being azo bodily form formula at amino ortho position one side azo-group exists, the hydroxyl ortho position then exists with quinone hydrazone isomeric forms, and the transfer transport direction is as follows:

Then the existence of strong electron-withdrawing group nitro and other electron withdrawing group such as sulfonic group, carboxylic acid group on the A ring will help the red shift of dyestuff absorbing wavelength, also help the highest absorption to the displacement of long wave direction and have to electron substituent group on the B ring.

4. consider from carving white angle that after the reductive agent effect, azoic dyestuff fracture fragment should be easy to wash-out from the fiber, introduce carboxyl in the molecule or sulfo group favourable to the wash-out of fragment.In addition, the fracture fragment should not oxidation yellowing.Paying special attention to it combines this and partly goes back primary fragment and be difficult for the oxidation yellowing with fiber.Therefore, the sulfuryl that ethyl sulfone type active gene has strong electrophilic is coupled to aromatic ring, and cloud density amino on the fragment is greatly descended, and alkalescence weakens and is difficult for oxidation, suits especially to be used for discharge printing as background color.For example: beta-sulfuric ester ethyl sulfonyl type active group and β-(N-methyl-sulfoethyl amine base) ethyl sulfone type active group.

Based on above-mentioned design, be as first diazo component of the acid coupling of this black-and-blue component dyestuff (I): Second diazo component of alkaline coupling is:

As the coupling component of orange component dyestuff (II) as:

As the coupling component of red component dyestuff (III) as: Can be used as the amine of diazo component of dyestuff (II) and dyestuff (III) such as the amine of above-mentioned dyestuff (I) second diazo component.They can be identical with second diazo component of dyestuff (I), also can be different.

The diazo component of above-mentioned each component dyestuff can execute or anti-method 0～20 ℃ of diazotization, the coupling first time of dyestuff (I) is below 20 ℃, and H-acid coupling component is added drop-wise in the diazonium liquid, o'clock is coupled in pH≤3 to react completely.The coupling of the coupling second time of dyestuff (I) and dyestuff (II) and (III) is all at 10～25 ℃, and time finish pH=6～8.Three kinds of component dyestuffs can synthesize the back assembly separately to be mixed, and also can the wet method assembly mix in building-up process, and spraying drying obtains black dyes then.

Black dyes of the present invention dyes silk and can dye with ionogen (as salt or anhydrous sodium sulphate) is short in neutral medium, or to regulate dye liquor pH with acid or glacial acetic acid be 4.5～6 times short dying, make dye adsorption on fiber, regulating dye bath with soda ash or sodium bicarbonate then, is 7～9 times and fibroin reaction fixation at pH.

The white discharge of black silk can close formaldehydes with hyposulfite and carve white agent, and as rongalite, the carving white zine is carved white calcium or tin protochloride and is the white agent of carving.Wherein with white ability the best of carving of rongalite (Sodium Thiosulfate is closed formaldehyde), the discharge printing effect of tin protochloride is relatively poor relatively.Silk black matrix after the discharge printing is pitch-black, and decorative pattern is pure white, and fastness is good.

Black and active dye of the present invention also can be used for direct printing and nitrogen-containing fiber and the coloration of textile materials and the stamps such as wool, polyamide fibre of silk.

Silk dyeing of the present invention is to be pieced together to mix by 2～3 component dyestuffs to form with the characteristics of black and active dye; Under synthetic or reductive agent effect, all can not decomposite the current disabled arylamine that carcinogenic toxicity is arranged; After dyeing on the silk, color and luster is pitch-black; Have good washable, sweat proof and water-fast wet colour fastness and sun-resistant fastness such as soak; When carrying out discharge printing as background color, discharge printing place decorative pattern is pure white.

Embodiment 1

P-Nitroaniline ortho-sulfonic acid 21.8 parts (0.1 mole) and water are heated to for 250 parts and make it dissolving more than 80 ℃, rapid on the rocks being cooled to below 10 ℃, add 0.25 mole of concentrated hydrochloric acid, add 80% sodium nitrite solution (containing 6.9 parts of Sodium Nitrites) then, 10 ℃ of following diazotization.After reacting completely, will contain 34.1 parts of pH of H-acid and be 6～6.5 about 15% H acid solution and slowly splash in the above-mentioned first diazonium liquid, the pH value of reaction solution must be controlled at below 3.Analyse with ply of paper and to be controlled to diazonium salt and H acid all disappears.After once being coupled to terminal point, regulate about pH to 7 with soda ash liquid, the second diazonium liquid with the concentration made from 28.1 parts of 4-(beta-sulfuric ester ethyl sulfonyl) aniline about 15%, in pH=6.5～7, the secondary coupling is saltoutd under the room temperature, filter, drying obtains black-and-blue component dyestuff (I)-1, about 100 parts of folding hundred amounts.

Component dyestuff (I)-1 is pieced together the mixed reactive black that can be used for proteic matrix dyeing and discharge printing with dyestuff (II)-1, dyestuff (III)-1 in following ratio:

The black dyes assembly is mixed than being exemplified below:

Formula number	Component dyestuff (weight percent) (I)-1: (II)-1: (III)-1	Dyeing silk crepe de Chine consumption hectogram fiber heavy (%)	Color on the real silk crepe de Chine
Formula number	Component dyestuff (weight percent) (I)-1: (II)-1: (III)-1		Color on the real silk crepe de Chine	①	90∶10∶0	7	Blue light is black
②	83∶17∶0	7．5	Green glow is black	①	90∶10∶0	7	Blue light is black
②	83∶17∶0	7．5	Green glow is black	③	71∶8∶9	8．3	Blue or green ruddiness is black
④	62∶14∶24	9	Ruddiness is black	③	71∶8∶9	8．3	Blue or green ruddiness is black

Embodiment 2

Listed dyestuff is 4. water-soluble by 8～10% hectogram fiber amounts of reusing among the embodiment 1; bath raio 1: 10～40 (relevant with dyeing process; that low bath raio is got in dye gigging; that rope dyes or contaminates gets high bath raio); 40 ℃ the real silk crepe de Chine gone into to dye, add anhydrous sodium sulphate 40～80g/L, rise to 95～98 ℃ by 40 ℃ in 30 minutes; add soda ash 2g/L after 10 minutes, fixation is 30～60 minutes under this temperature and pH.Dye complete, washing, 2～3g/L nonionic or anionic detergent be 80 ℃ of soap boilings 10～15 minutes, washing, drying, the silk color and luster that obtains is pitch-black plentiful.

Embodiment 3

Black silk carving can be starched in vain by below preparation carving in vain:

120～200 parts of rongalite

0～50 part in urea

Water x part

3～10 parts in whitening agent

The former paste of stamp y part

Add up to 1000 parts

Behind the manual wire mark, under 0.04～0.08MPa, evaporate 12～15min, washing, destarch, washing, drying, it is pure white to obtain the stamp bottom, records decorative pattern part whiteness and can reach more than the 60 whiteness units.

Claims

1, a class piece together to be mixed by azoic dye and the black and active dye that obtains, it is characterized in that it is that to be main black-and-blue dyestuff press the column weight amount with the orange of logical formula II, (III) and orchil compares with mixed forming by logical formula I:

In the formula: R ₁=H ,-COOH ,-SO ₃H;

R ₂＝H，－CH ₃，－C ₂H ₅，－OCH ₃，－OC ₂H ₅，－Cl；