CN1075760A - Rare-earth dyeing assistant and preparation technology thereof - Google Patents
Rare-earth dyeing assistant and preparation technology thereof Download PDFInfo
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- CN1075760A CN1075760A CN 92110218 CN92110218A CN1075760A CN 1075760 A CN1075760 A CN 1075760A CN 92110218 CN92110218 CN 92110218 CN 92110218 A CN92110218 A CN 92110218A CN 1075760 A CN1075760 A CN 1075760A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/32—Material containing basic nitrogen containing amide groups leather skins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
- D06P1/65118—Compounds containing hydroxyl groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/653—Nitrogen-free carboxylic acids or their salts
- D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/67341—Salts or hydroxides of elements different from the alkaline or alkaline-earth metals or with anions containing those elements
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Coloring (AREA)
Abstract
Rare-earth dyeing assistant is to be multicomponent, the multifunctional dyeing auxiliary agent of main component with the macromolecule rare-earth complex.It is made of ethylenediamine, polyethylene polyamine, trimethylamine, ethylene glycol, epoxychloropropane, monoxone, rare earth etc.Its collection level dyeing, fixation, increase and be deeper than one, can improve the adhesion of dyestuff and crust leather, increase colorfastness, can increase color depth (saturation degree, lightness) simultaneously; Improve the colourity of dye-uptake, saving dyestuff, reduction waste water.In addition, can be used as the chromium absorbing agent that the leather network is tanned, save arsenic, reduce the Cr in the waste liquid
2O
3Content simultaneously, improves the clean absorption rate of fatting agent, saves fatting agent; Play the fixedly effect of grease, this rare-earth additive except be used for leather help dye, also can be applicable to cotton, artificial cotton, fur, hair, fiber crops, flax, helping of chemical fibre and dye.
Description
DN rare-earth additive involved in the present invention is to be many components, the multifunctional dyeing auxiliary agent of Main Ingredients and Appearance with the macromolecule rare-earth complex.
Prior art in the prior art of the present invention field is:
On the current international market in " back to nature " in vogue still, leather and fur products is required to have the natural stype of " thin, light, soft ".Thereby the wherein thin natural graining that is meant thin coating maintenance leather, this just requires will redye dab on the leather processing technology, be coated with and dye combination; Especially suede, water dye to remove from office to redye and are not coated with, and this has just proposed new higher requirement to leather coloring.
The present used proprietary dyestuff rareness of leather industry, and acidity, direct dyeing fastness commonly used are poor, tone is not full, and dye dosage is big during dyeing, the cost height, chroma in waste water is dark.Be difficult to dye dark-toned leather when particularly the crust leather after the retanning of anionic acrylic resin retanning agent is with anionic acidity, direct dyeing, particularly dye the black leather.This has just hindered the extensive use of acrylic resin retanning agent in leather retanning.
Acrylic resin retanning agent is one of important retanning material of leather.It has been subjected to process hides worker's welcome since coming out always.During China's the 8th Five-Year Plan for national economic and social development with acrylic resin retanning agent as key popularized project.But, be difficult to dye dark-toned leather, particularly black leather during direct dyeing because the acrylic resin retan is with acid; And black is because historical reasons is lasting on market.Therefore, this colouring problem is troubling leather worker both at home and abroad always, and to this, the leather worker has done a large amount of work both at home and abroad, also obtains certain achievement, but does not fundamentally solve.Many researchers once used various means to strive capturing the global problem that this leather industry faces jointly both at home and abroad, as the exploitation ampholytic acrylic resins retanning agent; With slaine preliminary treatment acrylic resin retanning crust leathers such as hexamethylenetetramine, ammonium sulfate and alum; Germany Hoechst company has human ACID DYES and basic-dyeable fibre to match to solve the colouring problem of resin retan.All these measures have certain effect, but see all undesirablely from the indexs such as dye-uptake of dyefastness, gorgeous degree and dyestuff, do not get a desired effect; And some method also increases cost suddenly, operates also rather loaded down with trivial details.
Purpose of design of the present invention is:
Dyeing is the important means of beautifying leather.Different crust leather states and kind have nothing in common with each other to the requirement of dyeing, also have many problems.Design of the present invention is primarily aimed at the problem of the following aspect of dyeing process in the curriery:
(1) colouring problem of solution acrylic resin retanning crust leather.
Retanning is called as " Golden Touch " in leather industry, and acrylic resin retanning performance in retanning agent is the best, is described as miracle type retanning agent, is China's " the Seventh Five-Year Plan " scientific achievement.But the existence of a large amount of carboxyls has a strong impact on the combination of crust leather to subsequent handling dyestuff and fatting agent in the big molecule of acrylic resin, and the crust leather surface colour is light, and especially " dying and deceive " becomes distinct issues.
The colouring problem of using DN serial rare-earth auxiliary agent to solve acrylic resin is incomparable with other any materials and method.DN serial rare-earth auxiliary agent can change the electriferous state of crust leather, improve of the absorption of resin retanning crust leather to anionic dyestuff and fatting agent, resin retanning crust leather with the processing of DN series auxiliary agent, the leather color of being dyed is pure, tone is full, bright-coloured, has solved the colouring problem of acrylic resin retanning crust leather, even it is also very good to dye the black effect, reached the degree that chromium retanning crust leather dyes black, some index has also surpassed the chromium retan.
(2) improve dyefastness, reduce dye dosage, simplify production technology.
" thin, light, soft " is one of important trend of leather products, for the various garment grain leathers that needs are covered with paint, lacquer, colour wash, etc., redyes dab and is and improve the quality and the fine way of class; For the suede garment leather of not covering with paint, lacquer, colour wash, etc., then higher to the dyeing requirement, not only require color and luster full, pure, but also need good fastness.
DN serial rare-earth auxiliary agent is used for leather coloring, its level dyeing, the effect that increases dark and fixation are all fairly obvious, can play and prevent the look flower, the leather color even of being dyed, pure, tone is full, bright-coloured, has improved the dye-uptake of dyestuff to leather, can improve dyefastness 0.5-1 level, save dyestuff 10-25%, the secondary dyeing (chromatography) of suede garment leather can be changed into once dyeing, simplified production technology.
Design of the present invention:
The present invention synthesizes the macromolecule complex body earlier, then with itself and rare earth complex, and composite again other material, thus synthesize the rare earth high polymer complex compound.
1, rare-earth additive help that to dye function as follows:
A. the macromolecule complex body is synthetic:
Anionic dye (acid, direct dyestuff) and crust leather fiber are mainly with the electrovalent bond combination, and the electrovalent bond adhesion is not strong; Moreover it is not the sulfonic group isoreactivity base hydrophily of dye molecule is strong, thereby water-fast.Desire improves colorfastness, must improve the bonding state of dyestuff and fiber.
Sulfonic group effect among middle ortho-nitrogen ion and the D-SO3H is played tint retention, simultaneously
Can play the effect of regulating molecular weight.
Have among product B in reaction (2), (3), the C-NH-,-the nitrogenous active group of NH2, under the low situation of pH value, do not show electrically; When under the high situation of pH value, become
,
Thereby can react with anionic dye like this and generate the color lake.
Product B, C and the combination of acrylic resin retan in reaction (2), (3) increase its cation group, help like this dying on the anionic dye.
The HOCH2CH2OH of reaction in (4), can regulate positive charge in the strand, avoid simultaneously that crosslinked to cause into grain excessively by force coarse.
B. graft reaction
In the grafting
After, product C, F more help the chromium in the chrome leather to carry out coordination, are simultaneously and rare earth ion increase complexing power.
C. with the complex reaction of rare earth ion:
More than each product can with rare earth ion generation complex reaction, thereby form rare-earth complex.The hapto that complexing takes place is-NH
2,-OH ,-COOH isoreactivity group.
Like this, delocalization effect takes place with dyestuff, the crosslinked multicomponent system of having formed of fiber in rare-earth complex, so maximum system energy descends, absorbing wavelength moves to long wave, and hyperchromic effect takes place.Moreover increase the dyestuff binding site, and increase the dyestuff dye-uptake, absorption peak is strengthened, make color and luster dense.The rare earth complex ion causes the dyestuff absorption spectrum to narrow down simultaneously, makes the finished leather tone full, pure.
D. composite other surfactant Pluronic(polyoxypropylene-polyoxyethylene block copolymer):
Law of compound according to surfactant adds Pluronic series in its system, improve permeability and level-dyeing property.
2, detailed proportioning
A, ethylenediamine (NH2-CH2CH2-NH2) are 0.05-0.4mol
B, polyethylene polyamine [NH2(CH2CH2NH) mCH2CH2NH2] be 0.4-0.9mol
D, ethylene glycol (OH-CH2CH2OH) are 0.02-0.2mol
F, monoxone (CICH2COOH) are the 0.05-0.4mol of total solid amount
G, mixed chlorinated rare earth (content is 30-50%) are total solid 15-50% that measures.
3, prepared process:
A, in reactor, add monomer ethylenediamine, polyethylene polyamine, ethylene glycol, trimethylamine and a certain amount of water and stir and made it stir (reactant concentration 60-80%) in 15-30 minute, be warming up to 40-60 ℃ then, add epoxychloropropane, in 30-60 minute, add, and temperature control should not be higher than 60 ℃, knows in 15-30 minute that then temperature to 75-95 ℃ of scope, is incubated 0.5-4.0 hour, be cooled to about 40-65 ℃, can obtain product A like this.
B, reactant is inserted in the reactor, temperature is controlled in the 0-5 ℃ of scope, drips NaOH and monoxone (CICH2COOH) and obtains product B like this.
C, product B is regulated PH4-6 with lemon or acetic acid, add rare earth chloride then and carry out complex reaction, obtain product C like this.
D, with product C and surfactant Pluronic(polyoxypropylene-polyoxyethylene block copolymer) compound, obtain the DN rare-earth additive like this.Product B is carried out complexing with different chloride rare earths, can obtain the DN rare-earth additive of different cultivars like this:
Product B and mixed chlorinated rare earth carry out complexing, can obtain rare-earth additive DN-1, are used for helping of anion retan such as acrylic resin retanning and dye.
Product B and lanthanum concentrate rare earth chloride carry out complexing, can obtain rare-earth additive DN-2, are used for helping of chromium retan and dye.
Product B and few europium rare earth chloride carry out complexing, can obtain rare-earth additive DN-3, can be used for helping of suede and dye.
Product B and pure neodymium chloride carry out complexing, can obtain rare-earth additive DN-4, are used for helping of fur and dye.
The present invention compared with prior art, it collects level dyeing, fixation increases and is deeper than one, can improve the adhesion of dyestuff and crust leather, increases colorfastness; Simultaneously can increase color depth (saturation degree, lightness); Improve dye-uptake, save dyestuff, reduce the colourity of waste water.In addition, can be used as the chromium absorbing agent of leather chrome tanning, save arsenic, reduce the Cr2O3 content in the waste liquid.Simultaneously, improve the clean absorption rate of fatting agent, save fatting agent; Play the fixedly effect of grease.This rare-earth additive is except being used for the leather dyeing auxiliaries, can also be applied to cotton, artificial cotton, fur, fiber crops, flax, helping of chemical fibre and dye.
Embodiment:
The monomer ethylenediamine that in reactor, adds 0.05-0.4mol, 0.4-0.9mol polyethylene polyamine, 0.02-0.2mol trimethylamine, 0.02-0.2mol ethylene glycol and a certain amount of water stir and to make it stir (reactant concentration 60%-80%) in 15-30 minute, be warming up to 40-60 ℃ then, the epoxychloropropane that adds 0.5-3.0mol, in 30-60 minute, add, and be incubated 0.5-4.0 hour, be cooled to about 40-65 ℃, can obtain product A, product A is inserted in the reactor, temperature is controlled in the 0-5 ℃ of scope, the amount that drips NaOH be polyethylene polyamine 1-3 doubly and to drip chloroacetic amount be that the 1-3 of polyethylene polyamine doubly promptly obtains product B; Product B is regulated PH=4-6 with 0.001-2 citric acid or acetic acid, add rare earth chloride (content 30-50% consumption is 15-50%) then and carry out complex reaction, promptly obtain product C; Product C and the 10-30% that presses finished product are added surfactant Pluronic(polyoxypropylene-polyoxyethylene block copolymer) compound, promptly obtain the DN rare-earth additive.
Claims (2)
1, a kind of DN serial rare-earth dyeing assistant is characterized in that:
Ethylenediamine (NH2-CH2CH2-NH2-) is 0.05-0.4mol
Polyethylene polyamine [NH2 (CH2CH2NH)
mCH2CH2NH2] be 0.4-0.9mol
Trimethylamine
Be 0.02-0.2mol
Ethylenediamine (OH-CH2CH2-OH) is 0.02-0.2mol
Epoxychloropropane (
) be 0.5-3.0mol
Monoxone (CICH2COOH) is 0.05-0.4mol
Mixed chlorinated rare earth (content is 30-50%) is the 15-50% of total solid amount.
2, a kind of preparation technology of DN rare-earth dyeing assistant is characterized in that:
A. adding monomer ethylenediamine, polyethylene polyamine, ethylene glycol, trimethylamine and the stirring of a certain amount of water in reactor made it stir (reactant concentration 60%-80%) in 15-30 minute, be warming up to 40-60 ℃ then, add epoxychloropropane, in 30-60 minute, add, and temperature control should not be higher than 60 ℃, is warming up in 15-30 minute then in the 75-95 ℃ of scope, is incubated 0.5-4.0 hour, be cooled to about 40-65 ℃, can obtain product A like this;
B. reactant is inserted in the reactor, temperature is controlled in the 0-5 ℃ of scope, and the amount that drips NaOH is that 1-3 times of polyethylene polyamine and the amount that drips monoxone (CICH2COOH) are 1-3 times of polyethylene polyamine, obtains product B like this;
C. product B is regulated about PH=4-6 with citric acid or acetic acid, add rare earth chloride then and carry out complex reaction, obtain product C like this;
D. with product C and the 10-30% and the surfactant Pluronic(polyoxypropylene-polyoxyethylene block copolymer of pressing finished product) compound, obtain the DN rare-earth additive like this.
Product B is carried out complexing with different rare earth chlorides, can obtain the DN rare-earth additive of different cultivars like this.
Product B and mixed chlorinated rare earth carry out complexing, can obtain rare-earth additive DN-1, are used for helping of anion retan such as acrylic resin retanning and dye.
Product B and lanthanum concentrate rare earth chloride carry out complexing, can obtain rare-earth additive DN-2, are used for helping of chromium retan and dye.
Product B and few europium rare earth chloride carry out complexing, can obtain rare-earth additive DN-3, can be used for helping of suede and dye.
Product B and pure neodymium chloride carry out complexing, can obtain rare-earth additive DN-4, are used for helping of fur and dye.
Priority Applications (1)
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CN 92110218 CN1075760A (en) | 1992-09-17 | 1992-09-17 | Rare-earth dyeing assistant and preparation technology thereof |
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---|---|---|---|
CN 92110218 CN1075760A (en) | 1992-09-17 | 1992-09-17 | Rare-earth dyeing assistant and preparation technology thereof |
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Family
ID=4944684
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CN 92110218 Pending CN1075760A (en) | 1992-09-17 | 1992-09-17 | Rare-earth dyeing assistant and preparation technology thereof |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103243587A (en) * | 2013-05-28 | 2013-08-14 | 宁夏成丰工贸有限公司 | Technique for dyeing Tan sheep skin |
CN104963219A (en) * | 2015-07-09 | 2015-10-07 | 上海工程技术大学 | Method for improving dyeing rate and fixation rate of reactive dye on kawo kawo fibers |
CN105332296A (en) * | 2015-12-10 | 2016-02-17 | 缪琼华 | Accelerating agent for dyeing of reactive dyes |
CN105350357A (en) * | 2015-11-17 | 2016-02-24 | 安徽三宝棉纺针织投资有限公司 | Method using rare earth for assisted dyeing of pure cotton fabric |
CN105386337A (en) * | 2015-12-14 | 2016-03-09 | 唐晓琦 | Acidic dye dyeing method of modified viscose fibers |
CN105442349A (en) * | 2015-12-10 | 2016-03-30 | 缪琼华 | Preparation method of dyeing accelerant for reactive dyeing |
CN105463885A (en) * | 2015-12-22 | 2016-04-06 | 安徽三宝棉纺针织投资有限公司 | Pure cotton fabric dyeing assistant and preparation method thereof |
CN107083686A (en) * | 2017-05-22 | 2017-08-22 | 苏州凯邦生物技术有限公司 | A kind of Dyeing of Linen Fabric pre-treating method of utilization catalase |
-
1992
- 1992-09-17 CN CN 92110218 patent/CN1075760A/en active Pending
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103243587A (en) * | 2013-05-28 | 2013-08-14 | 宁夏成丰工贸有限公司 | Technique for dyeing Tan sheep skin |
CN104963219A (en) * | 2015-07-09 | 2015-10-07 | 上海工程技术大学 | Method for improving dyeing rate and fixation rate of reactive dye on kawo kawo fibers |
CN104963219B (en) * | 2015-07-09 | 2017-07-04 | 上海工程技术大学 | The method for improving dye-uptake and degree of fixation of the reactive dye on bombax cotton |
CN105350357A (en) * | 2015-11-17 | 2016-02-24 | 安徽三宝棉纺针织投资有限公司 | Method using rare earth for assisted dyeing of pure cotton fabric |
CN105332296A (en) * | 2015-12-10 | 2016-02-17 | 缪琼华 | Accelerating agent for dyeing of reactive dyes |
CN105442349A (en) * | 2015-12-10 | 2016-03-30 | 缪琼华 | Preparation method of dyeing accelerant for reactive dyeing |
CN105386337A (en) * | 2015-12-14 | 2016-03-09 | 唐晓琦 | Acidic dye dyeing method of modified viscose fibers |
CN105463885A (en) * | 2015-12-22 | 2016-04-06 | 安徽三宝棉纺针织投资有限公司 | Pure cotton fabric dyeing assistant and preparation method thereof |
CN107083686A (en) * | 2017-05-22 | 2017-08-22 | 苏州凯邦生物技术有限公司 | A kind of Dyeing of Linen Fabric pre-treating method of utilization catalase |
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