CN106282436A - A kind of method utilizing reactive dye that chrome tanning crust leather is dyeed - Google Patents
A kind of method utilizing reactive dye that chrome tanning crust leather is dyeed Download PDFInfo
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- CN106282436A CN106282436A CN201610770110.5A CN201610770110A CN106282436A CN 106282436 A CN106282436 A CN 106282436A CN 201610770110 A CN201610770110 A CN 201610770110A CN 106282436 A CN106282436 A CN 106282436A
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- water
- tanning agent
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- wet blue
- crust leather
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
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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
- 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
- D06P1/38—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 reactive dyes
-
- 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
- D06P3/3286—Material containing basic nitrogen containing amide groups leather skins using reactive dyes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a kind of method utilizing reactive dye that chrome tanning crust leather is dyeed, step is: first with chrome tanning agent and aldehyde tanning agent, the wet blue of backwater is carried out retanning, carry out retanning with the both sexes acroleic acid polymerization resin rich in primary amino radical and carboxylate radical again, then dye with reactive dye.The present invention is by chrome tanning agent, aldehyde tanning agent and both sexes acroleic acid polymerization resin retanning, add the chromium content in wet blue, improve crust leather alkali resistance, in chrome tanning collagen fiber, introduce more free amino group simultaneously, add the avtive spot that crust leather reacts with reactive dye；The collocation of retanning agent and selection make the dyeing pH of reactive dye and temperature more suit with tolerable temperature and the pH of crust leather, solving reactive dye and be difficult to use in a difficult problem for crust leather dyeing, the crust leather after dyeing has higher Bearable dry and wet wipe fastness and water-fastness fastness.
Description
Technical field
The present invention relates to the colouring method of a kind of leather, be specifically related to one and utilize reactive dye that chrome tanning crust leather is contaminated
The method of color, belongs to leather processing technique field.
Background technology
Dyeing is an important procedure in the tanning production course of processing, can give chrome tanning crust leather by dyeing beautiful
Color and beautiful outward appearance, cover the disability of natural leather grain, meet the aesthetic needs of consumer, adding of improving product
Value.Dyeing generally for chrome tanning wet blue, it should meet following requirements: bright in colour, bright, clear, attractive in appearance；Color even
Unanimously, colourless flower；There is higher fastness, the most easy to change etc..The main acid using textile industry in leather industry at present
Property dyestuff and direct dyes etc. dye, and the hydrophilic group of these dyestuffs is sulfonate radical, is typically only capable to and chrome tanning collagen fiber
Combine in the way of ionic bond, hydrogen bond or Van der Waals force, it is impossible to form firm covalent bond and combine, thus there will be dyeing base
Remove from office resistance to dry, the problem such as wet rubbing fastness is poor, dyestuff absorbance difference, the crust leather that dyes are the most water-fastness and soap.
Reactive dye, also known as chemically-reactive dyes, are one of dyestuffs the most commonly used in textile industry.Reactive dye have color
Compose the features such as complete, bright in colour, excellent performance, the suitability be strong.Reactive dyestuff molecule comprises parent dye and active group two
Individual key component.When dyeing the fibers such as cotton, hair, albumen, reactive dye can be with the active group on fiber
There is chemical reaction, form firm covalent bond, thus after dyeing, fiber has higher waterlogging-wiping-resistant fastness and washable heavily fortified point
Fastness.But at present reactive dye are seldom directly used in the dyeing of chrome tanning crust leather, its reason have following some: one is chrome tanning collagen side
Active group on chain is limited, does not has enough reaction site, is unfavorable for reactive dyeing；Two is logical when being reactive dyeing
Often need to carry out in the basic conditions fixation.When the pH of body lotion is more than 7, easily cause the detanning of chrome tanning crust leather；Three is chrome tanning
Temperature during crust leather dyeing typically requires and controls below 60 DEG C, and reaction temperature required during some reactive dyeing is relatively
High.Thus up to now, very limited about the research utilizing reactive dye that chrome tanning crust leather is dyeed, there are no and carry out work
Industry metaplasia is produced and the document report of actual application.
At present, there is research worker by the method for reactive dye modification is solved the problems referred to above, such as patent
201410566809.0,201510280729.3 carry out chemical modification to reactive dye before dyeing, to improve the firm of dyeing
Degree, but these method of modifying complex operations and gained modified active dye strength is low, transport inconvenience, be unfavorable for that industrialization pushes away
Wide application.
Based on above description understand, how to overcome reactive dye crust leather dyeing present in a difficult problem, it is achieved reactive dye
The dyeing of chrome tanning crust leather has been become a technical problem urgently to be resolved hurrily.
Summary of the invention
For reactive dye crust leather dyeing present in a difficult problem, the invention provides one and utilize reactive dye to chrome tanning
Crust leather carries out the method dyeed, and chrome tanning crust leather is processed before dyeing by the method, solves reactive dye and dyes crust leather
Difficult problem, improves the fastness of dyeing.
For all deficiencies that there is reactive dye modification, inventor changes thinking, it is intended to adopts and makes in other ways to live
Property dyestuff can play good Color in crust leather.Finally, start with from crust leather and searched out solution, obtained this
Bright method.Retanning process is improved by the present invention, adds the site reacted with reactive dye, improves the alkaline-resisting of crust leather
Ability, reduces dyeing pH and dyeing temperature, makes reactive dye play good Color in crust leather.Use the present invention
It is high that the dyeing crust leather that method obtains has color fastness, dry-cleaning water-fastness, resistance to, the characteristic of Bearable dry and wet wipe.
The concrete technical scheme that the present invention uses is as follows:
What the present invention provided utilizes the method that chrome tanning crust leather dyes by reactive dye, comprises the following steps: by backwater
Wet blue first carry out retanning with chrome tanning agent and aldehyde tanning agent, then carry out retanning with both sexes acroleic acid polymerization resin, then with living
Property dyestuff dyes；The effective ingredient of described both sexes acroleic acid polymerization resin is the both sexes third rich in primary amino radical and carboxylate radical
Olefin(e) acid polymer.
In the inventive method, described chrome tanning crust leather refers to the wet blue obtained after chrome tanning agent and aldehyde tanning agent retanning.This
The wet blue that bright method is suitable for can be that pig wet blue, ox head layer wet blue, sheep wet blue, goat wet blue or cow split are blue
The animal wet blues such as wet skin.In the inventive method, reaction mechanism that crust leather is dyeed by reactive dye is as it is shown in figure 1, first
Utilize chrome tanning agent and aldehyde tanning agent that the wet blue after shaving is carried out retanning, to increase the chromium content of crust leather and resistance to alkali ability；So
In rear use molecule, the both sexes acroleic acid polymerization resin rich in amino and carboxylate radical carries out retanning filling to crust leather.Pass through both sexes
Carboxylic acid ion in acroleic acid polymerization resin carries out ligand complex with the chromium in chrome tanning crust leather, improves the resistance to of chromic compound
Alkali ability, introduces a large amount of free amino group in chrome tanning collagen fiber simultaneously, provides sufficient reaction site for reactive dyeing.
After above-mentioned process, it is possible to use crust leather is dyeed by reactive dye, it is high that the dyeing crust leather finally given has color fastness,
Dry-cleaning water-fastness, resistance to, the characteristic of Bearable dry and wet wipe.
In the present invention, the effective ingredient of both sexes acroleic acid polymerization resin is the acroleic acid polymerization rich in amino and carboxylate radical
Thing, the structural formula such as following formula of the described acrylate copolymer rich in amino and carboxylate radical (being called for short acrylate copolymer or polymer)
Shown in I, the equal molecular mass of number is 2000～30000, in formula I, and vinyl amine construction unitPoly-
Mass fraction in compound is 30～70%；
In the present invention, both sexes acroleic acid polymerization resin can be prepared according to the method disclosed in prior art, also voluntarily
Can buy from market.The solid content of both sexes acroleic acid polymerization resin is 10～30wt%.Both sexes acrylate copolymer tree
Fat serves the effect of mordant, is used with the collocation of chrome tanning agent and aldehyde tanning agent by it, improves the alkaline-resisting degree of crust leather, increases
Add the reaction site of crust leather and reactive dye, made reactive dye that crust leather Color to be greatly promoted.
Further, the method that the present invention utilizes reactive dye to dye chrome tanning crust leather, prepares dyeing crust leather.Specifically
Comprise the following steps:
(1) wet blue after shaving is weighed, standby；
(2) backwater: wet blue is added in rotary drum, addition 200～the water of 300% in rotary drum, control water temperature 30～40
DEG C, it being subsequently adding 1.0～the oxalic acid of 1.5% or formic acid, 1.0～paregal O-15 of 1.5%, regulation pH is 3.2～3.5, turns
Dynamic 60～90min, draining；Water, oxalic acid or formic acid, paregal O-15 addition all on the basis of the quality of wet blue；
(3) retanning: add 100～the water of 200% in rotary drum, controlling temperature is 30～40 DEG C, be subsequently adding 1.5～
The chrome tanning agent of 4.5%, rotates 30～90min, adds the aldehyde tanning agent of 1～3%, rotates 1～4h, is eventually adding 1.5～2.5%
Sodium acetate, rotate 1～4 hour, body lotion pH reaches 3.6～4.0, draining；Water, chrome tanning agent, aldehyde tanning agent, the addition of sodium acetate
All on the basis of the quality of wet blue；
(4) neutralize: the crust leather after retanning being processed washes 10～30min by normal-temperature water in rotary drum, draining；It is subsequently adding
200～the water of 250%, control water temperature 30～40 DEG C, add 1.0～2.0% neutralize tannin and 1.0～the sodium bicarbonate of 2.5%,
Rotating 60～120min, body lotion pH reaches 5.0～6.5, draining；10～30min are washed the most again by normal-temperature water；Water, neutralization list
Rather, the addition of sodium bicarbonate is all on the basis of the quality of wet blue；
(5) both sexes acroleic acid polymerization resin retanning: the crust leather after neutralisation treatment is added in rotary drum, add 100～
The water of 250%, controlling temperature is 30～40 DEG C, is subsequently adding the both sexes acroleic acid polymerization resin of 2～6%, rotate 60～
150min, discharge opeing；The addition of water and both sexes acroleic acid polymerization resin is all on the basis of the quality of wet blue；
(6) dyeing: by both sexes acroleic acid polymerization resin retanning process after crust leather put in rotary drum, add 100～
The water of 200%, controlling temperature is 45～50 DEG C, is subsequently adding the reactive dye of 0.5～6%, rotates 60～150min, exists simultaneously
Point 3～5 additions 1.5～the sodium bicarbonate of 3.5% in dyeing course, regulation body lotion pH is maintained at 5.0～6.5, discharge opeing after dyeing；
Water, reactive dye, sodium bicarbonate addition all on the basis of the quality of wet blue；
(7) stuffing: add 100～the water of 250% in rotary drum, controlling temperature is 50～55 DEG C, be subsequently adding 10～
The fatting agent of 20%, rotates 90～120min, adds the formic acid of 2.0～3.0%, and the pH of regulation body lotion is 3.6～4.0, row
Liquid, add water after discharge opeing washing 10～30min, goes out drum and takes horse standing；Water, fatting agent, formic acid addition all with the matter of wet blue
On the basis of amount.
In the inventive method, described chrome tanning agent can be arbitrarily to may be used for chrome tanning agent in crust leather.
In the inventive method, described aldehyde tanning agent is in glutaraldehyde tanning agent, modified glutaraldehyde tanning agent and fatty aldehyde tanning agent
Plant or multiple, the glutaraldehyde tanning agent of preferably mass ratio 10:3-5 and the mixture of modified glutaraldehyde tanning agent.
Further, the mass ratio of glutaraldehyde tanning agent and fatty aldehyde tanning agent is preferably 10:3.5.
In the inventive method, described reactive dye are halo s-triazine reactive dye and sulphuric acid vinyl-sulfone reactive dyes
In one or more, can be such as the one in reactive brilliant red k-2g, Reactive Light Yellow K-4G and Reactive Turquoise Blue KN-G or many
Kind, their structural formula is as follows.Preferably, described reactive dye are reactive brilliant red k-2g or/and Reactive Light Yellow K-4G.
In the inventive method, described fatting agent can use any fatting agent disclosed in prior art.
The present invention utilizes reactive dye to dye crust leather, has the advantages that
(1) chromium content in wet blue is added by chrome tanning agent, aldehyde tanning agent and both sexes acroleic acid polymerization resin retanning,
Improve crust leather alkali resistance, in chrome tanning collagen fiber, introduce more free amino group simultaneously, add crust leather and activity dye
The avtive spot of material reaction；The collocation of retanning agent and selection make the dyeing pH of reactive dye and temperature and crust leather tolerable temperature and
PH more suits, and solves reactive dye and is difficult to use in a difficult problem for crust leather dyeing.
(2) chrome tanning agent and aldehyde tanning agent can form firm coordinate bond or covalent bond with the active group on collagen fiber
In conjunction with, and the carboxylic acid ion in both sexes acroleic acid polymerization resin can with chrome tanning agent coordination and be anchored at collagen fiber it
Between, the water-fastness ability of crust leather obtained is strong.
(3) reactive dye can form covalent bond with the primary amino radical generation chemical reaction in both sexes acroleic acid polymerization resin
In conjunction with, thus the crust leather after dyeing has higher Bearable dry and wet wipe fastness and water-fastness fastness, solves current dye
The problems such as the crust leather Bearable dry and wet wipe fastness of color method gained is poor, dyestuff absorbance difference, dyeing crust leather are the most water-fastness and soap.
(4) retanning of the present invention, colouring method simplicity, beneficially industrializing implementation, the method is particularly suitable for washable leather
And finished leather waterlogging-wiping-resistant fastness is required the production of higher leather products.
Accompanying drawing explanation
Fig. 1 utilizes the reaction mechanism figure that chrome tanning crust leather is dyeed by reactive dye.
Detailed description of the invention
The present invention utilizes the method that chrome tanning crust leather is dyeed by reactive dye, comprises the following steps:
Step one: batching is weighed.Wet blue after shaving is carried out batching weigh, and depending on as other material usage
According to.
Step 2: backwater: wet blue is added in rotary drum, addition 200～the water of 300% in rotary drum, control water temperature 30
～40 DEG C, be subsequently adding 1.0～the oxalic acid of 1.5% or formic acid, 1.0～paregal O-15 of 1.5%, regulation pH be 3.2～
3.5, rotate 60～90min, discharge opeing；Water, oxalic acid or formic acid, paregal O-15 addition all with the quality of wet blue as base
Accurate.
Step 3: retanning: addition 100～the water of 200% in rotary drum, controlling temperature is 30～40 DEG C, is subsequently adding 1.5
～the chrome tanning agent of 4.5%, rotate 30～90min, add the aldehyde tanning agent of 1～3%, rotate 1～4h, be eventually adding 1.5～
The sodium acetate of 2.5%, rotates 1～4 hour, and body lotion pH reaches 3.6～4.0, discharge opeing；Water, chrome tanning agent, aldehyde tanning agent, sodium acetate
Addition is all on the basis of the quality of wet blue.
Step 4: neutralize: the crust leather after retanning being processed washes 10～30min by normal-temperature water in rotary drum, draining；Then
Add 200～the water of 250%, control water temperature 30～40 DEG C, add 1.0～2.0% neutralize tannin and 1.0～2.5% little
Soda, rotates 60～120min, and body lotion pH reaches 5.0～6.5, discharge opeing；10～30min are washed the most again by normal-temperature water；Water, in
With tannin, sodium bicarbonate addition all on the basis of the quality of wet blue.
Step 5: both sexes acroleic acid polymerization resin retanning: addition 100～the water of 250% in rotary drum, controlling temperature is
30～40 DEG C, it is subsequently adding the both sexes acroleic acid polymerization resin of 2～6%, rotates 60～150min, discharge opeing；Water and both sexes third
The addition of olefin(e) acid fluoropolymer resin is all on the basis of the quality of wet blue.
Step 6: dyeing: addition 100～the water of 200% in rotary drum, controlling temperature is 45～50 DEG C, is subsequently adding 0.5
～the reactive dye of 6%, rotate 60～150min, point 3～5 additions 1.5～little Su of 3.5% in dyeing course simultaneously
Beating, regulation body lotion pH is maintained at 5.0～6.5, discharge opeing after dyeing；Water, reactive dye, sodium bicarbonate addition all with wet blue
On the basis of quality.
Step 7: stuffing: addition 100～the water of 250% in rotary drum, controlling temperature is 50～55 DEG C, is subsequently adding 10
～the fatting agent of 20%, rotating 90～120min, add the formic acid of 2.0～3.0%, the pH of regulation body lotion is 3.6～4.0,
Discharge opeing, add water after discharge opeing washing 10～30min, goes out drum and takes horse standing；Water, fatting agent, formic acid addition all with wet blue
On the basis of quality.
Step 8: be dried and finishing process is carried out according to common process.
In said method, the consumption of various reagent and water all on the basis of the quality of wet blue add, such as 1.5～
What the chrome tanning agent of 4.5% represented is consumption is wet blue quality the 1.5 of chrome tanning agent～the aldehyde tanning agent of 4.5%, 1～3% represent
Be consumption is wet blue quality the 1 of aldehyde tanning agent～the both sexes acroleic acid polymerization resin of 3%, 2～6% represent both sexes propylene
The consumption of acid copolymer resin is the 2 of wet blue quality～the water meter of 6%, 200～300% shows that the consumption of water is wet blue quality
200～300%, the consumption of other reagent also illustrates that such meaning.
Below by way of specific embodiment, the present invention will be further elaborated, it should be appreciated that, the description below is only
In order to explain the present invention, its content is not defined.Person skilled in art can be according to foregoing invention content to this
Some nonessential adjustment and improvement are made in invention.
In the present invention, each reagent used all can be commercially available from market.Such as, chrome tanning agent used is Chromitan
B (Basf company produces, and chromic oxide content is about 26%, and basicity is about 33%).Glutaraldehyde tanning agent is Relugan GT-50
(Basf company produces, and working substance content is about 50%, and pH is about 3.7).Modified glutaraldehyde tanning agent is Relugan GTW (Basf
Company produces, and working substance content is about 45%, and pH is about 7.0).Fatty aldehyde tanning agent is NOVALTAN PF (Zschimmer&
Schwarz company, working substance content is 45%, and pH is about 7.0).Both sexes acroleic acid polymerization resin is XELOREX F3000
(Basf company produce, effective ingredient is the both sexes acrylate copolymer rich in primary amino radical and carboxylate radical, structural formula as shown in formula I,
The equal molecular mass of number is 2000～30000, and vinyl amine construction unit mass fraction in both sexes acrylate copolymer is 40-
60%, solid content is about 20%, and pH is about 9.0).Neutralizing tannin is that (Lanxess company produces Tanigan PAK, and working substance contains
Amount is about 96%, and pH is about 6.8).Fatting agent used is that (Trumpler company produces Trupon OSL, and working substance content is about
93%, pH are about 7.0) and Tropon SWS (Trumpler company produces, working substance content about 78%, and pH is about 7.5).
In following examples of implementation, if no special instructions, the various reagent that added, water are all with the quality of wet blue as base
Accurate.
Embodiment 1
Utilize reactive dye that wet blue is dyeed, preparation dyeing crust leather, step is as follows:
(1) raw material skin is weighed: ox head layer wet blue, thickness 1.2mm.
(2) backwater.In rotary drum, add ox head layer wet blue, add the water of 250%, control water temperature 30 DEG C, be subsequently adding
The oxalic acid of 1.0%, paregal O-15 of 1.0%, regulation pH is 3.2～3.5, rotates 60min, discharge opeing.
(3) retanning.Adding 200% water in rotary drum, controlling temperature is 35 DEG C, is subsequently adding 2.5% chrome tanning agent
Chromitan B, rotates 30min, adds 2% glutaraldehyde tanning agent Relugan GT-50, rotates 1.5h, is eventually adding 2.5%
Sodium acetate, after rotating 3 hours, body lotion pH reaches 3.6-4.0, discharge opeing.
(4) neutralize.Crust leather after above-mentioned retanning being processed washes 15min, draining by normal-temperature water in rotary drum；It is subsequently adding
250% water, controls water temperature 40 DEG C, adds in 1.0% and tannin Tanigan PAK, 1.0% sodium bicarbonate, rotates 60min, bath
The pH of liquid reaches 5.0-6.0, discharge opeing；15min is washed the most again by normal-temperature water.
(5) resin retanning: add 150% water in rotary drum, controlling temperature is 35 DEG C, adds 2% both sexes acroleic acid polymerization
Resin, rotates 90min, discharge opeing.
(6) dyeing.Adding 100% water in rotary drum, controlling temperature is 50 DEG C, adds 3% reactive brilliant red k-2g, rotates
90min dyes, and divides 3-5 time in the period of dyeing and adds 1.5% sodium bicarbonate, and the pH of regulation body lotion is 5.0-6.5, dyeing knot
Discharge opeing after bundle.
(7) stuffing.Adding 150% water in rotary drum, controlling temperature is 50 DEG C, is subsequently adding the fatting agent Trupon of 8%
The fatting agent Tropon SWS of OSL and 8% rotates 90min, adds the formic acid of 3.0%, and the pH of regulation body lotion is 3.6-4.0,
Discharge opeing.Add water after discharge opeing washing 15min, goes out drum and takes horse standing.
(8) it is dried and finishing process is carried out according to common process.
Embodiment 2
Utilize reactive dye that wet blue is dyeed, preparation dyeing crust leather, step is as follows:
(1) raw material skin is weighed: U.S.'s cow split wet blue, thickness 1.2mm.
(2) backwater.In rotary drum, add cow split wet blue, add the water of 200%, control water temperature 35 DEG C, be subsequently adding
The oxalic acid of 1.0%, paregal O-15 of 1.5%, regulation pH is 3.2～3.5, rotates 90min, discharge opeing.
(3) retanning.Adding 100% water, controlling temperature is 30 DEG C, adds 3.5% chrome tanning agent Chromitan B, rotates
60min, adds 1.5% modified glutaraldehyde tanning agent Relugan GTW, rotates 1.5h, is eventually adding 2.0% sodium acetate, rotates 4
After hour, body lotion pH reaches 3.6-4.0, discharge opeing.
(4) neutralize.Crust leather after above-mentioned process is washed 10min, draining by normal-temperature water in rotary drum；It is subsequently adding
200% water, controls water temperature 40 DEG C, adds in 1.5% and tannin Tanigan PAK, and sodium bicarbonate 1.5% rotates 60min, body lotion
PH reach 5.0-6.5, discharge opeing；Then 20min is washed by normal-temperature water.
(5) resin retanning: add 100% water, controlling temperature is 30 DEG C, adds the both sexes acroleic acid polymerization resin of 3%,
Rotate 120min, discharge opeing.
(6) dyeing.Adding 150% water, controlling temperature is 50 DEG C, adds 4% Reactive Light Yellow K-4G, rotates 120min and carries out
Dyeing, simultaneously point 5 addition 1.5% sodium bicarbonate in dyeing course, the pH of regulation body lotion is 5.0-6.5, discharge opeing.
(7) stuffing.Adding 200% water, controlling temperature is 50 DEG C, adds 10% fatting agent Trupon OSL and 10% stuffing
Agent Tropon SWS rotates 90min, is subsequently adding the formic acid of 3.0%, and the pH of regulation body lotion is 3.6-4.0, discharge opeing；Add after discharge opeing
Normal-temperature water washing 20min, goes out drum and takes horse standing.
(8) it is dried and finishing process is carried out according to common process.
Embodiment 3
Utilize reactive dye that wet blue is dyeed, preparation dyeing crust leather, step is as follows:
(1) raw material skin is weighed: domestic sheep wet blue, thickness 1.0mm.
(2) backwater.In rotary drum, add wet blue, add the water of 300%, control water temperature 40 DEG C, be subsequently adding 1.5%
Formic acid, paregal O-15 of 1.0%, regulation pH is 3.2～3.5, rotates 60min, discharge opeing.
(3) retanning.Adding 100% water, controlling temperature is 40 DEG C, adds 1.5% chrome tanning agent Chromitan B, rotates
90min, adds 2.0% fatty aldehyde tanning agent NOVALTAN PF, rotates 1.5h, is eventually adding 1.5% sodium acetate, rotates 3 hours
After, body lotion pH reaches 3.6-4.0, discharge opeing.
(4) neutralize.Crust leather after above-mentioned process is washed 20min, draining by normal-temperature water in rotary drum；Add 250% water,
Control water temperature 35 DEG C, add in 2.0% and tannin Tanigan PAK, sodium bicarbonate 2.5%, rotate 90min, the pH of body lotion and reach
6.0-6.5, discharge opeing；Then normal-temperature water washing 30min.
(5) resin retanning: add 250% water, controlling temperature is 40 DEG C, adds the both sexes acrylate copolymer tree of 3.5%
Fat, rotates 90min, discharge opeing；
(6) dyeing.Adding 200% water, controlling temperature is 45 DEG C, adds 5% Reactive Turquoise Blue KN-G, rotates 120min and carries out
Dyeing, simultaneously point 5 addition 2.5% sodium bicarbonate during dyeing, the pH of regulation body lotion is 6.0-6.5, discharge opeing.
(7) stuffing.Adding 150% water, controlling temperature is 55 DEG C, adds 6% fatting agent Trupon OSL, 6% fatting agent
Tropon SWS rotates 120min, is subsequently adding the formic acid of 2.0%, and the pH of regulation body lotion is 3.6-4.0, discharge opeing；Use after discharge opeing
Normal-temperature water washing 30min, goes out drum and takes horse standing.
(8) it is dried and finishing process is carried out according to common process.
Embodiment 4
Dyeing crust leather is prepared, except for the difference that: raw material skin used is goat wet blue according to the method for embodiment 1.
Embodiment 5
Dyeing crust leather is prepared, except for the difference that: reactive dye used in step (6) are according to the method for embodiment 1
Reactive Light Yellow K-4G and the mixture of Reactive Turquoise Blue KN-G.
Embodiment 6
Dyeing crust leather is prepared, except for the difference that: raw material skin used in step 1 is Corii Sus domestica according to the method for embodiment 1
Wet blue.
Embodiment 7
Utilize reactive dye that wet blue is dyeed, preparation dyeing crust leather, step is as follows:
(1) raw material skin is weighed: with embodiment 2.
(2) backwater: with embodiment 2.
(3) retanning: add 150% water, controlling temperature is 30 DEG C, adds 4.5% chrome tanning agent Chromitan B, rotates
60min, adds 1% modified glutaraldehyde tanning agent Relugan GTW, rotates 1.5h, is eventually adding 2.0% sodium acetate, rotates 4 little
Shi Hou, body lotion pH reach 3.6-4.0, discharge opeing.
(4) neutralize: with embodiment 2.
(5) resin retanning: add 100% water, controlling temperature is 30 DEG C, adds the both sexes acroleic acid polymerization resin of 6%,
Rotate 60min, discharge opeing.
(6) dyeing.Adding 150% water, controlling temperature is 50 DEG C, adds 1% Reactive Light Yellow K-4G, rotates 150min and carries out
Dyeing, simultaneously point 5 addition 1.5% sodium bicarbonate in dyeing course, the pH of regulation body lotion is 5.0-6.5, discharge opeing.
(7) stuffing: with embodiment 2.
(8) it is dried and finishing process is carried out according to common process.
Embodiment 8
Dyeing crust leather is prepared, except for the difference that: the step of step (3) retanning is: add 100% according to the method for embodiment 2
Water, controlling temperature is 30 DEG C, adds 3.5% chrome tanning agent Chromitan B, rotates 60min, adds 1.11% glutaraldehyde tanning agent
Relugan GT-50,0.39% modified glutaraldehyde tanning agent Relugan GTW, rotate 4h, be eventually adding 2.0% sodium acetate, rotates
After 4 hours, body lotion pH reaches 3.6-4.0, discharge opeing.
Comparative example 1
Dyeing crust leather is prepared, except for the difference that: in step (5), the resin of resin retanning is solid according to the method for embodiment 1
Content is the acrylic acid-acrylamide copolymer aqueous solution of 10wt%.The equal molecule of number of acrylic acid-acrylamide copolymer used
Quality is 15000-25000, and (acrylic acid-acrylic acyl is prepared in plasma initiation can to use patent CN200910067685.0
The method of amine copolymer thing) disclosed in method prepare.
Comparative example 2
Dyeing crust leather is prepared, except for the difference that: in step (5), the resin of resin retanning is for containing according to the method for embodiment 1
Hydroxy acrylic acid ester aqueous dispersion, this aqueous dispersion uses the patent CN201110256265.4 (aqueous acrylamide of a kind of hydroxyl
Acid ester polymer and preparation method thereof) in method disclosed in embodiment 1 prepare.
Comparative example 3
Dyeing crust leather is prepared, except for the difference that: the step of step (3) retanning is: add 100% according to the method for embodiment 2
Water, controlling temperature is 30 DEG C, adds 3.5% chrome tanning agent Chromitan B, rotates 60min, adds 0.75% amino resins multiple
Tanning agent GDAR, 0.75% aromatic series tanning agent SCP, rotate 1.5h, be eventually adding 2.0% sodium acetate, after rotating 4 hours, and body lotion pH
Reach 3.6-4.0, discharge opeing.Wherein, the method that amino resins retanning agent GDAR uses Wang Xue river et al. to provide prepare (Wang Xuechuan,
Zhang Ting, the most torrential；The impact of content of formaldehyde in Retanning Agent on Leather is commonly used in process hides；Chinese leather；2015 (9): 6-9), aromatic series
Tanning agent SCP uses the method thanking to weighing apparatus et al. offer to prepare and (thanks weighing apparatus, Sun Qingyong, Liao Xuepin, Shi Bi；Formaldehydeless amino resins retanning
The application and research of agent GDAR；Chinese leather；13 phases in 2014).
Comparative example 4
Dyeing crust leather is prepared, except for the difference that: the both sexes acroleic acid polymerization resin of step (5) according to the method for embodiment 2
In, the content of acrylate copolymer shown in formula I is 40wt%, vinyl amine construction unit matter in both sexes acrylate copolymer
Amount mark is 80～90%, and the equal molecular mass of number is 40000～50000, purchased from Basf company.
Comparative example 5
Dyeing crust leather is prepared, except for the difference that: the stain used by step (6) is general acidic according to the method for embodiment 2
Dyestuff.
After crust leather natural drying prepared by above-described embodiment and comparative example, according to China's light industry standard QB/
T1808-1993, QB/T1327-1991 and GB/T3921-2008 measure resistance to dry, the wet rubbing fastness of each crust leather and water-fast
Washing property.Specific experiment the results are shown in Table 1.
The colorfastness of the crust leather that table 1 embodiment and comparative example prepare and water-wash resistance data
Result shows, the resistance to xerotripsis fastness utilizing the crust leather that the inventive method obtains is 5 grades, and moisture-proof rubbing fastness is 4-5 level,
Crust leather chromatic aberration after washing is little, and colorfastness is high.
Claims (10)
1. the method utilizing reactive dye to dye chrome tanning crust leather, is characterized in that: the wet blue of backwater is first used chromium
Tanning agent and aldehyde tanning agent carry out retanning, then carry out retanning with both sexes acroleic acid polymerization resin, then dye with reactive dye；
The effective ingredient of described both sexes acroleic acid polymerization resin is the both sexes acrylate copolymer rich in primary amino radical and carboxylate radical.
Method the most according to claim 1, is characterized in that: the described both sexes acroleic acid polymerization rich in primary amino radical and carboxylate radical
Shown in the following formula I of structural formula of thing, its equal molecular mass of number is 2000～30000, and vinyl amine construction unit is at both sexes propylene
Mass fraction in acid polymer is 30～70%；
。
Method the most according to claim 1 and 2, is characterized in that: in described both sexes acroleic acid polymerization resin, rich in primaquine
The content of the both sexes acrylate copolymer of base and carboxylate radical is 10～30wt%.
Method the most according to claim 1, is characterized in that specifically including following steps:
(1) wet blue after shaving is weighed, standby；
(2) backwater: wet blue is added in rotary drum, addition 200～the water of 300% in rotary drum, control water temperature 30～40 DEG C, so
Rear addition 1.0～the oxalic acid of 1.5% or formic acid, 1～paregal O-15 of 1.5%, regulation pH is 3.2～3.5, rotate 60～
90min, discharge opeing；Water, oxalic acid or formic acid, paregal O-15 addition all on the basis of the quality of wet blue；
(3) retanning: add 100～the water of 200% in rotary drum, controlling temperature is 30～40 DEG C, is subsequently adding 1.5～4.5%
Chrome tanning agent, rotates 30～90min, adds the aldehyde tanning agent of 1～3%, rotates 1～4 h, is eventually adding the acetic acid of 1.5～2.5%
Sodium, rotates 1～4 hour, and body lotion pH reaches 3.6～4.0, discharge opeing；Water, chrome tanning agent, aldehyde tanning agent, sodium acetate addition all with indigo plant
On the basis of the quality of wet skin；
(4) neutralize: the crust leather after retanning being processed washes 10～30min by normal-temperature water in rotary drum, draining；It is subsequently adding 200
～the water of 250%, control water temperature 30～40 DEG C, the neutralization tannin of addition 1.0～2.0 % and 1.0～the sodium bicarbonate of 2.5%, rotate
60～120min, body lotion pH reaches 5.0～6.5, discharge opeing；10～30min are washed the most again by normal-temperature water；Water, neutralize tannin, little
The addition of soda is all on the basis of the quality of wet blue；
(5) both sexes acroleic acid polymerization resin retanning: added in rotary drum by the crust leather after neutralisation treatment, adds 100～250%
Water, controlling temperature is 30～40 DEG C, is subsequently adding the both sexes acroleic acid polymerization resin of 2～6%, rotates 60～150min, row
Liquid；The addition of water and both sexes acroleic acid polymerization resin is all on the basis of the quality of wet blue；
(6) dyeing: the crust leather after both sexes acroleic acid polymerization resin retannings being processed is put in rotary drum, adds 100～200%
Water, controlling temperature is 45～50 DEG C, is subsequently adding the reactive dye of 0.5～6%, rotates 60～150min, simultaneously at dyeing course
In add 1.5～the sodium bicarbonate of 3.5% points for 3～5 times, regulation body lotion pH is maintained at 5.0～6.5, discharge opeing after dyeing；Water, activity dye
Material, sodium bicarbonate addition all on the basis of the quality of wet blue；
(7) stuffing: add 100～the water of 250% in rotary drum, controlling temperature is 50～55 DEG C, is subsequently adding 10～20% add
Fat agent, rotates 90～120min, adds the formic acid of 2.0～3.0%, and the pH of regulation body lotion is 3.6～4.0, and discharge opeing, after discharge opeing
Add water washing 10～30min, goes out drum and takes horse standing；Water, fatting agent, formic acid addition all on the basis of the quality of wet blue.
5. according to the method according to any one of claim 1-4, it is characterized in that: described chrome tanning agent is Chromitan B；Described
Aldehyde tanning agent is one or more in glutaraldehyde tanning agent, modified glutaraldehyde tanning agent and fatty aldehyde tanning agent.
Method the most according to claim 5, is characterized in that: described aldehyde tanning agent be mass ratio 10:3-5 glutaraldehyde tanning agent and
The mixture of modified glutaraldehyde tanning agent.
Method the most according to claim 6, is characterized in that: described aldehyde tanning agent be mass ratio 10:3.5 glutaraldehyde tanning agent and
The mixture of modified glutaraldehyde tanning agent.
8. according to the method according to any one of claim 1-5, it is characterized in that: described wet blue is pig wet blue, ox head layer
Wet blue, sheep wet blue, goat wet blue or cow split wet blue.
9. according to the method according to any one of claim 1-5, it is characterized in that: described reactive dye are that halo s-triazine is lived
One or more in property dyestuff and sulphuric acid vinyl-sulfone reactive dyes.
Method the most according to claim 9, is characterized in that: described reactive dye are reactive brilliant red k-2g, reactive brilliant yellow K-
One or more in 4G and activity kingfisher orchid KN-G.
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| CN110396837A (en) * | 2019-07-31 | 2019-11-01 | 焦作隆丰皮草企业有限公司 | A kind of preparation process of colouring method and the Tuscany leather using this method |
| JPWO2021145188A1 (en) * | 2020-01-14 | 2021-07-22 | ||
| CN115558725A (en) * | 2022-09-29 | 2023-01-03 | 焦作隆丰皮草企业有限公司 | Process for improving illumination resistance of wool surface of shorn sheepskin product |
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| CN105384883A (en) * | 2015-12-25 | 2016-03-09 | 上海金狮化工有限公司 | Method for preparing amphoteric retanning agent |
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| EP0795613A1 (en) * | 1996-03-11 | 1997-09-17 | Rohm And Haas Company | Method of treating leather with amphoteric polymers |
| CN104927395A (en) * | 2015-05-28 | 2015-09-23 | 齐鲁工业大学 | Modification method for reactive dye for leather |
| CN105384883A (en) * | 2015-12-25 | 2016-03-09 | 上海金狮化工有限公司 | Method for preparing amphoteric retanning agent |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110396837A (en) * | 2019-07-31 | 2019-11-01 | 焦作隆丰皮草企业有限公司 | A kind of preparation process of colouring method and the Tuscany leather using this method |
| CN110396837B (en) * | 2019-07-31 | 2022-04-22 | 焦作隆丰皮草企业有限公司 | Dyeing method of toscarna leather |
| JPWO2021145188A1 (en) * | 2020-01-14 | 2021-07-22 | ||
| CN113939603A (en) * | 2020-01-14 | 2022-01-14 | 美多绿汽车皮革株式会社 | Method for producing leather |
| JP7116850B2 (en) | 2020-01-14 | 2022-08-10 | ミドリオートレザー株式会社 | leather manufacturing method |
| CN115558725A (en) * | 2022-09-29 | 2023-01-03 | 焦作隆丰皮草企业有限公司 | Process for improving illumination resistance of wool surface of shorn sheepskin product |
| CN115558725B (en) * | 2022-09-29 | 2024-01-09 | 隆丰革乐美时尚有限公司 | Process for improving illumination resistance of wool surface of sheep sheared product |
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