CN105907900B - It is a kind of based on vegetable tanning agent without chrome retanned cattle hide upper leather clean method for producing - Google Patents

Abstract

The present invention relates to tanning chemistries and field of engineering technology, there is provided it is a kind of based on vegetable tanning agent without chrome retanned cattle hide upper leather technology, with the white wet leather of more tanned oxes of metal combination tanning agent for raw material skin, using the collocation of various plants tannin extract, to ox, wet leather carries out the processing of retanning filling twice in vain, and novel green chrome-free tanning agent is added in after retanning and further carries out tannin extract fixation and stuffing processing；Without using chrome tanning agent in implementation process, the vividness of colored crust leather will not be influenced because of the color of tannin extract in itself even with a large amount of vegetable tanning agent, production technology simply easily realizes that production cost is appropriate, is suitble to produce in enormous quantities;Upper leather Chrome-free, formaldehydeless as obtained by making the production technology, shrinkage temperature >=90 DEG C, tear edge >=40N, with good gas permeability and permeable gas, crust leather color uniformly full, tone it is bright-coloured it is beautiful, color fastness is high, the every physico performance of crust leather is satisfied by professional standard, and properties for follow is good.

Description

It is a kind of based on vegetable tanning agent without chrome retanned cattle hide upper leather clean method for producing

Technical field

It is more particularly to a kind of yellow without chrome retanned based on vegetable tanning agent the present invention relates to tanning chemistry and field of engineering technology Bovine cerebellum clean method for producing.

Background technology

The reserves of China's chromium are fewer and fewer, are not enough to go around, and raw material skin has 20- during tanning and retanning 30% chromium cannot be its absorption and utilization, discharged with sewage, cause the pollution of environment and the waste of vast resources, and After joining WTO since China, more focus on environmental protection and environmental quality, therefore taken in leather production and environment Harmonious, environment amenable Leather Chemicals（That is green material）And technology（Clean micronizing technology）, increasingly It attracts attention and supports, the research of leather chrome-free tanning and Chrome-free retanning Technology is the inexorable trend of future development.

In conclusion exploitation chrome-free tanning and no chrome retanned new technology are industry research hot spots, it is clean leather-making technology Important component and leather industry sustainable development one of key point.

Invention content

Therefore, for it is above-mentioned the problem of, the present invention provide it is a kind of clear without chrome retanned cattle hide upper leather based on vegetable tanning agent Clean production method, it is described based on vegetable tanning agent without not making in chrome retanned cattle hide upper leather clean method for producing implementation process With chrome tanning agent, the bright-coloured of colored crust leather will not be influenced because of the color of tannin extract in itself even with a large amount of vegetable tanning agent Degree, production technology simply easily realize that production cost is appropriate, are suitble to produce in enormous quantities；And as obtained by making the production technology Upper leather Chrome-free, formaldehydeless, shrinkage temperature >=90 DEG C, tear edge >=40N have good gas permeability and permeable gas, crust leather Color uniformly full, tone it is bright-coloured it is beautiful, color fastness is high, the every physico performance of crust leather is satisfied by professional standard, and follow-up Processing performance is good.

To realize above-mentioned technical problem, the solution taken of the present invention is：It is a kind of based on vegetable tanning agent without chrome retanned Cattle hide upper leather clean method for producing, in turn includes the following steps：

Step 1 will carry out conventional water squeezing stretching, extension, shaving processing without the white wet leather of chrome tanning ox, weigh white wet leather after shaving Weight, the component of agents useful for same is determined by the percentage of the weight in subsequent treatment process step；

Step 2, rinsing tempering：In rotary drum add in 30-32 DEG C, the water of 200-250%, 1.0-1.5% rinse aid, The oxalic acid of 1.5-2.0% rotates 90-120min, then solution ph 3.0-3.2 exhausts solution, and washing is primary；

Step 3 neutralizes：30-32 DEG C, the water of 100-150% are added in rotary drum, the glutaraldehyde tanning agent of 1.5-2.0% turns Dynamic 60min, then exhausts solution, then adds in rotary drum 30-32 DEG C, the water of 100-150%, the sulfurous acid of 1.0-1.5% Sodium, the neutralizing retanning agent of 1.0-1.5% rotate 30-40min, then solution ph 4.1-4.2 exhausts solution, wash Once；

Step 4, retanning filling：30-32 DEG C, the water of 80-100% are added in rotary drum, the low pH retannings of 1.0-1.5% are pre- Inorganic agent, the substituted type syntans of 2.0-3.0%, 1.0-2.0% modification wattle extract, rotate 30-40min, add The acrylic acid of 2.0-3.0% and styrol copolymer, the synthetic polymer softening agent of 2.0-3.0%, 2.0-3.0% acrylic acid Polymer rotates 60-90min, adds the quebracho extract of 8.0-10%, the wattle extract of 5.0-6.0%, 2.0-3.0% Er Qiang base Er Ben Sulfone classes syntans, 4.0-5.0% substituted type syntans, rotate 60-90min, add 4.0- 5.0% modification wattle extract, the modification chestnut extract of 4.0-5.0%, the protein filling of 3.0-4.0%, 2.0-3.0% Acrylic acid and styrol copolymer, the styrene maleic anhydride copolymer of 2.0-3.0%, 1.0-2.0% lanolin fatting agent, 60-90min is rotated, adds the both sexes melamine of 2.0-3.0%, rotates 20-30min, then keeps turning 2min, stop The working condition that 40min is constantly recycled is to next day;

Step 5 is fixed：Next day add in 2.0-3.0% more metal combination tanning agents, rotate 60-90min, add 50-52 DEG C, The water of 150-200% rotates 5-10min, adds in the formic acid of 0.5-1.0%, rotates 20-30min, add in 0.3-0.5% oxalic acid, The iron removing reagent of 0.3-0.5%, the EDTA of 0.2-0.5% rotate 20-30min, then exhaust solution, and washing is primary；

Step 6, dyeing and fat-liquoring：30-32 DEG C, the water of 80-100% are added in rotary drum, adds in the dyestuff of 2.0-3.0%, is turned Dynamic 30-40min adds 50-52 DEG C, the water of 100-150%, add in the lanolin of 1.0-1.5%, the life neat's foot oil of 1.0-1.5%, The self-emulsifying neat's foot oil of 2-3%, the acrylic acid of 2-3% are mixed with styrol copolymer, the sulphation neat's foot oil of 1-2% and sperm oil Object is closed, rotates 40-60min, adds the formic acid of 0.5-1.0%, 30-40min is rotated, washes out drum；

Step 7, conventional final finishing.

It is further：The white wet leather of the no chrome tanning ox is obtained by more metal combination tanning agent tannings.

It is further：More metal combination tanning agents are matched for the Zirconium-aluminum-titanium of Jin Kun Chemical Co., Ltd.s of Mianzhu City production Conjunction tanning agent (but China is defended, but time, Zirconium-aluminum-titanium multi-metal complex pulvis such as vast stretch of wooded country and preparation method thereof China Patent No.： ZL 200710048440)。

It is further：Low pH retannings pretreating agent is the Sai Latan of De Rui leather technologies Co., Ltd in the step 4 AR（pH≤1.5）；The acrylic acid and the MS that styrol copolymer is the strange chemical companies of Race；The synthetic polymer softening agent is The SYNTHOL GS606 of Smit chemical companies.

By using preceding solution, the beneficial effects of the invention are as follows：

1st, it is described based on vegetable tanning agent without not used in chrome retanned cattle hide upper leather clean method for producing implementation process Chrome tanning agent or containing chrome tanning agent, not only alleviates environmental pollution, eliminates harm of the Cr VI to human body, and reduce and be produced into This；And the production technology process reasonable design, the phenolic hydroxyl group in tannin molecule combined with collagenous fibres with hydrogen bond formation after also Complex can be formed with polyvalent metal ion, change tannin extract chromatography, while these metal ions can also be with adjacent collagen peptide Carboxyl in chain side group is complexed, and not only increases the dye-uptake of dyestuff, also improves the dyefastness of dyestuff, and changes The tone of tannin extract, widened spectral range, therefore, will not be because of tannin extract in itself even with a large amount of vegetable tanning agent Color and the vividness for influencing colored crust leather；It is described based on vegetable tanning agent without chrome retanned cattle hide upper leather clean method for producing Production technology simply easily realizes that production cost is appropriate, is suitble to produce in enormous quantities.

2nd, processing is fixed using more metal combination tanning agents after retanning filling, more metal combination tanning agents are by a variety of Metal ion complexation forms, and more metals have collaboration tanning effect, and more metal combination tanning agents are added in after a large amount of tannin extract retanning fillings, More stable cross-linked structure can not only be formed between tropocollagen molecule, but also can be with vegetable extract molecule with coordinate bond and ionic bond Form recombines, and can not only promote the absorption of vegetable extract, and strengthens the binding strength of vegetable extract and collagen, makes Obtaining crust leather has more preferably dyefastness, and follow-up fatting agent dosage is few also still to make finished leather softness excellent.

3rd, the upper leather as obtained by being made based on vegetable tanning agent without chrome retanned cattle hide upper leather clean method for producing Chrome-free, formaldehydeless, shrinkage temperature >=90 DEG C, tear edge >=40N have good gas permeability and permeable gas, colored crust leather face Color uniformly full, tone it is bright-coloured it is beautiful, color fastness is high, the every physico performance of crust leather is satisfied by professional standard, and it is follow-up plus Work is functional.

Specific embodiment

Carry out the embodiment that the present invention will be described in detail below with reference to specific embodiment, how skill is applied to the present invention whereby Art means solve technical problem, and the realization process for reaching technique effect can fully understand and implement according to this.If it does not refer in particular to Conventional means bright, that the technological means employed in embodiment is well known to those skilled in the art, used reagent and production Product are also available commercial.The various processes and method not being described in detail are conventional methods as known in the art, used The source of reagent, trade name and it is necessary to list its constituent person, are indicated on the first appearance.

It is a kind of based on vegetable tanning agent without chrome retanned cattle hide upper leather clean method for producing, in turn include the following steps：

Step 1 will carry out conventional water squeezing stretching, extension, shaving processing without the white wet leather of chrome tanning ox, weigh white wet leather after shaving Weight, the component of agents useful for same is determined by the percentage of the weight in subsequent treatment process step；

Step 2, rinsing tempering：30 DEG C of addition, 250% water, 1.0% rinse aid in rotary drum（The auspicious leather chemical industry of moral The Borron SAF of company）, 2.0% oxalic acid（Regular industrial oxalic acid）, 120min, solution ph 3.0-3.2 are rotated, then Solution is exhausted, washing is primary；

Step 3 neutralizes：30 DEG C of addition, 150% water in rotary drum add in 2.0% glutaraldehyde tanning agent (BASF The Relugan GT50 of work company）, 60min is rotated, then exhausts solution, then 30 DEG C of addition, 150% water in rotary drum, Add in 1.5% sodium sulfite（Regular industrial sodium sulfite）, 1.5% neutralizing retanning agent（Lang Sheng Chemical Co., Ltd.s PAK-S）, 35min is rotated, then solution ph 4.1-4.2 exhausts solution, washing is primary；

Step 4, retanning filling：30 DEG C of addition, 100% water in rotary drum add in 1.5% low pH retannings pretreating agent （The Sai Latan AR of De Rui leather technologies Co., Ltd）, 2.0% substituted type syntans（Lang Sheng Chemical Co., Ltd.s TANIGAN BN）, 2.0% modification wattle extract（The Unitan ME of You Nite companies), 30min is rotated, adds in 2.0% Acrylic acid and styrol copolymer（The MS of the strange chemical companies of Race）, 2.0% synthetic polymer softening agent（Smit chemical companies SYNTHOL GS606）, 2.0% acrylate copolymer（The LEUKOTAN 8090 of Lang Sheng Chemical Co., Ltd.s）, rotation 60min adds in 8.0% quebracho extract（The ATO of UNITAN）, 5.0% wattle extract（The Unitan of You Nite companies FS）, 2.0% Er Qiang base Er Ben Sulfone class syntanses（The BLANCOTAN BC of Shi Hua Science and Technology Ltd.s）, 4.0% replacement Type syntans（The TANIGAN BN of Lang Sheng Chemical Co., Ltd.s）, 60min is rotated, adds in 5.0% modification wattle extract （The Unitan ME of You Nite companies), 5.0% modification chestnut extract（The KPS of UNITAN）, 3.0% protein filling (Xiamen The SD of ten thousand tonneau chemical companies), 2.0% acrylic acid and styrol copolymer（The MS of the strange chemical companies of Race）, 2.0% benzene second Alkene copolymer-maleic anhydride (the TANINTAN OT-Z of Ming Zhong Chemical Co., Ltd.s), 1.0% lanolin fatting agent (the LIKERSOL ZBN of Biokimica) rotates 60min, adds 2.0% both sexes melamine（The limited public affairs of many chemical industry of inscription The TANINTAN RX-L of department）, 20min is rotated, then keeps turning 2min, stops working condition that 40min constantly recycles to next day;

Step 5 is fixed：Next day adds in 2.0% more metal combination tanning agents, rotates 60min, adds 50 DEG C, 200% water, 8min is rotated, adds in 1.0% formic acid（Regular industrial formic acid）, 20min is rotated, adds in 0.5% oxalic acid, 0.3% iron removing reagent （The TANINAUX CL of Ming Zhong Chemical Co., Ltd.s）, 0.2% EDTA（Zhejiang Shenghui Chemical Industry Co., Ltd）, 20min is rotated, so Solution is exhausted afterwards, washing is primary；

Step 6, dyeing and fat-liquoring：30 DEG C of addition, 100% water in rotary drum add in 3.0% dyestuff, rotate 35min, mend Add 50 DEG C, 150% water, add in 1.0% lanolin (the LIKERSOL ZBN of Biokimica), 1.0% life neat's foot oil（De Rui The auspicious treasured ICA of leather of leather technology Co., Ltd）, 3% self-emulsifying neat's foot oil（The BITOIL OPE of Tag Chemical Co., Ltd.）、 2% acrylic acid and styrol copolymer（The MS of the strange chemical companies of Race）, 2% sulphation neat's foot oil and the mixture of sperm oil （The 178 of Atlas company）, 40min is rotated, adds 0.5% formic acid, 30min is rotated, washes out drum；

Step 7, conventional final finishing：Take --- water squeezing stretching, extension --- vacuum drying --- extension dries dry --- oscillation of horse standing It draws soft.

As it is above-mentioned based on vegetable tanning agent without chrome retanned cattle hide upper leather clean method for producing make obtained by vamp Chrome-free, formaldehydeless, shrinkage temperature >=90 DEG C are removed from office, tear edge >=40N has good gas permeability and permeable gas, colored crust leather Color uniformly full, tone it is bright-coloured it is beautiful, color fastness is high, the every physico performance of crust leather is satisfied by professional standard, and follow-up Processing performance is good.

It is described based on vegetable tanning agent without in chrome retanned cattle hide upper leather clean method for producing implementation process do not use chromium Tanning agent will not influence the vividness of colored crust leather even with a large amount of vegetable tanning agent because of the color of tannin extract in itself, Production technology simply easily realizes that production cost is appropriate, is suitble to produce in enormous quantities.

The foregoing descriptions are merely the embodiment using this origination techniques content, any those skilled in the art use this wound Make done modifications and changes, all belong to the scope of the claims of this creation opinion, and be not limited to those disclosed embodiments.

Claims (2)

1. it is a kind of based on vegetable tanning agent without chrome retanned cattle hide upper leather clean method for producing, which is characterized in that include successively Following steps：

Step 1 will carry out conventional water squeezing stretching, extension, shaving processing without the white wet leather of chrome tanning ox, weigh the weight of white wet leather after shaving, The component of agents useful for same is determined by the percentage of the weight in subsequent treatment process step；

Step 2, rinsing tempering：30-32 DEG C of addition, the water of 200-250%, the rinse aid of 1.0-1.5%, 1.5- in rotary drum 2.0% oxalic acid rotates 90-120min, then solution ph 3.0-3.2 exhausts solution, and washing is primary；

Step 3 neutralizes：30-32 DEG C, the water of 100-150%, the glutaraldehyde tanning agent of 1.5-2.0%, rotation are added in rotary drum Then 60min exhausts solution, then 30-32 DEG C, the water of 100-150%, the sulfurous acid of 1.0-1.5% are added in rotary drum Sodium, the neutralizing retanning agent of 1.0-1.5% rotate 30-40min, then solution ph 4.1-4.2 exhausts solution, wash Once；

Step 4, retanning filling：Add in 30-32 DEG C, the water of 80-100% in rotary drum, the retanning pretreating agent of 1.0-1.5%, The substituted type syntans of 2.0-3.0%, the modification wattle extract of 1.0-2.0% rotate 30-40min, add 2.0- 3.0% acrylic acid and styrol copolymer, the synthetic polymer softening agent of 2.0-3.0%, 2.0-3.0% acroleic acid polymerization Object, rotate 60-90min, add the quebracho extract of 8.0-10%, the wattle extract of 5.0-6.0%, 2.0-3.0% two The substituted type syntans of Qiang base Er Ben Sulfone classes syntans, 4.0-5.0% rotates 60-90min, adds 4.0-5.0%'s Modified wattle extract, the modification chestnut extract of 4.0-5.0%, the protein filling of 3.0-4.0%, 2.0-3.0% acrylic acid with Styrol copolymer, the styrene maleic anhydride copolymer of 2.0-3.0%, 1.0-2.0% lanolin fatting agent, rotate 60- 90min adds the both sexes melamine of 2.0-3.0%, rotates 20-30min, then keeps turning 2min, stops 40min and constantly follow The working condition of ring is to next day;

Step 5 is fixed：Next day adds in more metal combination tanning agents of 2.0-3.0%, rotates 60-90min, adds 50-52 DEG C, 150- 200% water rotates 5-10min, adds in the formic acid of 0.5-1.0%, rotates 20-30min, adds in oxalic acid, the 0.3- of 0.3-0.5% 0.5% iron removing reagent, the EDTA of 0.2-0.5% rotate 20-30min, then exhaust solution, and washing is primary；

Step 6, dyeing and fat-liquoring：30-32 DEG C, the water of 80-100% are added in rotary drum, adds in the dyestuff of 2.0-3.0%, rotation 30-40min adds 50-52 DEG C, the water of 100-150%, adds in the lanolin of 1.0-1.5%, life neat's foot oil, the 2- of 1.0-1.5% 3% self-emulsifying neat's foot oil, the acrylic acid of 2-3% and styrol copolymer, the sulphation neat's foot oil of 1-2% and the mixing of sperm oil Object rotates 40-60min, adds the formic acid of 0.5-1.0%, rotates 30-40min, washes out drum；

Step 7, conventional final finishing.

2. it is according to claim 1 based on vegetable tanning agent without chrome retanned cattle hide upper leather clean method for producing, it is special Sign is：The white wet leather of the no chrome tanning ox is obtained by more metal combination tanning agent tannings.