CN109628654A - A kind of manufacture craft that water proof type is removed from office without chromed tanned leather - Google Patents
A kind of manufacture craft that water proof type is removed from office without chromed tanned leather Download PDFInfo
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- CN109628654A CN109628654A CN201811543748.0A CN201811543748A CN109628654A CN 109628654 A CN109628654 A CN 109628654A CN 201811543748 A CN201811543748 A CN 201811543748A CN 109628654 A CN109628654 A CN 109628654A
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/02—Fleshing, unhairing, samming, stretching-out, setting-out, shaving, splitting, or skiving skins, hides, or leather
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/40—Softening or making skins or leather supple, e.g. by staking, boarding, or crippling machines, by dry mills
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/58—Drying
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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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
-
- 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
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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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
- C14C3/08—Chemical tanning by organic agents
-
- 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
- C14C3/28—Multi-step processes
-
- 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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
-
- 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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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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
-
- 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
Abstract
The present invention relates to the technical field of manufacturing process of leather, a kind of manufacture craft that water proof type is removed from office without chromed tanned leather is provided, tanning in conjunction with first carrying out not pickling Chrome-free with more metal combination tanning agents using organic silicon modified polyurethane resin, organic synthesis tanning agent, more metal combination tanning agents are recycled to carry out without chrome retanned and fixation, it is filled using waterproof polymer and waterproof currying agent and stuffing, gained has excellent waterproofness without chromed tanned leather leather, and has both good physicochemical property and properties for follow simultaneously；The technique is in implementation process using no ammonia deashing and softening together bath, not pickling Chrome-free combination tanning, without the clearer production technologies such as chrome retanned and Chrome-free fixation, prepared water proof type Chrome-free leather green ecological environmental protection, waterproof performance is excellent, and the pollution of heavy metal chromium is eliminated from source, process flow is simple, it is practical, it is suitble to industrial application.
Description
Technical field
The present invention relates to tanning chemistry and field of engineering technology, in particular to production work that a kind of water proof type is removed from office without chromed tanned leather
Skill.
Background technique
All the time, domestic and international leather manufacture mainly uses chrome tanning, and resulting chromate waste water, contains solid waste containing chromium
Chromium discards the pollutions of chromium such as leather and fur products and brings serious pollution to environment, this problem has become restriction leather industry and continues
The technical bottleneck of development.Therefore, many developed countries will all develop Chrome-free Ecology Leather manufacturing technology as leather work in the world
The most important developing direction of industry, and Chrome-free leather manufacture technology is also classified as the key technology of " made in China 2025 " by China.Through
It crosses vast process hides worker constantly to explore for many years, has been developed for a variety of nothings such as organic tan, vegetable tanning, non-chromium metal tan
Chrome tanning technology, but leather obtained by every kind of tannage has a shortcoming, such as organic tanning is not thermo-labile, washable, vegetable leather with
Zirconium tanned leather plate is not firmly soft etc..Therefore, for exploitation mating type without chrome tanning technology, preparing novel non-chrome tanning leather has important show
Sincere justice.
Other than no chromed tanned leather leather, functional leather is other one big hot spot direction of current leather industry research.Care for name
Think justice, function leather is exactly leather on the basis of meeting traditional performance, with certain characteristic functions or performance, wherein just wrapping
Include Waterproof leather.Currently, the research of Waterproof leather is more, but is substantially based on chrome tanning wet blue leather, subsequent hygrometric state
Its waterproofness is assigned in dyeing and finishing, and is fixed using chrome tanning agent or chromate-containing materials, but since the addition of waterproof material is to leather
Physical mechanical property and organoleptic properties bring negative effect, and this problem is not well solved still.Therefore, it develops
A kind of having a good application prospect without chromed tanned leather leather with excellent waterproofness.
Summary of the invention
Therefore, for above-mentioned problem, the present invention proposes a kind of manufacture craft that water proof type is removed from office without chromed tanned leather, and first using has
Machine silicon modified polyurethane resin, the tanning in conjunction with more metal combination tanning agents progress Chrome-free of organic synthesis tanning agent, recycle more metals
Cooperate tanning agent to carry out without chrome retanned and fixation, select to have the waterproof polymer of waterproof action and waterproof currying agent be filled and
Stuffing, and waterproofness collocation design and adjustment are carried out to tanning and hygrometric state dyeing and finishing, finally prepare the nothing with excellent waterproofness
Chrome tanning leather, and have both good physicochemical property and properties for follow simultaneously；In addition, the technique uses nothing in implementation process
Ammonia deashing and softening with bath, not pickling Chrome-free combination tanning, without the clearer production technologies such as chrome retanned and Chrome-free fixation, it is prepared to prevent
The green ecological environmental protection of water type Chrome-free leather, waterproof performance is excellent, and the pollution of heavy metal chromium, process flow are eliminated from source
Simply, practical, it is suitble to industrial application.
To realize above-mentioned technical problem, a kind of solution that the present invention takes are as follows: production that water proof type is removed from office without chromed tanned leather
Technique successively comprises the technical steps that: grey pelt fleshing, weighing → deliming → softening → chrome-free tanning → standing, squeezes split
→ final finishing is fixed in water, shaving, weighing → rewetting → without chrome retanned → neutralization → filling → dyeing → stuffing → Chrome-free；Wherein,
The deliming, softening process use same bath process, the deliming, softening same bath process in be added without ammonia deliming agent, soft without ammonia
Change enzyme and carries out deashing and softening；
The chrome-free tanning process uses not pickling Chrome-free combination process for tanning, the not pickling Chrome-free combination process for tanning
Middle addition organic silicon modified polyurethane resin, organic synthesis tanning agent, more metal combination tanning agents carry out Chrome-free combination tanning；
Be added in the Chrome-free retanning procedures more metal combination tanning agents, glutaraldehyde tanning agent, amphoteric amine resin tanning agent etc. into
Row is without chrome retanned；
The filling, dyeing, stuffing process use same bath process, and the filling is dyed, is added in the same bath process of stuffing
Acrylate resin tanning agent, waterproof polymer, vegetable extract, amino resin tanning agent, dyestuff, waterproof currying agent are filled, dye
And stuffing；
Aluminium tanningagent is added in the Chrome-free fixed step, more metal combination tanning agents carry out Chrome-free and fix.
Further, reagent dosage is with the percentages of the grey pelt weight of split back layer, the deliming, softening are the same as bath
Technique are as follows: be added in rotary drum 28-30 DEG C water 50-100%, 1-3% without ammonia deliming agent, rotate 60-90min, be added
0.1-0.5% without ammonia macerating enzyme, rotate 30-60min, check that buttocks notch is in uniform colorless state, terminal bath foam with phenolphthalein
PH is 7.5-8.5, drain, washing.
Further, reagent dosage is with the percentages of the grey pelt weight of split back layer, the not pickling Chrome-free knot
Close process for tanning are as follows: the anti-strand agent of 25-30 DEG C water 20-50%, 0.1-0.2% are added in rotary drum, rotates 10min；It is added
The organic silicon modified polyurethane resin of 1-2% rotates 60min；The organic synthesis tanning agent of 3-6% is added, rotates 120min；It is added
More metal combination tanning agents of 5-15% rotate 180min, then turn 5min, stop 55min, repeat 5-8 times；0.1-0.5% is added
Automatic alkali extracting agent, rotate 180min, adjust bath foam pH to 3.8-4.2；It adds the hot water of 100-150% in two times again, adjusts
Bath temperature rotates 120min to 40-42 DEG C, and drain is roused out.
Wherein, the organic synthesis tanning agent is Granofin Easy F-90, and more metal combination tanning agents are zirconium-aluminium-
Titanium cooperates at least one of tanning agent, iron-zirconium-aluminium cooperation tanning agent, zirconium-aluminium-silicon cooperation tanning agent.
Further, reagent dosage is with the percentages without the white wet leather weight of chrome tanning after shaving, the no chrome retanned work
Skill are as follows: 25-30 DEG C of water 50-100% is added in rotary drum, the formic acid of 0.5-1% is added, rotates 30min, adjust bath foam pH to
3.0-3.2；The glutaraldehyde tanning agent of 1-2% is added, rotates 30min；More metal combination tanning agents of 5-10%, rotation is added
120min；The sodium formate of 1-2% is added, rotates 60min；The sodium bicarbonate of addition 0.5-1.0% in three times, every minor tick 30min,
Adjust bath foam pH to 3.8-4.2；The amphoteric amine resin tanning agent of 1-3% is added, rotates 60min, drain, washing.
Further, reagent dosage with after shaving without chrome tanning it is white it is wet leather weight percentages, it is described filling, dyeing,
The same bath process of stuffing are as follows: 25-30 DEG C of water 30-50% is added in rotary drum, the waterproof polymer of 3-6%, the propylene of 2-4% is added
Acid resin tanning agent rotates 60min；The waterproof currying agent of 1-3% is added, rotates 40min；The amino resin tanning agent of addition 4-8%,
The vegetable extract of 2-6%, the both sexes acrylate copolymer tanning agent of 2-4%, 1-3% dyestuff, rotate 120min, detection buttocks cut
Mouth dyestuff full impregnated；The silane crosslinker of 1-2%, the waterproof currying agent of 6-10% is added, rotates 90min；It is added 100-150%'s
50-60 DEG C of hot water rotates 60min；The formic acid of points of 4 times addition 1.5-3%, every minor tick 20-30min, adjust bath foam pH to
3.5-3.7, drain, washing.
Wherein, the waterproof polymer is water proof type organosilicon polymer, at least one in water proof type acrylate copolymer
Kind；The amino resin tanning agent is at least one of Lauxite, melamine resin, dicyandiamide resin；The plant evergreen chinquapin
Glue is at least one of chestnut extract, tara mimosa extract；The waterproof currying agent is siliceous waterproof currying agent, synthesis waterproof stuffing
At least one of agent, content of wax waterproof currying agent.
Further, reagent dosage is with the percentages without the white wet leather weight of chrome tanning after shaving, the Chrome-free regular worker
Skill are as follows: 35-40 DEG C of water 200-250% is added in rotary drum, the aluminium tanningagent of 1-2% is added, rotates 30min；The anti-of 1-2% is added
Water fatting agent rotates 30min；More metal combination tanning agents of 3-6% are added, rotate 90min；The waterproof stuffing of 0.5-1% is added
Agent, rotates 20min, and drain is washed 2 times, roused out.
Further, the finishing process include take horse standing → water squeezing stretching, extension → vacuum drying → extension dry it is dry →
It is soft to vibrate drawing, wherein in 20-30%, extension dries dry rear crust leather moisture and controls in 8-12% the control of crust leather moisture after vacuum drying.
By using preceding solution, the beneficial effects of the present invention are: the production work that the water proof type is removed from office without chromed tanned leather
Skill, first using organic silicon modified polyurethane resin, the tanning in conjunction with more metal combination tanning agents progress Chrome-free of organic synthesis tanning agent, then
Be filled and add using waterproof polymer and waterproof currying agent without chrome retanned and fixation using more metal combination tanning agents
Rouge, gained has excellent waterproofness without chromed tanned leather leather, and has both good physicochemical property and properties for follow simultaneously；
The manufacture craft that the water proof type is removed from office without chromed tanned leather is in implementation process using no ammonia deashing and softening with bath, not pickling
Chrome-free combination tanning fixes clearer production technology with bath and Chrome-free without chrome retanned, packed dyeing stuffing, eliminates pickling operation,
And the pollution of heavy metal chromium is eliminated from source, ammonia nitrogen and chloride ion contamination is greatly lowered, simplification of flowsheet, contracting can be dropped
Short production cycle and low pollution treatment cost have significant economic benefit and environmental benefit.
In conclusion the water proof type Chrome-free leather that the water proof type is prepared without the manufacture craft that chromed tanned leather is removed from office, green
Ecological, environmental protective, waterproof performance is excellent, and organoleptic properties and Physical Mechanical are able to satisfy Industry code requirements, fabrication processing letter
It is single, it is easy to operate, it is practical, it is suitble to industrialization production application.
Specific embodiment
The present invention is specifically described below by specific embodiment, whereby to the present invention how applied technology method
Technical problem is solved, and the realization process for reaching technical effect can fully understand and implement, it is necessary to indicated herein
It is that the present embodiment is served only for that invention is further explained, should not be understood as limiting the scope of the invention, the neck
The person skilled in the art in domain can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
Unless otherwise specified, the conventional hand that technological means employed in embodiment is well known to those skilled in the art
Section, used reagent and product are also available commercial.The various processes and method being not described in detail are in this field
Well known conventional method, the source of agents useful for same, trade name and it is necessary to list its constituent person, on the first appearance
It indicates.
A kind of manufacture craft that water proof type is removed from office without chromed tanned leather, comprises the technical steps that:
Step 1 soaks to ox raw material skin, liming, fleshing, split processing, preparation softening pelt, and after weighing split
Head layer ash pelt weight；
Step 2, deliming, softening are with bath (percentages for the head layer ash pelt weight that reagent dosage is weighed with step 1):
Being added without ammonia deliming agent (DLY of Ting Jiang new material company), rotation 60min for 30 DEG C of water 80%, 2% is added in rotary drum
0.3% without ammonia macerating enzyme the U5 of chemical company (desai your), rotate 40min, check that buttocks notch is in uniform colorless with phenolphthalein
State, terminal bath foam pH are 8.0, drain.
Step 3, chrome-free tanning (percentages for the head layer ash pelt weight that reagent dosage is weighed with step 1): in rotary drum
The anti-strand agent (TJ-A9626 of Ting Jiang new material company) of the interior water 30%, 0.1% for being added 25 DEG C, rotates 10min；It is added
1.5% organic silicon modified polyurethane resin (KT 4031 of Kate's new material company) rotates 60min；Be added 4% it is organic
Syntans (F-90 of this tal fibre chemical company) rotates 120min；12% more metal combination tanning agents (female chemical industry public affairs of gold are added
The Zirconium-aluminum-titanium of department cooperates tanning agent), 180min is rotated, then turns 5min, stops 55min, be repeated 6 times；Addition 0.4% mentions automatically
Alkaline agent (BTB-08 of Bao Sika chemical company) rotates 180min, adjusts bath foam pH to 3.9；Add 120% heat in two times again
Water adjusts bath temperature to 40 DEG C, rotates 120min, and drain is roused out.
Step 4 will obtain the white wet leather tiling of no chrome tanning and stand two days, then carry out water squeezing and shaving, and after weighing shaving
Weight without the white wet leather of chrome tanning, the parts by weight of agents useful for same in subsequent treatment process step are determined by the weight；
Step 5, rewetting (reagent dosage is with the percentages for the white wet leather weight of shaving that step 4 weighs): it is added in rotary drum
40 DEG C of water 200%, be added 0.6% formic acid (regular industrial formic acid), 0.5% fatty aldehyde (BASF chemical company
PF), 60min, drain are rotated；
Step 6, without chrome retanned (reagent dosage is with the percentages of the white wet leather weight of shaving that step 4 weighs): in rotary drum
30 DEG C of water 80% is added, 0.5% formic acid is added, rotates 30min, adjusts bath foam pH to 3.0；2% glutaraldehyde tanning is added
Agent (GT-50 of BASF chemical company) rotates 30min；More metal combination tanning agents of addition 5% be (Ting Jiang new material company
Zirconium-aluminium-silicon cooperates tanning agent), rotate 120min；1% sodium formate (regular industrial sodium formate) is added, rotates 60min；In three times
0.6% sodium bicarbonate (regular industrial sodium bicarbonate) is added, every minor tick 30min adjusts bath foam pH to 4.2；2% both sexes are added
Amino resin tanning agent (MAU of Tang Pule chemical company) rotates 60min, drain, washing；
Step 7 neutralizes (reagent dosage is with the percentages for the white wet leather weight of shaving that step 4 weighs): being added in rotary drum
30 DEG C of water 150% is added in 2% waterproof and polymer (A of BASF chemical company), 1% sodium formate, rotation
20min；0.5% sodium bicarbonate is added, rotates 60min, terminal bath foam pH is 4.8, drain, washing.
(reagent dosage is with the percentage for the white wet leather weight of shaving that step 4 weighs with bath for step 8, filling, dyeing, stuffing
Meter): 30 DEG C of water 30% is added in rotary drum, the 2% water proof type organosilicon polymer (TJ- of Ting Jiang new material company is added
A9991), 3% water proof type acrylate copolymer (SOF of De Rui chemical company), 2% acrylate resin tanning agent (BASF
The RE of chemical company), rotate 60min；1.5% siliceous waterproof currying agent (CD of BASF chemical company) is added, 1% contains
Wax waterproof currying agent (HQ of Schill+Seilacher company) rotates 40min；2% melamine resin tanning agent (soup is added
The HB of Pu Le chemical company), 2% dicyandiamide resin tanning agent (DF-585 of this tal fibre chemical company), 2% Lauxite
(SK-10 of Sai Qi chemical company), 2% tara mimosa extract (TARA), 3% quebracho extract (KPS), 2% both sexes acrylic acid tree
Rouge tanning agent (TGR of De Rui chemical company), 2% black dyestuff, rotate 120min, detect buttocks notch dyestuff full impregnated；It is added 1%
Silane crosslinker (KT 3007 of Kate's new material company), 3% siliceous waterproof currying agent, 3% content of wax waterproof stuffing
Agent, 2% synthesis waterproof currying agent (WP of Schmitt chemical company), rotate 90min；60 DEG C of hot water of 100-150% are added,
Rotate 60min；Divide 4 formic acid for being added 3%, every minor tick 20min adjusts bath foam pH to 3.5-3.7, drain, washing.
Step 9, Chrome-free fix (reagent dosage is with the percentages for the white wet leather weight of shaving that step 4 weighs): in rotary drum
35 DEG C of water 200% is added, 1.5% aluminium tanningagent (BN of BASF chemical company) is added, rotates 30min；Addition 1% contains
Silicon waterproof currying agent rotates 30min；5% more metal combination tanning agents are added, rotate 90min；The siliceous waterproof of addition 1% adds
Rouge agent, rotates 20min, and drain is washed 2 times, roused out.
Step 10, final finishing: take horse standing → water squeezing stretching, extension → vacuum drying → extension dry it is dry → oscillation draw it is soft, wherein very
For the control of crust leather moisture in 20-30%, extension dries dry rear crust leather moisture control in 8-12% after sky is dry.
The manufacture craft that line leather is fallen in above-mentioned environmental protection has the advantage that
A, in step 2 deashing and softening using no ammonia deliming agent and without ammonia macerating enzyme with bathing progress, can effectively mitigate useless
Ammonia and nitrogen pollution in liquid, and mitigated using two kinds of material effects, permeate deep characteristic, so that pelt deashing and softening process is slow
With and it is uniform, it is deeply thorough, be ready for next step Chrome-free Combined tanning system.
B, in step 3 use not pickling Chrome-free Combined tanning technique, first using organic silicon modified polyurethane resin KT4031 into
Row pretreatment, KT4031 is a kind of cation polyurethane silica gel, and on the one hand it has preferably emulsification wetting action, right before tanning
Intradermal fiber is sufficiently soaked, and fiber is further dispersed；On the other hand its cation having electrically, can effectively close skin
Carboxyl isoreactivity group on interior collagenous fibres, guarantees the infiltration of subsequent tanning agent, so that pickling operation is eliminated, it can be with economized
Work material, simplification of flowsheet and shortening production cycle；In addition, KT4031 itself has certain as polyphosphazene polymer silicon materials
Waterproof action, for it is subsequent improve leather waterproofness lay the foundation.Organic synthesis tanning agent F-90 and zirconium-are used after pretreatment
Aluminium-titanium cooperation tanning agent carries out Chrome-free combination tanning, they are all the novel non-chrome tanning agents that environmental-protecting performance is high, tanning properties are good, but
It is all the presence of respective defect, the soft not enough consolidation of F-90 tanning and heat resistance is poor, Zirconium-aluminum-titanium tanning plate is firmly not soft, resistance to
Hot good, the two combination tanning can be played the role of learning from other's strong points to offset one's weaknesses.When tanning, the spy of F-90 resistant to high pH, good penetrability is utilized
Property, tanning first is carried out to pelt, on the one hand to collagenous fibres can be made slightly to be formed, tan can be cooperated with Zirconium-aluminum-titanium in intradermal introducing
On the other hand the active group of agent coordination can make bath foam pH value be reduced to 4-5 or so, be conducive to Zirconium-aluminum-titanium and match after its first tanning
It closes tanning agent and gos deep into deeper, more evenly to intradermal, make that tanning is combined to reach optimal collaboration tanning effect.And the tanning later period mends
Liquid heating also carries out in two times, and this can enable tanning agent infiltrations deeper into tanning better effect is uniform, to assign white without chrome tanning
The wet good physicochemical property of leather.Chrome-free combination tanning from source eliminate heavy metal chromium pollution, and the metals such as zirconium, aluminium, titanium from
Introducing for son has also laid good basis for the absorption of subsequent waterproof material and fixation.
C, it will obtain standing two days without the white wet leather tiling of chrome tanning in step 4, this, which is conducive to remove from office, dissociates between interior fiber
Tanning agent molecule coordination promotes them to be coordinated with active group on collagen, enhances tanning effect.
D, during step 5 rewetting, degreasing agent is not used, and fatty aldehyde PF is used to carry out rewetting, one side fatty aldehyde
The natural oil dispersed in leather can be helped, promotes white wet leather to ease back, on the other hand it will not influence the anti-of subsequent waterproof material
Aqueous energy, and additionally aid them and be uniformly distributed in leather.
E, it is first carried out using glutaraldehyde tanning agent GT-50 and zirconium-aluminium-silicon cooperation tanning agent without chrome retanned in step 6, both
With good collaboration tanning effect, more stable cross-linked structure can be formed between tropocollagen molecule in removing from office, and to remove from office Nei Gejin
Belong to ion distribution more evenly, on the one hand play the role of supplementing tanning, guarantees that leather has good physicochemical property, on the other hand increase
Adding in leather can carry out with the metal ions such as zirconium, aluminium subsequent waterproof material ins conjunction with for the combination and fixing of subsequent waterproof material
Prepare.And the addition of glutaraldehyde tanning agent can also increase the organoleptic properties such as the flexibility of crust leather, and to promote subsequent waterproof material
The infiltration of material makes their difference more evenly.Both sexes ammonia melamine resin tanning agent is added below, is on the one hand contained using itself
Some carboxyls, amino isoreactivity group can play fixed zirconium-aluminium-silicon cooperation tanning agent work with the metal ions compatibility such as zirconium, aluminium
With on the other hand utilizing the yin-yang of itself is double electrically to promote the combinations and fixation of subsequent waterproof polymer.
F, first neutralized in step 7 using in waterproof with polymer A, sodium formate, using they neutralization performance compared with
Guarantee to neutralize slow uniform so that crust leather first slowly improves pH for mitigation and the preferable characteristic of permeance property.It is added and neutralizes afterwards
The more strong sodium bicarbonate of performance is gradually neutralized into leather further along the dynamics that front neutralizes, and three's collocation ensure that neutralization is deep
Thoroughly and uniformly, it is evenly distributed and lays the foundation from outside to inside along the cross section of leather for subsequent waterproof currying agent.Also, waterproof neutralizes
Polymer not only plays the role of uniformly neutralizing, with neutralization deeply with uniformly, can leather in first preliminarily form waterproof layer,
Assign leather certain waterproof action.
G, first selection is that waterproof has the water proof type organosilicon polymer TJ-A9991 of filling capacity, waterproof again in step 8
Type acrylate copolymer SOF, collocation acrylate resin tanning agent RE carry out first step filling, and on the one hand they can faster, more
Even is deep into depths in leather, establishes waterproof system from inside, can first play the first step in another aspect polymer and then leather
Filling effect is ready for subsequent main filling；Then selection waterproof performance is good can assign the siliceous of the soft and full property of crust leather again
On the one hand waterproof currying agent CD, content of wax waterproof currying agent HQ further strengthen anti-water system using two kinds of good waterproofness of material
On the other hand system utilizes flexibility, the lubricity of two kinds of materials, softens, lubricant fiber to crust leather, utilize subsequent tannin extract etc.
The infiltration of filler；The chestnut that reselection has amino resins, amphoteric amino-resin, permeability and the fillibility of selection fillibility good
The wooden tannin extract and tara mimosa extract carry out main filling, on the one hand assign the good body bone of crust leather and performance, on the other hand play closing front
The effect of the waterproof polymer and dubbin of addition makes it form good waterproof layer in leather；Then low temperature is carried out with bath to add
Dubbin, on the one hand can be improved the absorptivity of packing material and waterproof currying agent, and the waterproof being added after on the other hand filling adds
Rouge agent not only filling layer surface can form waterproof layer in leather, can also deeply fill together with the filler of the subsequent infiltration in part
In layer so that waterproof currying agent permeates more preferably uniformly and deeply, with remove from office in the metal ion complexations knot such as equally distributed zirconium, aluminium
It closes, builds more preferably firm waterproof layer structure.And during stuffing, it is also added into silane crosslinker KT 3007, utilizes it
Good bridging property is crosslinked various waterproof currying agents, forms more preferably firm waterproof construction, improves waterproofness
Energy.Finally, formic acid is added several times, bath foam pH is gradually reduced, so that absorption and combination that waterproof currying agent uniformly mitigates, assign
The more preferably uniform waterproof performance of crust leather.
H, aluminium tanningagent BN is first added in step 12 to be added filling stuffing process by waterproof polymer that crust leather absorbs, waterproof
Rouge agent carries out tentatively fixed, the combination and fixation of guarantee crust leather interior waterproof material；Then divide 2 addition waterproof currying agent CD,
And secondary fixation is carried out using zirconium-aluminium-silicon cooperation tanning agent, on the one hand reinforce the fixation of leather inner waterproofing material, on the other hand assigns
Crust leather surface more preferably water proof anti-soil performance, so that comprehensive guarantee crust leather has good waterproof performance.
The water proof type Chrome-free leather being prepared by the manufacture craft that above-mentioned water proof type is removed from office without chromed tanned leather, green ecological ring
It protects, waterproof performance is excellent, and organoleptic properties and Physical Mechanical are able to satisfy Industry code requirements.Through detecting, water proof type is without chromed tanned leather
The dynamic water-proof number of leather is greater than 50,000 times, and for static water absorption rate less than 20%, tear edge is greater than 60N, and shrinkage temperature is greater than 90 DEG C,
Soft plentiful flexible, grain consolidation is careful and smooth.And the fabrication processing is simple, easy to operate, practicability
By force, it is suitble to industrialization production application.
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 patents of this creation opinion, and is not limited to those disclosed embodiments.
Claims (9)
1. the manufacture craft that a kind of water proof type is removed from office without chromed tanned leather, successively comprises the following steps: grey pelt fleshing, split, weighing →
Deliming, softening → chrome-free tanning → standing, water squeezing, shaving, weighing → rewetting → without chrome retanned → neutralization → filling, dyeing, plus
Rouge → Chrome-free fixes → final finishing, it is characterised in that:
The deliming, softening process use same bath process, the deliming, softening same bath process in be added without ammonia deliming agent, nothing
Ammonia macerating enzyme carries out deashing and softening；
The chrome-free tanning process uses not pickling Chrome-free combination process for tanning, adds in the not pickling Chrome-free combination process for tanning
Enter organic silicon modified polyurethane resin, organic synthesis tanning agent, more metal combination tanning agents and carries out Chrome-free combination tanning；
More metal combination tanning agents, glutaraldehyde tanning agent, amphoteric amine resin tanning agent etc. are added in the Chrome-free retanning procedures and carries out nothing
Chrome retanned；
The filling, dyeing, stuffing process use same bath process, and the filling is dyed, propylene is added in the same bath process of stuffing
Acid resin tanning agent, waterproof polymer, vegetable extract, amino resin tanning agent, dyestuff, waterproof currying agent are filled, dye and add
Rouge；
Aluminium tanningagent is added in the Chrome-free fixed step, more metal combination tanning agents carry out Chrome-free and fix.
2. the manufacture craft that water proof type according to claim 1 is removed from office without chromed tanned leather, it is characterised in that: reagent dosage is with split
The percentages of the grey pelt weight of back layer, the deliming, the same bath process of softening are as follows: 28-30 DEG C of water 50- is added in rotary drum
100%, 1-3% without ammonia deliming agent, rotate 60-90min, be added 0.1-0.5% without ammonia macerating enzyme, rotate 30-60min,
Check that buttocks notch is in uniform colorless state with phenolphthalein, terminal bath foam pH is 7.5-8.5, drain, washing.
3. the manufacture craft that water proof type according to claim 1 is removed from office without chromed tanned leather, it is characterised in that: reagent dosage is with split
The percentages of the grey pelt weight of back layer, the not pickling Chrome-free combination process for tanning are as follows: 25-30 DEG C is added in rotary drum
The anti-strand agent of water 20-50%, 0.1-0.2% rotate 10min；The organic silicon modified polyurethane resin of 1-2%, rotation is added
60min；The organic synthesis tanning agent of 3-6% is added, rotates 120min；More metal combination tanning agents of 5-15%, rotation is added
Then 180min turns 5min, stop 55min, repeats 5-8 times；The automatic alkali extracting agent of 0.1-0.5% is added, rotates 180min, adjusts
Bath foam pH to 3.8-4.2；It adds the hot water of 100-150% in two times again, adjusts bath temperature to 40-42 DEG C, rotate 120min,
Drain is roused out.
4. the manufacture craft that water proof type according to claim 1 or 3 is removed from office without chromed tanned leather, it is characterised in that: organic conjunction
It is Granofin Easy F-90 at tanning agent；More metal combination tanning agents are that Zirconium-aluminum-titanium cooperates tanning agent, iron-zirconium-aluminium cooperation
At least one of tanning agent, zirconium-aluminium-silicon cooperation tanning agent.
5. the manufacture craft that water proof type according to claim 1 is removed from office without chromed tanned leather, it is characterised in that: reagent dosage is with shaving
Percentages afterwards without the white wet leather weight of chrome tanning, the Chrome-free retanning process are as follows: 25-30 DEG C of water 50- is added in rotary drum
100%, the formic acid of 0.5-1% is added, rotates 30min, adjusts bath foam pH to 3.0-3.2；The glutaraldehyde tanning agent of 1-2% is added,
Rotate 30min；More metal combination tanning agents of 5-10% are added, rotate 120min；The sodium formate of 1-2% is added, rotates 60min；
The sodium bicarbonate of 0.5-1.0% is added in three times, every minor tick 30min adjusts bath foam pH to 3.8-4.2；The both sexes of 1-3% are added
Amino resin tanning agent rotates 60min, drain, washing.
6. the manufacture craft that water proof type according to claim 1 is removed from office without chromed tanned leather, it is characterised in that: reagent dosage is with shaving
Percentages afterwards without the white wet leather weight of chrome tanning, the filling, dyeing, the same bath process of stuffing are as follows: be added 25-30 DEG C in rotary drum
The waterproof polymer of 3-6%, the acrylate resin tanning agent of 2-4% is added in water 30-50%, rotates 60min；The anti-of 1-3% is added
Water fatting agent rotates 40min；The both sexes acrylic acid of the amino resin tanning agent of 4-8%, the vegetable extract of 2-6%, 2-4% is added
The dyestuff of Polymer Tanning Agent, 1-3% rotates 120min, detects buttocks notch dyestuff full impregnated；The silane crosslinker of addition 1-2%,
The waterproof currying agent of 6-10% rotates 90min；The 50-60 DEG C of hot water of 100-150% is added, rotates 60min；Divide 4 additions
The formic acid of 1.5-3%, every minor tick 20-30min adjust bath foam pH to 3.5-3.7, drain, washing.
7. the manufacture craft that water proof type according to claim 1 or 6 is removed from office without chromed tanned leather, it is characterised in that: the water resistant polyurea
Conjunction object is at least one of water proof type organosilicon polymer, water proof type acrylate copolymer；The vegetable extract is chestnut evergreen chinquapin
At least one of glue, tara mimosa extract；The amino resin tanning agent is Lauxite, in melamine resin, dicyandiamide resin
At least one；The waterproof currying agent be siliceous waterproof currying agent, synthesis waterproof currying agent, in content of wax waterproof currying agent extremely
Few one kind.
8. the manufacture craft that water proof type according to claim 1 is removed from office without chromed tanned leather, it is characterised in that: reagent dosage is with shaving
Percentages afterwards without the white wet leather weight of chrome tanning, the Chrome-free technique for fixing are as follows: 35-40 DEG C of water 200- is added in rotary drum
250%, the aluminium tanningagent of 1-2% is added, rotates 30min；The waterproof currying agent of 1-2% is added, rotates 30min；It is added 3-6%'s
More metal combination tanning agents rotate 90min；The waterproof currying agent of 0.5-1% is added, rotates 20min, drain is washed 2 times, roused out.
9. the manufacture craft that water proof type according to claim 1 is removed from office without chromed tanned leather, it is characterised in that: the finishing process
Including take horse standing → water squeezing stretching, extension → vacuum drying → extension dry it is dry → oscillation draw it is soft, wherein vacuum drying after crust leather moisture control
For system in 20-30%, extension dries dry rear crust leather moisture control in 8-12%.
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| CN111321260A (en) * | 2020-03-31 | 2020-06-23 | 河南中牛实业有限公司 | Environment-friendly chromium-free retanning method for leather |
| CN111893223A (en) * | 2020-08-28 | 2020-11-06 | 焦作隆丰皮草企业有限公司 | Retanning splitting process for environment-friendly vegetable elastic leather product |
| CN112501364A (en) * | 2020-12-08 | 2021-03-16 | 兴业皮革科技股份有限公司 | Preparation method of ecological functional leather based on nano material |
| CN113201605A (en) * | 2021-04-15 | 2021-08-03 | 兴业皮革科技股份有限公司 | Tanning process for multi-component chrome-free combined tanned white wet leather of cattle and application thereof |
| CN113201606A (en) * | 2021-05-06 | 2021-08-03 | 兴业皮革科技股份有限公司 | Production process of heavy metal-free tanned cow leather |
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| CN113462824A (en) * | 2021-06-11 | 2021-10-01 | 中国皮革制鞋研究院有限公司 | Method for improving performance of organic chrome-free tanned leather |
| CN113621741A (en) * | 2021-08-18 | 2021-11-09 | 东莞诺德科技有限公司 | Preparation process of waterproof leather |
| CN114231669A (en) * | 2021-09-28 | 2022-03-25 | 柏德皮革(中国)有限公司 | Process for compacting leather crust |
| CN114941043A (en) * | 2022-06-28 | 2022-08-26 | 河南中牛实业有限公司 | Retanning and dyeing method and application of environment-friendly cattle leather |
| CN115838841A (en) * | 2022-11-28 | 2023-03-24 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Method for preparing waterproof leather by using zeolite tanning agent and application thereof |
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| CN111893223A (en) * | 2020-08-28 | 2020-11-06 | 焦作隆丰皮草企业有限公司 | Retanning splitting process for environment-friendly vegetable elastic leather product |
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| CN113462824B (en) * | 2021-06-11 | 2022-03-18 | 中国皮革制鞋研究院有限公司 | Method for improving performance of organic chrome-free tanned leather |
| CN113462824A (en) * | 2021-06-11 | 2021-10-01 | 中国皮革制鞋研究院有限公司 | Method for improving performance of organic chrome-free tanned leather |
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