CN109097507A

CN109097507A - A kind of water-soluble polyamines base silane coupling agent replaces the silane tanning process of enzyme preparation

Info

Publication number: CN109097507A
Application number: CN201710723150.9A
Authority: CN
Inventors: 阳庆文; 陈磊; 帅晓强; 蓝华全; 徐沙; 卢宁沙
Original assignee: CHENGDU KAITE ORGANOSILICON NEW MATERIALS TECHNOLOGY Co Ltd
Current assignee: CHENGDU KAITE ORGANOSILICON NEW MATERIALS TECHNOLOGY Co Ltd
Priority date: 2017-06-21
Filing date: 2017-08-22
Publication date: 2018-12-28
Anticipated expiration: 2037-08-22
Also published as: CN109097507B

Abstract

The present invention relates to leather sectors.Replace the silane tanning process of enzyme preparation more particularly to a kind of water-soluble polyamines base silane coupling agent.Water soluble polymer polyamines base silane coupling agent thoroughly replaces biological enzyme formulation to soak for process hides, ruin hair, liming, multiple ash, the processes such as deliming, and completely abolish traditional enzyme bating process, as crosslinking agent, it can effectively maintain or reinforce the crosslinking degree of the natural cross-linked structure of materials with hide glue fibril, as polyamines base silane coupling agent, it can make materials with hide glue fibril safely effectively submissive softening, quality accident is scrapped to eliminate biological enzyme formulation leather loose side mass defect caused by the not easily-controllable or uncontrollable destruction of the natural cross-linked structure of materials with hide glue fibril or collagen resolution, biological enzyme formulation has been effectively relieved to traditional leather-making technology operator's bring leather loose side, collagen clears up the serious psychological pressure for scrapping quality accident, it can save for 50% or more time, conserve water 40% or more, substantially reduce pollutant discharge amount and water, electricity , human resources consumption, realize " good skin go out in silica gel ash cylinder ", process operator can easily control and obtains the soft high-quality silica gel voluptuousness without pine, plentiful flexible leather quality.

Description

A kind of water-soluble polyamines base silane coupling agent replaces the silane tanning process of enzyme preparation

Technical field

The present invention relates to field of leather, and in particular to a kind of water-soluble polyamines base silane coupling agent replaces the silane of enzyme preparation Tanning process.

Background technique

It is (main using the tannin extract extracted from plant 1. traditional vegetable tanning method is the method that the mankind are used for leather manufacture earliest Wanting ingredient is tannin) carry out tan leather.Vegetable tanning skin is unique environment protection ecological type leather in tan leather, will not burning Noxious material is released, present some pet grains are exactly to be made into this skin particle.This leather quality is more thick and solid, plate Firmly, tough and tensile, it is easy to absorb liquid, convenient for three-dimensional plasticity after water suction, color is the light brown yellow of tannin extract true qualities；Through oxygen after use Change, sunshine and the factors such as the absorption of liquid can be deepened gradually, prolonged day note is the solarization of vegetable tanning skin at dark brown.Tradition Vegetable tanning skin is chiefly used in military products, mechanical fitting, basketball, waistband, sole, leather trunk casket and carving skin modeling, therefore claims " heavy leather "；Because of its tanning It is bitter with the taste of tannin, and it is commonly called as " puckery skin ", " tree cream skin ", " tannin extract skin " etc..

2. the present invention selects water soluble polymer silane coupling agent, i.e. water soluble organic polymer bridged polysilsesquioxane Presoma is implanted into tannin extract tanning during forming organic silica gel under alkaline condition and plants organic silica gel just like chest enlarge shaping Enter female breast and obtain plentiful soft fine and smooth voluptuousness, can thoroughly change that people are hard to traditional vegetable tanning dermatotome, feel is poor in this way Cognition, obtaining good hand feeling, softness and grain consolidation, loose side, skin do not meet or exceed the completely new silicon of the light leathers such as chrome leather The flexible vegetable tanning skin of glue -- tannin extract Combined tanning, this micromicro and human skin intimate contact, not only pro-skin it is comfortable again to skin without times What is poisoned, and can not only be made summer sleeping mat, can also be made personal brassiere, underwear pants etc., will generate leather to traditional leather industry The innovation of life property is overturned, and has immeasurable environmental protection and commercial value.

3. water soluble polymer silane coupling agent

3.1 silane coupling agent

Silane coupling agent contains the inorganic functionalized silicon group of organic-philic carbon functional group and parent simultaneously, can be in inorganic and bios Molecular bridge is formed between face, to play the role of chemical thickening, enhancing, increase-volume, improve composite property.It is silane coupled Agent can indicate that X is the functionalized silicon group of hydrolyzable condensation with [Q-R '-Si (R) nX (3-n)], and Q is organo-functional group (carbon official Can roll into a ball), R is the inert alkyl being bonded with silico-carbo, and R ' is the dying links base that functionalized silicon is rolled into a ball to X and carbon functional group Q bonding and is got up Group.

The main product molecular weight in silane coupling agent market is small at present, mostly category oil-soluble, cannot be evenly dispersed in water It is stabilized, a large amount of alcohol suppression hydrolysis in acid condition is needed to be cured into macromolecular before use, this process is vulnerable to environment temperature, wet A variety of conditions such as degree, medium pH value, metal impurities influence, and application experience is strong, it is difficult to control, thus have certain limitation.It is more The macromolecule silane coupling agent of degree of functionality is cured using hydrolysis is preceding not required to, but is substantially still oil-soluble, not environmentally friendly enough, cannot be direct Using water as reaction medium.As the function hybrid material technology of sol-gel method preparation in recent years continues to develop, to silane coupling agent Reactivity, the controllability of reaction, repeatability and the convenience of operation and the feature of environmental protection etc. made higher requirement, Thus it is necessary to small molecule silane coupling agent is carried out high functionality, producing high-molecular and water solubilityization.

3.2 from oil-soluble, small molecule to water-soluble, macromolecule

The producing high-molecular of the molten type small molecule silane coupling agent of oil, multiple functionalized and Water-borne modification are by Si―H addition reaction and acidity Silane balanced reaction is by hydrophilic radical, multiple specific functionalized silicon groups, carbon functional group and macromolecule similar with matrix structure What bridge linkage group was directly realized with polysiloxanes chain link.

There are four types of methods for the producing high-molecular of small molecule silane coupling agent: (1) more alkoxysilyl groups being grafted on organic carbon height On strand；(2) more alkoxysilyl groups are grafted on organosilicon macromolecule chain；(3) more alkoxysilyl groups are grafted on organic Silicon, organic carbon high-molecular block copolymer chain on；(4) the resulting macromolecular of three of the above or macromolecule silane coupling agent again with It is modified that small molecule silane coupling agent or modified macromer silane coupling agent carry out response type.Gained molecular weight is generally higher than 10000, Even up to 30000 or more.

Introduced in the above process multiple and different functionalized silicon bases can be achieved at the same time producing high-molecular with it is multiple functionalized.From D4/ The monomers such as DMC, small molecule silane coupling agent, containing hydrogen silicone oil, carbon system organic monomer containing active function groups start, and are added by silicon hydrogen At modes such as, copolymerization/polycondensation/grafting, according to the application performance of final products, by the organic high score of small molecule silane coupling agent silicon systems Sonization, carbon system organic polymer and silicon systems-carbon system organic hybrid producing high-molecular and further modified with functional group can obtain To the macromolecule silane coupling agent of the functional group containing Liang Lei.

Since functionalized silicon base and carbon functional group all have reactivity, contacting with the active hydrogen in water can react, because And to obtain can the evenly dispersed silane coupling agent being stabilized in water, it is necessary to which these active function groups of safekeeping make it Self-crosslinking will not occur before arriving at substrate surface or inactivated with water hydroxyl solution.The Water-borne modification of small molecule silane coupling agent be from The hydrophilic pre-polymerization of monomer starts, and arrives hydrophilic chain extension, further acid water dispersion chain extension, forms macromolecular, high molecular step by step Hydrophily covalent bonding system, while realizing the multiple functionalized of silane coupling agent, producing high-molecular and water-soluble self-emulsifying.

Type, the number of hydrophilic radical, carbon functional group and functionalized silicon group on water soluble polymer silane coupling agent master, side chain Amount and distribution can be designed according to application demand, to obtain be directed to different substrate materials surface wetting permeability can it is excellent, can often The cured unique novel environmental close friend functional material of temperature.

Wherein, n=15~150, R1: epoxyhydrocarbyl or triethoxy silicon substrate alkyl or alkyl, R2: 1 alkyl of polyethers or Epoxy group alkyl or triethoxy silicon substrate alkyl or alkyl, R3: 1 alkyl of alkyl or polyethers, R4: triethoxy silicon substrate alkyl Or isocyanates alkyl, R5: epoxy group alkyl or trimethoxy silicon substrate alkyl, R6: 2 alkyl of polyethers, R7: 3 alkyl of polyethers or three Ethyl-silicone alkyl, R8: 4 alkyl of polyethers, R9: polyamines polyene base alkyl or isocyanates alkyl, except, it can also connect sulfur-bearing hydrocarbon Base, fluorine-containing alkyl etc..Bridge linkage group-[Bridge]-can are as follows: polymethyl siloxane, acrylic resin, polyurethane resin, epoxy Resin, polyaminoacid etc..

To improve service performance, water soluble polymer silane coupling agent need to be considered in compounding design: (1) as needed Increase the kind and number of functionalized silicon group and carbon functional group: the functionalized silicon group number of water soluble polymer silane coupling agent is reachable Six, nine, 12 is even several, thus available presoma enormous amount, and coupling crosslinking simultaneously can further expansion presoma net Network, the type and quantity for allowing to the different performance material of hydridization are virtually limitless, after sol gel reaction, molecule table Sign can be considered the bridged polysilsesquioxane of three-dimensional-structure, and multiple carbon functional groups such as hydroxyl alkyl, mercapto alkyl, ammonia alkyl, carboxylic The introducing of alkyl, alkylene, epoxyhydrocarbyl, isocyanates alkyl, fluorohydrocarbon base then can increase silane coupling agent forerunner's volume grid Application adaptability；(2) accordingly extend the-R arm that functional group connect with main chain, be exposed outside functional group sufficiently as far as possible, avoid Because steric hindrance is shielded；(3) bridge crosslinking structure of group similar with substrate surface, side chain or macromolecular is introduced to improve water The similitude of soluble macromolecular silane coupling agent and material substrate surface makes it be easy that net is collectively formed with the substrate of different speciality The polysiloxanes sol-gel of network shape, body shape.

Since water soluble polymer silane coupling agent occasion can be flexibly designed to specifically according to the specific application Functional group combination, it is thus possible to the single and not soluble in water limitation of small molecule silane coupling agent functional group is broken through, by silane Coupling agent expands to all substrate surfaces such as organic and inorganic, organic-biological-inorganic that are related to from existing application field and is coupled hydridization Field that is modified, promoting similar compatibility, especially using water as the occasion of reaction medium such as: process hides, synthetic leather, textile finishing；Skin Leather, suede, wool spinning product wash the submissive nursing of anti-shrinkage；The metal surfaces such as automobile, machinery lubrication and antirust, anti-corrosive processing；It is aqueous Coating and Waterproof ink adhesion and water resistance improvement processing: the surface organic modifications such as nano-powder, Hollow Glass Sphere, Water resistant processing；The composite modifications such as stone modeling, wood moulding, plastic-steel；Biological sol-gel hybridization material preparation；LED, medical human It is implanted into material, biomedical engineering etc..

Summary of the invention

1. silane tanning

" silane tanning " is the neologisms that Chengdu Kaite Organosilicon New Materials Technology Co., Ltd. creates.It is led in profession Domain, the meaning of a neologisms, often the more than new combination of text, even more expects the new things of new opplication from green wood.It is organic Silicon product is just used as always a trend due to good wetability, permeability, dispersibility, flexibility, two during the last ten years It is had an optimistic view of by leather industry, it may bring a progress, primary to change.

Organosilicon system is introduced into the process from rawhide to resultant Leather, the disadvantage of traditional process hides is solved, early in eighties of last century Just enter the imagination of process hides expert, but it is big to suffer from professional span, it must fusion polymer synthetic chemistry, water soluble organic polymer The professional knowledge of four aspect such as bridged polysilsesquioxane precursor synthesis chemistry, process hides chemical materials, tanning technology, and There is no operable ready-made material, the application method that more not can refer to is tantamount to climb cloud in terms of the difficulty of realization.

Nowadays, what Wenjiang district of Chengdu city Ming Nida fluosilicic skin application study pilot plant produced has silicon substrate reactivity The exploitation of the silane-modified skin material system of the third generation and related application system of the present invention " silane tanning ", makes older generation expert's Scientific research conception goes to market, grease it in from laboratory finally.Silane tanning is a kind of using nonhazardous, free of contamination water-soluble Based on property polymethyl siloxane bridged polysilsesquioxane presoma macromolecule silane coupling agent frame with quality-improving, at This reduction and emission reduction of saving water and energy are silane sol-gel tanning technical system of characteristic.In silane tanning system, tanning quilt It treats as combining tradition in various degree according to market and raw material skin concrete condition for the preparation of organic-biological-inorganic hybrid material Material carries out inorganization, the half inorganization, sol-gel that organises modification to native biopolymer materials with hide glue fibril to obtain It is expected that service performance.Application of the present invention by organosilicon material in leather sector is advanced to from existing covering with paint, stuffing workshop section Preparation and tanning retanning workshop section, have filled up domestic and international this technological gap, silane coupled with water soluble polymer before water factory's tan Based on agent on the basis of process hides material, it is more that silane tanning water-saving and emission-reducing low-carbon environment-friendly simplicity technical system is established substantially Year, the completely new road of a water-saving and emission-reducing was opened up out in traditional tanning, based oneself upon Ecology Leather clean manufacturing, not only laid siege to terminal production Product are environmental and ecological, and emphasis process of producing product is environmental and ecological always, to from material and the control pollution of technique source, improve and pass System leather industry high energy consumption, high water consume, high pollution situation promote leather-making technology simplicity, scientific, art up and promotion tan The development of leather practice and modernization, there is active influence.

2. the selection of silane tanning agent

Chemically angle is seen, is, half inorganic, organic polybase idol for example inorganic using polybase coupling agent on the process nature of tanning Join agent and carry out that inorganization, half inorganization, organising is coupled hybrid modification to natural organic high-molecular materials with hide glue fibril, is use Transition metal ions hydroxyl compound containing 3d, 4d or 5d unoccupied orbital or its alkoxide (i.e.-OH is replaced by-OR base) contain hydroxyl On base unit (or hydroxy unit can be restored in water) or the organic compound and materials with hide glue fibril of other active carbon functional groups Active hydrogen occur condensation cross-linking or addition-crosslinked reaction.

Traditional tanning is leading progress tanning with alkali formula trivalent chromium.In acid water environment, trivalent chromium is usually as center Ion is taken off by the active hydrogen that d2sp3 hydridization form is formed on complex, with materials with hide glue fibril with three electron rich ligands The R-O-Cr that water crosslinking is formed can be considered a kind of poly- chromium oxygen alkane, due to the stable structure of chromium, hard, by the modified collagen of chromium Fiber is endowed good stability and rigidity.Theoretically chromium ion maximum can form octahedral coordination knot with six ligands Structure, but since the electron orbit energy level of chromium atom and carbon atom and symmetry mismatch, it is difficult to form electron cloud between chromium and carbon Flowing is difficult to form covalent bond, therefore after the trivalent chromic ion (d2sp3) of hexa-coordinate and three electron rich ligands Remaining three hollow co-ordination positions can not receive alkyl, i.e., cannot form Cr-C key, therefore the Organic of chromium is insufficient, makes Used time must preferably could permeate to materials with hide glue fibril under low ph value aqueous solution state, corresponding poly- chromium oxygen alkane chromed tanned leather obtained I.e. wet blue is flexible also insufficient, and rear process must fill grease largely to increase soft and moist cunning, if being long placed in skin base, then grease is lost, very It is easy the hard aging of plate, influences quality.Although current trivalent chromium is still the leading material of traditional tanning system, due to its sexavalence There is harm to environment and human body in the toxicity of state ion, earth chromium resource is also increasingly deficient in addition, therefore finds and more preferably replace Never stop for tanning agent.Theoretically, as long as three or three or more hydroxyls or alkoxy alkoxide ligand compound can be formed Object has the function of that the transition metal of 3d, 4d or 5d unoccupied orbital or semimetallic elements may all have tanning, wherein with can be directly With carbon it is that-R the person of being connected is preferred, while also requires good stability, hard and soft and Ji, safe and non-toxic.

On the periodic table of elements, it can be connected with three or three or more hydroxyls or alkoxy simultaneously and can be connected directly with-R Element is the silicon with 3d unoccupied orbital.The inorganic silicon dioxide of nano-scale can be used as a kind of hydrogen bond filler for process hides, but It is active inadequate, it is insufficient as tanning agent use.In organosilicon, silane coupling agent is exactly 3 structure of R-Si (OR '), only on the market Oil-soluble small molecule silane coupling agent it is not soluble in water, and-the R of institute's band is short and small, and the kind and number of functional group are also limited, therefore It is also not suitable for using as process hides tanning agent.Water soluble polymer silane with multiple activated silica functional groups and carbon functional group is even Joining agent for process hides is a bold thinking, uses poly- times of water soluble organic polymer bridging of synthesis exclusively for process hides water field Half siloxane precursors have inorganic and organic tanning agent characteristic concurrently simultaneously, nontoxic and pollution-free, and silicon reserves are quite abundant on the earth, It therefore may be the suitable choosing of tanning agent.

3. silane tanning agent is compared with chrome tanning agent

Si atomic radius is larger on the functionalized silicon group-Si (OR ') 3 of silane coupling agent, and 3d track is entirely empty, electron deficient, and- (OR) oxygen atom 2p track electron rich in 3, the two orbital energy level is close, symmetry matching, the unity of opposites, phase in same molecule It is inverted into.(OR) 3 can delocalization alcoholysis be polybase structure-(OH) 3, form 3-OH's of band in acid water environment with trivalent chromium Complex is similar, also can be dehydrated (or dealcoholysis) cross-linking reaction with the active hydrogen on materials with hide glue fibril.Water soluble polymer silicon Several functionalized silicon groups are had on alkane coupling agent master, side chain, therefore can be formed with the active hydrogen reaction on materials with hide glue fibril network-like Polysiloxanes sol-gel precursor framework.In polysiloxanes collosol-gelatum system, the tanning cross-linked phase of each layer of corium To homogeneous, can preferably avoid chromed tanned leather that because the raw heart, asperities unevenly occur for tanning, grab face and grain layer and lamina reticularis Isolated loose side problem.

The tetravalence Si atom of water soluble polymer silane coupling agent is in sp3 hydridization, is directly connected to form Si-R with carbon atom Covalent bond, therefore Organic is substantially better than trivalent chromium, also greatly increases with the similar compatibility of biological base material such as materials with hide glue fibril, Without must strictly be used at low ph values as chrome tanning, meanwhile, the macromolecular bridging-of water soluble polymer silane coupling agent R group can as needed it is flexible and changeable such as can be polysiloxanes, polyurethane, polyacrylic resin, polypeptide, grease, accordingly Also its different characteristics is assigned to adapt to play a role on different substrate materials surface and application.Chrome tanning agent and other metal tanning agents are such as Zirconium, titanium, aluminium etc. cannot be directly connected to form M-R organic metal covalent bond with carbon atom.So-called Organic Chromium coupling agent, titanate esters Coupling agent, aluminum alkoxide etc. " metallo-organic compound ", alkyl are also all connected with chromium, titanium, aluminium simply by oxygen indirectly.Cause This, in contrast, the reaction bonded of silane and materials with hide glue fibril is easier, and the flexibility of molecular structure is also bigger, is easier to assign Different functions.

In addition, water soluble polymer silane coupling agent itself also has unique stability and flexibility, by poly- silicon oxygen The modified materials with hide glue fibril of alkane sol-gel hybridization also correspondingly have unique stability, flexibility, anti-folding and anti-pressing elasticity, The persistence of the qualities such as the delicate soft texture of silica gel and these qualities.These characteristics are that the siloxane modified materials with hide glue fibril of chromium is difficult to Have.

4. silane tanning agent is compared with organic tanning agent

It can be with substrate surface active hydrogen cross-linking reaction with (or can restore to obtain in water) on the carbon atom of organic tanning agent Activity unit, such as can dehydrated crosslinking hydroxyl-OH, can dealcoholysis crosslinking alkoxy-OR, addition-crosslinkable isocyanates Base-N=C=O etc..The carbon atom in organic tanning agent molecule being both SP3 hydridization cannot be as the silicon atom on silane coupling agent Three hydroxyls or alkoxy can be steadily connected simultaneously, and it is alcohol that-an OH is connected on carbon atom, and even then dehydration is aldehyde to two-OH, even Then dehydration is carboxylic acid to three-OH, and even four-OH are then visually all dehydration at " carbon dioxide ".Therefore, hydroxyl alkyl structure (phenol hydroxyl Phenolic resin, tetra methylol phosphonium salt, melamine resin of base class etc.) and can be reduced into single or multiple hydroxy units in water Structure such as epoxy construction (epoxy resin), aldehyde radical structure (aldehyde tanning agent), carboxyl structure (acrylate resin tanning agent), oxazole alkyl structure (synthesized and be made by aldehyde, release aldehyde in water), (polyurethane resin tanning agent, can be considered containing hydroxyl by ammonia isocyanate structural The dialdehyde unit that base replaces) all there is certain flexibility.

Multiple activity can be had in characteristic [Q-R '-Si (R) nX (the 3-n)] structure of water soluble polymer silane coupling agent Functionalized silicon group X, with multiple and different active carbon functional group Q.Theoretically, as long as playing the activity of crosslinking tanning in organic tanning agent Carbon functional group, water soluble polymer silane coupling agent can connect, and it is the same also to play organic tanning agent to materials with hide glue fibril Effect, and cooperate with participation to form the modified network of sol-gel hybridization together with functionalized silicon group.

Carbon atom radius ratio silicon since organic tanning agent can only work by carbon functional group merely, and on organic tanning agent is former Sub- radius is small, to the modified macromolecule silicon being difficult to as while having functionalized silicon group and carbon functional group of the crosslinking hybrid of materials with hide glue fibril Alkane coupling agent be equally capable of forming uniformly with certain hole network-like sol-gel, thus the uniformity of tanning with And to less than necessarily having in the encapsulation ability of other process hides materials.

5. effect of the silane tanning agent in tanning

It sums up, effect of the water soluble polymer silane coupling agent played in tanning mainly has: (1) by active Functionalized silicon group is combined with carbon functional group with materials with hide glue fibril crosslinking, builds polysiloxanes-materials with hide glue fibril sol-gel Presoma network architecture system, and assign leather unique fine and smooth resilient flexible silica gel texture；(2) its excellent permeability, point Property and special performance of opposing each other and yet also complement each other are dissipated, to the multiple material in bath foam such as acid, alkali, chrome tanning agent, grease, filler, dyestuff, perfume (or spice) The osmotic absorptions in materials with hide glue fibril such as material, emulsion dispersion play unique with bath adjustment effect, therefore workshop section is dyed in retanning Water-saving and emission-reducing environmental protection scheme without washing can be realized；(3) silane-materials with hide glue fibril sol-gel precursor network still has Presoma activity still there is crosslinking to combine energy other materials in bath foam such as tanning agent, dyestuff, grease, filler, fragrance etc. Power enables these materials to go deep into fiber jointly and reactivity encapsulation is fixed on extensive polysiloxanes sol gel network Among system, thus the leather quality obtained can be kept for a long time.

6. silane tanning technology path

In fact, the manufacturing process of entire leather, from water field to covering with paint, from fur to skin base to finished product and each stage The upgrading of loose side exception leather recycles and leather, the washing in fur products later period are nursed, and can run through using water-soluble high score Sub- silane coupling agent.

In recent years, from water field tanning lab scale many times to pilot scale to the external leather processing of small lot, silane tanning is had accumulated A large amount of first-hand using data, the silane retanning staining technique that midway is not washed is mature, and big loose side wet blue passes through silicon Alkane sol-gel is modified also to upgrade production plain weave vamp, the dual-purpose leather of luggage.Using silane sol-gel leather tanning, alkali Skin, tannage or sour skin without wet blue workshop section can directly tanning go out skin base, thoroughly change low ph value chrome tanning, height over more than 100 years The stuffing of pH value high temperature and the tanning mode that must repeatedly wash.Though silane tanning bring user experience finished leather quality, Quality controllability, operation conveniency, water-saving and emission-reducing low-carbon environment-friendly etc. are all that conventional carbon skin tanning is incomparable.

In addition, the inclusiveness of silane tanning system is very good, a line such as trivalent chromium, organic tanning agent can not only be contained well Traditional skin material, can also contain other metals or mineral tanning agent such as zirconium, titanium, aluminium, iron, silicate etc., in addition usually not as Calcium, magnesium, zinc of tanning agent etc. are likely to preferably incorporate among silane tanning system, to materials with hide glue fibril after silanization It carries out organic-biological-inorganic hybrid to be modified altogether, makes hybrid modification that there is bigger adjustability.On the other hand, any gold is not added The silane tanning for belonging to tanning agent full stress-strain also may replace cumbersome traditional chamoising process process hides, and it is environmentally friendly, available to obtain soft exquisiteness, pro-skin Make the polysiloxanes Silicone Rubber of note body underwear fabric, this silica gel hide fiber is in cotton shape, has the note similar to memorial alloy Recall function, even if deforming through high-temperature shrinkage, once restoring room temperature, and the shape and feel before deformation, wet-heat resisting can be restored automatically Stability, mechanical strength are superior to traditional chamois leather, and with short production cycle, simple process.

It is led it can be seen that good water solubility, nontoxicity, free of contamination water soluble polymer silane coupling agent are applied in process hides Domain, the auxiliary agent for functioning not only as a kind of brilliance are introduced into each workshop section of traditional leather-making technology, or a kind of material to play a leading role Material, can be to build completely new emission reduction silane sol of saving water and energy-gel tanning technical system, according to raw material skin situation and city Field demand combines other traditional tanning agents in various degree, and contains and screen carbon skin material whereby.

7. silica gel-tannin extract Combined tanning scheme

In order to overcome the defect of traditional vegetable tanning skin, it can eliminate that vegetable tanning dermatotome is hard, dead soft, feel the invention proposes one kind Difference, and can promote that resultant leather quality, technological operation is easy, saved for 50% or more time, 40% or more the, scope of application that conserves water is wide The water-saving and emission-reducing silane tanning manufacturing process of the personal flexible vegetable tanning leather of pro-skin ecology of wide environment-friendly type silica gel-tannin extract Combined tanning. To achieve the goals above, the present invention is achieved through the following technical solutions:

The water-saving and emission-reducing silane tanning of the personal flexible vegetable tanning leather of pro-skin ecology of environment-friendly type silica gel-tannin extract Combined tanning manufactures work Skill, including fur silane soaks, silica gel packet ash pushes away hair, silane-akali sulphide ruins a mao liming, ash, silane-hydrogen peroxide are pre- de- again for silica gel Ash (eliminating akali sulphide), the main deliming of silane-hydrogen peroxide (eliminating akali sulphide), cationic silica pretreatment, leaching salt, pickling, silicon aldehyde First tan/silica gel-tannin extract combines first tan, cationic silica to ease back, stuffing, cation are filled in anion silica gel-tannin extract dyeing retanning Silica gel is fixed and mould proof processing etc., can save for 50% or more time, conserve water 40% or more, substantially reduce pollutant discharge amount And water, electricity, human resources consumption.

To achieve the goals above, the present invention is achieved through the following technical solutions: the water soluble polymer is more Amino containing silane coupling agent thoroughly replaces the water-saving and emission-reducing silane tanning process of biological enzyme formulation, including the immersion of fur silane, silica gel Packet ash pushes away hair, silane-akali sulphide ruins a mao liming, the multiple ash of silica gel, the pre- deliming of silane-hydrogen peroxide (eliminating akali sulphide), silane-dioxygen Just tan/silica gel-tannin extract combines first tan, sun for the main deliming of water (eliminating akali sulphide), cationic silica pretreatment, leaching salt, pickling, silicon aldehyde Ion silica gel eases back, anion silica gel-tannin extract dyeing retanning filling stuffing, cationic silica is fixed and mould proof processing.

The fur silane immersion step are as follows: weigh 100 parts of furs by weight in rotary drum, wash 10 minutes, be added normal 100-150 parts of warm water, 0.1-1 parts of KT1717,0.05-0.3 parts of KT3007,0.2-0.5 parts of nonionic degreasing agent, fungicide 0.1-0.3 parts, 0.3-1 parts of soda ash, 0.1-0.3 parts of vulcanized sodium, after slow rotation 3 hours, turn 30 minutes/stop 30 minutes, turn stop 8-10 hours, this step did not had to soaking enzyme, defatting enzyme, rouses, fleshing out, pushes away hair into silica gel packet ash；

The silica gel packet ash pushes away a mao step are as follows: weighs 5000 parts of water, 30-60 parts of KT1717, KT3007 15-40 by weight Part, 20-40 parts of auxiliary liming agent, 30-60 parts of nonionic degreasing agent, 60-100 parts of NaHS, 240-280 parts of vulcanized sodium；It stirs evenly, 3000-4000 parts of lime are slow added into, side edged stirs, and obtains packet mortar.Packet mortar is applied to rabbit flesh noodles, ridge line applies The amount of smearing suitably increases, and the overlapping of meat meat stands and stacks 6-12 hours, pushes away hair, into drum, ruin a mao liming into silane-akali sulphide；

Silane-the akali sulphide ruins a mao liming step are as follows: be added normal-temperature water 10-30 parts, 0.1-0.3 parts of KT1717, it is non-from Sub- degreasing agent 0.3-0.5 parts, 0.3-0.5 parts of auxiliary liming agent, 0.5-0.8 parts of NaHS, 0.5-0.8 parts of vulcanized sodium, turn at a slow speed After dynamic 1 hour, turn 30 minutes/stop 30 minutes, turn to stop 2 hours；KT1717 0.5-1 parts of addition, 0.5-1.5 parts of akali sulphide, lime 1-3 parts, turn 30 minutes/stop 30 minutes, turn stop 2 hours；KT1717 0.5-1 parts of addition, 0.5-1.5 parts of akali sulphide, lime 1-3 Part, turn 30 minutes/stop 30 minutes, turn stop 2-12 hours；Look into and ruin a mao situation, ruin hair shaft it is net after, be added KT1717 1-5 part, rotate 2 hours, it is added normal-temperature water 30-50 part, 1-2 part of lime, 0.1-0.3 parts of auxiliary liming agent, turns 30 minutes/stop 30 minutes, it was small turn to stop 2 When；Add 50-150 parts of normal-temperature water, 1-2 parts of lime, 0.1-0.3 parts of auxiliary liming agent, turn 30 minutes/stop 30 minutes, turn that stop 2 small Shi Hou, turn 5 minutes/stop 55 minutes, turn to stop 10-24 hour, this step does not have to liming enzyme and other alkaline enzymes, out bulging split, waste liquid Reservation can be used as liming liquid or multiple lixivium is recycled, subsequently into the multiple ash of silica gel；

The multiple grey step of the silica gel are as follows: weigh 100 parts of alkali skins by weight in rotary drum, a mao Lime Liquor 100- is ruined in addition 200 parts, add 1-2 parts of KT1717,0.3-0.5 parts of nonionic degreasing agent, 3-5 parts of lime, turn at a slow speed 30 minutes/stop 30 minutes, turn Stop 4-12 hours；This step does not have to other alkaline enzymes of liming enzyme, and waste liquid reservation can be used as liming liquid or multiple lixivium is recycled, will be grey Severe edema due to hypofunction of the spleen wash clean, into the pre- deliming of silane-hydrogen peroxide (eliminating akali sulphide)；

The pre- deliming of silane-hydrogen peroxide (the eliminating akali sulphide) step are as follows: be added normal-temperature water 50-100 parts, KT1717 2-4 Part, 0.3-0.5 parts of nonionic degreasing agent, slow rotation 2 hours；Add 5-8 parts of ammonium sulfate, 0.5-1 parts of deliming agent, slow rotation 2 Hour；Add 1-2 parts of hydrogen peroxide, slow rotation 4 hours, turn at a slow speed 30 minutes/stop 30 minutes, turn to stop 4-12 hours；This step does not have to The macerating enzymes such as pancreatin, 1398 alkaline enzymes are washed to ph value to be pre-processed after 6.5-7.5 into cationic silica；

The cationic silica pre-treatment step are as follows: be added 35 DEG C 30-50 parts of hot water, 3-5 parts of KT1717, KT4031 3- 5 parts, slow rotation 3 hours, into leaching salt；

The brining step are as follows: be added Nacl 8-10 parts, 8-10 parts of anhydrous sodium sulphate, 35 degree slow rotation 3 hours, into leaching Acid；

The acid soaking step are as follows: industrial 0.5-1.5 parts of formic acid is added, tune pH value range is 2.5-3, and slow rotation 8-12 is small When, first tan is combined into tan/silica gel-tannin extract at the beginning of silicon aldehyde；

Just tan/silica gel-tannin extract combines first tan step to the silicon aldehyde are as follows: KT2811 3-5 parts, acidproof oil 0.1-0.3 is added Part, 2-4 parts of KT2034, slow rotation 4-8 hours；Be added tannin extract 8-16 parts, acidproof 2-4 parts of oil, 4-6 parts of KT2034, 2-4 parts of KT5901, slow rotation 8-12 hours；Add acidproof 1-2 parts of oil, 2-4 parts of KT2034, temperature adjustment is to 45 DEG C, slow rotation 8-12 hours；Drum stands 48 hours out, and water squeezing, shaving ease back into cationic silica；

The cationic silica eases back step are as follows: weighing 100 parts by weight, just tanning is in rotary drum for shaving, washing two Secondary, temperature adjustment is to 45 DEG C；100-150 parts of water, 5-8 parts of KT4031,5-8 parts of KT1717,1-3 parts of KT2811 of 45 DEG C are added, in Speed rotation 4-6 hours adds 1-2 parts of sodium bicarbonate, and middling speed rotates 4-6 hours, this step is not required to use acid enzymatic treatment, into anion silicon Stuffing is filled in glue-tannin extract dyeing retanning；

Fatliquoring steps are filled in the dyeing retanning of the anion silica gel-tannin extract are as follows: with bath be added dyestuff X parts, 3-5 parts of tannin extract, 2-4 parts of KT5901,6-8 parts of KT2034,4-6 parts of KT2351, acidproof 3-5 parts of oil, grease 5-8 parts general, 45 DEG C of middling speed rotations It 8-12 hours, is fixed into cationic silica and mould proof processing；

The cationic silica is fixed and mould proof processing step are as follows: it is 3-3.5,45 DEG C of middling speeds that formic acid tune pH value, which is added, with bath Rotation 1 hour adds 1-3 parts of KT4031, and 0.3-0.5 parts of mould inhibitor, 45 DEG C of middling speeds rotate 2 hours, and washing twice, is roused, in dry out Arrange to obtain skin base.

Preferably, the KT1717 is the displacement neutralization silane that eases back, and KT1717 is the more ammonia in side of weak cation emulsion polymerization Alkyl polyhydroxy alkyl triethoxysilicane alkyl poly methyl silsesquioxane aqueous emulsion, also known as: water-soluble organic silicon macromolecule silane Coupling agent, low temperature are coupled self-cross linking type ammonia alkyl hydroxyl alkyl silicone oil, technical indicator are as follows: 20 DEG C of density 0.95g/ml, the hydrotrope contain Amount 20 ± 1%, aqueous solvent, pH value 6.5 ± 0.2, viscosity 40-50mPa.s, appearance are light blue lotion；

Preferably, the KT3007 is osmotic crosslink silane adjuvant, and KT3007 is multi-epoxy alcohol ether alkyl methyl polysilicone Alkane silane coupling agent isopropanol water solution, technical indicator are as follows: 20 DEG C of density 0.85g/ml, non-volatile component weight percent 36 ± 1%, aqueous solvent, pH value 6.5 ± 0.2, charge nonionic, viscosity 90-110mPa.s, appearance is light yellow to colorless and transparent liquid Body.

Preferably, the KT4031 is cation polyurethane retanning silica gel, and KT4031 is with coupling activity of cross-linking reaction Water-soluble cationic polyurethane high molecule silane coupling agent, while be also a kind of more oxyalkylsiloxane amino of strong cation type Formic acid esters-grease-silicon based polymers；Technical indicator are as follows: 20 DEG C of density 0.95g/ml-1.05g/ml, water solubles content 18- 22%, aqueous solvent, pH value 4.5 ± 0.3, viscosity 400-500mPa.s, appearance is milk yellow emulsion.

Preferably, the KT2811 is amino silane modified fatty aldehyde, and KT2811 is water-soluble organic silicon polyethylene polyamine Class alkalinity macromolecule silane coupling agent has good crosslinking hybrid modified and infiltration, peptizaiton.Technical indicator are as follows: pH value 2- 4, charge weak cation, appearance is light blue lotion.

Preferably, the KT2034 is continuous bubble voluptuousness filling gel, and KT2034 is lecithin and hydroxyl alkyl ammonia alkyl carboxylic hydrocarbon Quito alkoxyl silicone alkyl is modified the secondary derivative of polymethyl siloxane, technical indicator are as follows: 20 DEG C of density 0.92g/ml, the hydrotrope Content 26-30%, aqueous solvent, pH value 3.8 ± 0.2, viscosity 150-180mPa.s, appearance are the thick shape liquid of shallow milk yellow:

Preferably, the KT5901 is that silicon sulfone fills syntans, and KT5901 is silicon sulfone bridge crosslinking structure high quality fillibility The secondary hydrolysis of the naphtholsulfonic acid and SO2 organic derivative of energy, condensation polymer tanning agent, technical indicator are 20 DEG C of density: 1.10g/ ML-1.25g/mL, water solubles content 46%-50%, aqueous solvent, pH value: 4.0 ± 0.2, viscosity: 120mPaS-140mPa S, appearance are light brown translucent glop.

Preferably, the KT2351 is the elastic stuffing silicone oil that foams, and KT2351 is modified poly type silicone oil, modified-reaction type The emulsion type copolymer of silicone oil and ethyleneamino class, carboxyl class monomer etc., technical indicator are as follows: 20 DEG C of density 1.10g/ml- 1.25g/ml, water solubles content 28-33%, aqueous solvent, pH value 4.5-5.5, viscosity 24000-26000mPa.s, appearance are yellow fraction The thicker shape liquid of color.

A kind of water-soluble polyamines base silane coupling agent of the present invention replaces the silane tanning process of enzyme preparation, and its advantages exist In: mode of operation simple and stable, process are easy-to-understand.It saved for 50% or more time, conserves water 40% or more, significantly reduces The resource consumptions such as pollutant discharge amount and water, electricity, manpower.

In traditional tanning process from fur into first tanning, retanning process Reusability biological enzyme formulation, to hide glue Leather loose side mass defect caused by the not easily-controllable or uncontrollable destruction of the natural cross-linked structure of fibrinogen or collagen resolution are scrapped Quality accident brings leather loose side, collagen resolution to scrap the serious psychology of quality accident to traditional leather-making technology operator Pressure.Water soluble polymer polyamines base silane coupling agent replaces biological enzyme formulation for process hides immersion, ruins hair, liming, multiple ash, de- Processes such as ash, and completely abolish traditional enzyme bating process can effectively maintain or reinforce materials with hide glue fibril naturally to hand over as crosslinking agent It is coupled the crosslinking degree of structure, as polyamines base silane coupling agent, materials with hide glue fibril safely effectively submissive softening can be made, to disappear In addition to biological enzyme formulation leather loose side quality caused by the not easily-controllable or uncontrollable destruction of the natural cross-linked structure of materials with hide glue fibril Quality accident is scrapped in defect or collagen resolution, and biological enzyme formulation has been effectively relieved to traditional leather-making technology operator's bring The serious psychological pressure of quality accident is scrapped in leather loose side, collagen resolution, realizes " good skin goes out in silica gel ash cylinder ", allows work Skill operator can easily control and obtain the soft high-quality silica gel voluptuousness leather quality without pine.

Detailed description of the invention

Attached drawing 1 is the structural representation formula of water soluble polymer silane coupling agent.

Attached drawing 2 is application technology route map of the water soluble polymer silane coupling agent in leather sector.

Specific embodiment

It is next combined with specific embodiments below that present invention be described in more detail.

Embodiment 1: thoroughly replace the section of biological enzyme formulation using water soluble polymer polyamines base silane coupling agent of the present invention Water emission reduction silane tanning process makes the flexible buffalo hide vegetable tanning summer sleeping mat leather of the personal pro-skin ecology of environment-friendly type silica gel-tannin extract Combined tanning, Including the immersion of fur silane, silane-akali sulphide ruin a mao liming, the multiple ash of silica gel, the pre- deliming of silane-hydrogen peroxide (eliminating akali sulphide), The main deliming of silane-hydrogen peroxide (eliminating akali sulphide), cationic silica pretreatment, leaching salt, pickling, the first tan/silica gel-tannin extract knot of silicon aldehyde Close first tan, cationic silica eases back, anion silica gel-tannin extract dyeing retanning filling stuffing, cationic silica is fixed and mould proof place Reason, the specific steps are as follows:

(1) fur silane soaks: weighing 100 parts of buffalo furs by weight in rotary drum, washes 10 minutes, normal-temperature water is added 150 parts, 0.5 part of KT1717,0.1 part of KT3007,0.3 part of nonionic degreasing agent, 0.1 part of fungicide, 0.5 part of soda ash, vulcanization After 0.3 part of sodium, slow rotation 3 hours, turn 30 minutes/stop 30 minutes, turn stop 10 hours, this step do not have to soaking enzyme, defatting enzyme, out Drum, fleshing, deburring ruin a mao liming into silane-akali sulphide；

(2) silane-akali sulphide ruins a mao liming: be added 20 parts of normal-temperature water, 0.3 part of KT1717,0.3 part of nonionic degreasing agent, 0.5 part of auxiliary liming agent, 0.6 part of NaHS, 0.6 part of vulcanized sodium, after slow rotation 1 hour, turn 30 minutes/stop 30 minutes, turn Stop 2 hours；Be added 0.5 part of KT1717,0.6 part of akali sulphide, 2 parts of lime, turn 30 minutes/stop 30 minutes, turn stop 2 hours；It is added 0.5 part of KT1717,0.6 part of akali sulphide, 2 parts of lime, turn 30 minutes/stop 30 minutes, turn stop 10 hours；It looks into and ruins a mao situation, ruin hair After clean, 3 parts of KT1717 are added, is rotated 2 hours, 30 parts of normal-temperature water, 1 part of lime, 0.2 part of auxiliary liming agent is added, turns 30 points Clock/stop 30 minutes turns to stop 2 hours；Add 80 parts of normal-temperature water, 2 parts of lime, 0.3 part of auxiliary liming agent, turn 30 minutes/stop 30 points Clock, turn stop 2 hours after, turn 5 minutes/stop 55 minutes, turn stop 24 hours, this step do not have to liming enzyme, out rouse split, waste liquid reservation can It is recycled as liming liquid or multiple lixivium, subsequently into the multiple ash of silica gel；

(3) the multiple ash of silica gel: weighing 100 parts of alkali skins in rotary drum by weight, and addition ruins 200 parts of mao Lime Liquor, adds 1 part of KT1717,0.5 part of nonionic degreasing agent, 3 parts of lime, turn at a slow speed 30 minutes/stop 30 minutes, turn stop 10 hours；This step is not With liming enzyme, waste liquid reservation can be used as liming liquid or multiple lixivium is recycled, and graywall is washed completely, into silane-hydrogen peroxide Pre- deliming (eliminating akali sulphide)；

(4) the pre- deliming of silane-hydrogen peroxide (eliminating akali sulphide): 50 parts of normal-temperature water of addition, 1 part of KT1717, nonionic degreasing 0.3 part of agent, slow rotation 2 hours；Add 3 parts of ammonium sulfate, 0.5 part of deliming agent, slow rotation 2 hours；Add 1 part of hydrogen peroxide, at a slow speed Rotation 4 hours, this step do not have to the macerating enzymes such as pancreatin, 1398 alkaline enzymes, and washing is clean, (eliminates into the main deliming of silane-hydrogen peroxide Akali sulphide)；

(5) the main deliming of silane-hydrogen peroxide (eliminating akali sulphide): 30 parts of normal-temperature water of addition, 2 parts of KT1717, nonionic degreasing 0.3 part of agent, slow rotation 2 hours；Add 8 parts of ammonium sulfate, 0.5 part of deliming agent, slow rotation 2 hours；Add 1 part of hydrogen peroxide, at a slow speed Rotation 4 hours, turn at a slow speed 30 minutes/stop 30 minutes, turn stop 10 hours；This step does not have to the macerating enzymes such as pancreatin, 1398 alkaline enzymes, water PH value is washed till to be pre-processed after 6.5-7.5 into cationic silica；

(6) cationic silica pre-processes: being added 35 DEG C 30 parts of hot water, 3 parts of KT1717,3 parts of KT4031, slow rotation 3 Hour, into leaching salt；

(7) soak salt: be added 8 parts of Nacl, 8 parts of anhydrous sodium sulphate, 35 DEG C slow rotation 3 hours, into pickling；

(8) pickling: being added industrial 1.5 parts of formic acid, and tunes pH value range is 2.5-3, and slow rotation 8 hours, at the beginning of silicon aldehyde Tan/silica gel-tannin extract combines first tan

(9) silicon aldehyde just tan/silica gel-tannin extract combine first tan: be added 4 parts of KT2811, it is oily 0.3 part acidproof, 4 parts of KT2034, Slow rotation 6 hours；12 parts of tannin extract, oily 4 parts acidproof, 6 parts of KT2034,3 parts of KT5901 is added, 35 DEG C of slow rotations 10 are small When；Add acidproof oily 2 parts, 4 parts of KT2034, temperature adjustment is to 45 DEG C, slow rotation 10 hours；Drum stands 48 hours out, water squeezing, shaving, It eases back into cationic silica；

(10) cationic silica eases back: weighing 100 parts by weight, just tanning washes temperature adjustment twice in rotary drum to shaving To 45 DEG C；100 parts of water, 6 parts of KT4031,6 parts of KT1717,2 parts of KT2811 of 45 DEG C are added, middling speed rotates 4 hours, adds small 2 parts of soda, middling speed rotates 4 hours, this, which is walked, is not required to use acid enzymatic treatment, adds into anion silica gel-tannin extract dyeing retanning filling Rouge；

(11) stuffing is filled in anion silica gel-tannin extract dyeing retanning: dyestuff X parts, 5 parts of tannin extract, KT5901 2 is added with bath Part, 5 parts of KT2034,5 parts of KT2351, it is oily 3 parts acidproof, 8 parts of fatting agent, 45 DEG C of middling speeds rotate 6 hours, into cationic silica Fixed and mould proof processing；

(12) cationic silica is fixed and mould proof processing: it is 3-3.5,45 DEG C of middling speeds rotations 1 that formic acid tune pH value, which is added, with bath Hour, add 2 parts of KT4031,0.3 part of mould inhibitor, 45 DEG C of middling speeds rotate 2 hours, and washing twice, is roused out, is arranged into drying Skin base.

The industrial products such as above-mentioned KT1717, KT3007, KT2811, KT4031, KT2034, KT5901, KT2351, from Chengdu City Wenjiang District Ming Nida fluosilicic skin application study pilot plant is bought.The environment-friendly type silica gel made using the present invention-tannin extract is combined The personal flexible buffalo hide vegetable tanning summer sleeping mat of pro-skin ecology of tan, it is cool without ice, mild exquisiteness when with human skin intimate contact, i.e., it is cool It is refreshing comfortable and uncomfortable without ice-cold stimulation, there is a fine and glossy smooth sense of silk and the coarse and stiff sense without linen-cotton.

Embodiment 2: thoroughly replace the section of biological enzyme formulation using water soluble polymer polyamines base silane coupling agent of the present invention Water emission reduction silane tanning process makes the flexible smooth surface rabbit brassiere internal layer parent of the personal pro-skin ecology of environment-friendly type silica gel-tannin extract Combined tanning Skin leather, including fur silane soaks, silica gel packet ash pushes away hair, silane-akali sulphide ruins a mao liming, the pre- deliming of silane-hydrogen peroxide (is eliminated Akali sulphide), the main deliming of silane-hydrogen peroxide (eliminate akali sulphide), cationic silica pretreatment, leaching salt, pickling, the first tan/silicon of silicon aldehyde Glue-tannin extract combines first tan, cationic silica to ease back, anion silica gel-tannin extract dyeing retanning filling stuffing, cationic silica are fixed And mould proof processing, the specific steps are as follows:

(1) fur silane soaks: weighing 100 parts of coneys by weight in rotary drum, washes 10 minutes, normal-temperature water is added 150 parts, 0.5 part of KT1717,0.1 part of KT3007,0.3 part of nonionic degreasing agent, 0.1 part of fungicide, 0.5 part of soda ash, vulcanization After 0.3 part of sodium, slow rotation 3 hours, turn 30 minutes/stop 30 minutes, turn stop 10 hours, this step do not have to soaking enzyme, defatting enzyme, out Drum, cuts off head, tail, four limbs, draining moisturizing pushes away hair into silica gel packet ash.

(2) silica gel packet ash pushes away hair: weighing 5000 parts of water, 40 parts of KT1717,20 parts of KT3007, auxiliary liming agent 20 by weight Part, 50 parts of nonionic degreasing agent, 80 parts of NaHS, 250 parts of vulcanized sodium；It stirs evenly, is slow added into 3000 parts of lime, side edged It stirs, obtains packet mortar.Packet mortar is applied to rabbit flesh noodles, ridge line applying amount suitably increases, and the overlapping of meat meat stands and stacks 6- 12 hours, hair is pushed away, into drum, ruins a mao liming into silane-akali sulphide.

(3) silane-akali sulphide ruins a mao liming: be added 20 parts of normal-temperature water, 0.3 part of KT1717,0.3 part of nonionic degreasing agent, 0.5 part of auxiliary liming agent, 0.6 part of NaHS, 0.6 part of vulcanized sodium, after slow rotation 1 hour, turn 30 minutes/stop 30 minutes, turn Stop 4 hours；Look into and ruin a mao situation, ruin hair shaft it is net after, be added 3 parts of KT1717, rotate 2 hours, be added 30 parts of normal-temperature water, lime 1 Part, 0.2 part of auxiliary liming agent, turn 30 minutes/stop 30 minutes, turn stop 2 hours；Add 80 parts of normal-temperature water, 2 parts of lime, liming help 0.3 part of agent, turn 30 minutes/stop 30 minutes, turn stop 2 hours after, turn 5 minutes/stop 55 minutes, turn stop 24 hours, this step do not have to leaching Grey enzyme, waste liquid reservation can be used as liming liquid or multiple lixivium is recycled, and (eliminates and vulcanizes subsequently into the pre- deliming of silane-hydrogen peroxide Alkali).

(4) the pre- deliming of silane-hydrogen peroxide (eliminating akali sulphide): 50 parts of normal-temperature water of addition, 1 part of KT1717, nonionic degreasing 0.3 part of agent, slow rotation 2 hours；Add 3 parts of ammonium sulfate, 0.5 part of deliming agent, slow rotation 2 hours；Add 1 part of hydrogen peroxide, at a slow speed Rotation 4 hours, this step do not have to the macerating enzymes such as pancreatin, 1398 alkaline enzymes, and washing is clean, (eliminates into the main deliming of silane-hydrogen peroxide Akali sulphide).

(5) the main deliming of silane-hydrogen peroxide (eliminating akali sulphide): 30 parts of normal-temperature water of addition, 2 parts of KT1717, nonionic degreasing 0.3 part of agent, slow rotation 2 hours；Add 8 parts of ammonium sulfate, 0.5 part of deliming agent, slow rotation 2 hours；Add 1 part of hydrogen peroxide, at a slow speed Rotation 4 hours, turn at a slow speed 30 minutes/stop 30 minutes, turn stop 10 hours；This step does not have to the macerating enzymes such as pancreatin, 1398 alkaline enzymes, water PH value is washed till to be pre-processed after 6.5-7.5 into cationic silica.

(6) cationic silica pre-processes: being added 35 DEG C 30 parts of hot water, 3 parts of KT1717,3 parts of KT4031, slow rotation 3 Hour, into leaching salt.

(7) soak salt: be added 8 parts of Nacl, 8 parts of anhydrous sodium sulphate, 35 DEG C slow rotation 3 hours, into pickling.

(8) pickling: being added industrial 1.5 parts of formic acid, and tunes pH value range is 2.5-3, and slow rotation 8 hours, at the beginning of silicon aldehyde Tan/silica gel-tannin extract combines first tan.

(9) silicon aldehyde just tan/silica gel-tannin extract combine first tan: be added 4 parts of KT2811, it is oily 0.3 part acidproof, 4 parts of KT2034, Slow rotation 6 hours；12 parts of tannin extract, oily 4 parts acidproof, 6 parts of KT2034,3 parts of KT5901 is added, 35 DEG C of slow rotations 10 are small When；Add acidproof oily 2 parts, 4 parts of KT2034, temperature adjustment is to 45 DEG C, slow rotation 10 hours；Drum stands 48 hours out, water squeezing, shaving, It eases back into cationic silica.

(10) cationic silica eases back: weighing 100 parts by weight, just tanning washes temperature adjustment twice in rotary drum to shaving To 45 DEG C；100 parts of water, 6 parts of KT4031,6 parts of KT1717,2 parts of KT2811 of 45 DEG C are added, middling speed rotates 4 hours, this step It is not required to use acid enzymatic treatment, adds 2 parts of sodium bicarbonate, middling speed rotates 4 hours, adds into anion silica gel-tannin extract dyeing retanning filling Rouge.

(11) stuffing is filled in anion silica gel-tannin extract dyeing retanning: dyestuff X parts, 5 parts of tannin extract, KT5901 2 is added with bath Part, 5 parts of KT2034,5 parts of KT2351, it is oily 3 parts acidproof, 8 parts of fatting agent, 45 DEG C of middling speeds rotate 6 hours, into cationic silica Fixed and mould proof processing.

The industrial products such as above-mentioned KT1717, KT3007, KT2811, KT4031, KT2034, KT5901, KT2351, from Chengdu City Wenjiang District Ming Nida fluosilicic skin application study pilot plant is bought.The environment-friendly type silica gel made using the present invention-tannin extract is combined The flexible smooth surface rabbit brassiere internal layer pro-skin leather of tan personal pro-skin ecology, when with papilla of breast intimate contact, soft exquisiteness, moisture-inhibiting is saturating Gas, comfortable penetrating, antimycotic antiseptic have good skin physiology respiratory function, have the fine and glossy smooth of silk and without the thick of linen-cotton It is rough stiff.

Embodiment 3: thoroughly replace the section of biological enzyme formulation using water soluble polymer polyamines base silane coupling agent of the present invention Water emission reduction silane tanning process makes the flexible sheepskin brassiere outer layer support lining of the personal pro-skin ecology of environment-friendly type silica gel-tannin extract Combined tanning Leather, including fur silane soaks, silica gel packet ash pushes away hair, silane-akali sulphide ruins a mao liming, ash, silane-hydrogen peroxide are pre- de- again for silica gel Ash (eliminating akali sulphide), the main deliming of silane-hydrogen peroxide (eliminating akali sulphide), cationic silica pretreatment, leaching salt, pickling, silicon aldehyde First tan/silica gel-tannin extract combines first tan, cationic silica to ease back, stuffing, cation are filled in anion silica gel-tannin extract dyeing retanning Silica gel is fixed and mould proof processing, the specific steps are as follows:

(1) fur silane soaks: weighing 100 parts of sheep skins by weight in rotary drum, washes 10 minutes, normal-temperature water is added 150 parts, 0.5 part of KT1717,0.1 part of KT3007,0.3 part of nonionic degreasing agent, 0.1 part of fungicide, 0.5 part of soda ash, vulcanization After 0.3 part of sodium, slow rotation 3 hours, turn 30 minutes/stop 30 minutes, turn stop 10 hours, this step do not have to soaking enzyme, defatting enzyme, out Drum, cuts off head, tail, four limbs, draining moisturizing pushes away hair into silica gel packet ash.

(2) silica gel packet ash pushes away hair: wrapping grey slurry formula are as follows: weigh 5000 parts of water, 40 parts of KT1717, KT3007 20 by weight Part, 20 parts of auxiliary liming agent, 50 parts of nonionic degreasing agent, 80 parts of NaHS, 250 parts of vulcanized sodium；It stirs evenly, is slow added into lime 3000 parts, side edged stirs, and obtains packet mortar.Packet mortar is applied to sheepskin flesh noodles, ridge line applying amount suitably increases, meat meat Overlapping stands and stacks 12-24 hours, pushes away hair, into drum, ruin a mao liming into silane-akali sulphide.

(3) silane-akali sulphide ruins a mao liming: be added 20 parts of normal-temperature water, 0.3 part of KT1717,0.3 part of nonionic degreasing agent, 0.5 part of auxiliary liming agent, 0.6 part of NaHS, 0.6 part of vulcanized sodium, after slow rotation 1 hour, turn 30 minutes/stop 30 minutes, turn Stop 4 hours；Look into and ruin a mao situation, ruin hair shaft it is net after, be added 3 parts of KT1717, rotate 2 hours, be added 30 parts of normal-temperature water, lime 1 Part, 0.2 part of auxiliary liming agent, turn 30 minutes/stop 30 minutes, turn stop 2 hours；Add 80 parts of normal-temperature water, 2 parts of lime, liming help 0.3 part of agent, turn 30 minutes/stop 30 minutes, turn stop 2 hours after, turn 5 minutes/stop 55 minutes, turn stop 24 hours this step do not have to liming Enzyme, waste liquid reservation can be used as liming liquid or multiple lixivium is recycled, subsequently into the multiple ash of silica gel.

(4) the multiple ash of silica gel: addition ruins 200 parts of mao Lime Liquor, adds 1 part of KT1717, and 0.5 part of nonionic degreasing agent, lime 3 parts, turn at a slow speed 30 minutes/stop 30 minutes, turn to stop 10 hours, this step does not have to liming enzyme, and waste liquid reservation can be used as liming liquid or multiple Lixivium is recycled, and graywall is washed completely, into the pre- deliming of silane-hydrogen peroxide (eliminating akali sulphide).

(5) the pre- deliming of silane-hydrogen peroxide (eliminating akali sulphide): 50 parts of normal-temperature water of addition, 1 part of KT1717, nonionic degreasing 0.3 part of agent, slow rotation 2 hours；Add 3 parts of ammonium sulfate, 0.5 part of deliming agent, slow rotation 2 hours；Add 1 part of hydrogen peroxide, at a slow speed Rotation 4 hours, this step do not have to the macerating enzymes such as pancreatin, 1398 alkaline enzymes, and washing is clean, (eliminates into the main deliming of silane-hydrogen peroxide Akali sulphide).

(6) the main deliming of silane-hydrogen peroxide (eliminating akali sulphide): 30 parts of normal-temperature water of addition, 2 parts of KT1717, nonionic degreasing 0.3 part of agent, slow rotation 2 hours；Add 8 parts of ammonium sulfate, 0.5 part of deliming agent, slow rotation 2 hours；Add 1 part of hydrogen peroxide, at a slow speed Rotation 4 hours, turn at a slow speed 30 minutes/stop 30 minutes, turn stop 10 hours；This step does not have to the macerating enzymes such as pancreatin, 1398 alkaline enzymes, water PH value is washed till to be pre-processed after 6.5-7.5 into cationic silica.

(7) cationic silica pre-processes: being added 35 DEG C 30 parts of hot water, 3 parts of KT1717,3 parts of KT4031, slow rotation 3 Hour, into leaching salt.

(8) soak salt: be added 8 parts of Nacl, 8 parts of anhydrous sodium sulphate, 35 DEG C slow rotation 3 hours, into pickling.

(9) pickling: being added industrial 1.5 parts of formic acid, and tunes pH value range is 2.5-3, and slow rotation 8 hours, at the beginning of silicon aldehyde Tan/silica gel-tannin extract combines first tan.

(10) silicon aldehyde just tan/silica gel-tannin extract combine first tan: be added 4 parts of KT2811, it is oily 0.3 part acidproof, 4 parts of KT2034, Slow rotation 6 hours；12 parts of tannin extract, oily 4 parts acidproof, 6 parts of KT2034,3 parts of KT5901 is added, 35 DEG C of slow rotations 10 are small When；Add acidproof oily 2 parts, 4 parts of KT2034, temperature adjustment is to 45 DEG C, slow rotation 10 hours；Drum stands 48 hours out, water squeezing, shaving, It eases back into cationic silica.

(11) cationic silica eases back: weighing 100 parts by weight, just tanning washes temperature adjustment twice in rotary drum to shaving To 45 DEG C；100 parts of water, 6 parts of KT4031,6 parts of KT1717,2 parts of KT2811 of 45 DEG C are added, middling speed rotates 4 hours, adds small 2 parts of soda, middling speed rotates 4 hours, this, which is walked, is not required to use acid enzymatic treatment, adds into anion silica gel-tannin extract dyeing retanning filling Rouge.

(12) stuffing is filled in anion silica gel-tannin extract dyeing retanning: dyestuff X parts, 5 parts of tannin extract, KT5901 2 is added with bath Part, 5 parts of KT2034,5 parts of KT2351, it is oily 3 parts acidproof, 8 parts of fatting agent, 45 DEG C of middling speeds rotate 6 hours, into cationic silica Fixed and mould proof processing.

(13) cationic silica is fixed and mould proof processing: it is 3-3.5,45 DEG C of middling speeds rotations 1 that formic acid tune pH value, which is added, with bath Hour, add 2 parts of KT4031,0.3 part of mould inhibitor, 45 DEG C of middling speeds rotate 2 hours, and washing twice, is roused out, into being dried Skin base.

The industrial products such as above-mentioned KT1717, KT3007, KT2811, KT4031, KT2034, KT5901, KT2351, from Chengdu City Wenjiang District Ming Nida fluosilicic skin application study pilot plant is bought.The environment-friendly type silica gel made using the present invention-tannin extract is combined The flexible smooth surface sheepskin brassiere outer layer support lining leather of tan personal pro-skin ecology, it is soft, high resilience, well-pressed and be easy to be formed, Feel is fine and smooth, comfortable penetrating；Interlayer especially between brassiere internal layer pro-skin rabbit and brassiere outer layer support lining sheepskin can be put The design for setting special efficacy breast health-care nursing Chinese medicine package has particularly dredging breast channels and collaterals, preventing mammary gland hyperplasia and breast cancer Nurse effect；Have simultaneously and lift breast tissue in poly-, is allowed to tall and straight plentiful sexuality, it can be to avoid the harmful sea of conventional toxic Pessimal stimulation or even injury of the brassieres such as silk floss, plastic foam filler to breast；In addition can absorbing sweat, be unlikely to deform, be easy to arrange Storage, self-cleaning etc. have more powerful function than same type of material.

It is provided for the embodiments of the invention technical solution above to be described in detail, specific case used herein The principle and embodiment of the embodiment of the present invention are expounded, the explanation of above embodiments is only applicable to help to understand this The principle of inventive embodiments；At the same time, for those skilled in the art, according to an embodiment of the present invention, in specific embodiment party There will be changes in formula and application range, in conclusion the contents of this specification are not to be construed as limiting the invention.

Claims

1. a kind of water-soluble polyamines base silane coupling agent replaces the silane tanning process of enzyme preparation, including the immersion of fur silane, silicon Glue packet ash pushes away hair, silane-akali sulphide ruins a mao liming, ash, the pre- deliming of silane-hydrogen peroxide (eliminating akali sulphide), silane-are bis- again for silica gel The main deliming of oxygen water (eliminate akali sulphide), cationic silica pretreatment, leaching salt, pickling, silicon aldehyde just tan/silica gel-tannin extract combine first tan, Cationic silica eases back, anion silica gel-tannin extract dyeing retanning filling stuffing, cationic silica is fixed and mould proof processing, special Sign is:

(1) the fur silane immersion step are as follows: weigh 100 parts of furs by weight in rotary drum, wash 10 minutes, room temperature is added 100-150 parts of water, 0.1-1 parts of KT1717,0.05-0.3 parts of KT3007,0.2-0.5 parts of nonionic degreasing agent, fungicide 0.1- 0.3 part, 0.3-1 parts of soda ash, 0.1-0.3 parts of vulcanized sodium, after slow rotation 3 hours, turn 30 minutes/stop 30 minutes, turn stop 8-10 Hour, this step does not have to soaking enzyme, defatting enzyme, rouses, fleshing out, pushes away hair into silica gel packet ash；

(2) the silica gel packet ash pushes away a mao step are as follows: weighs 5000 parts of water, 30-60 parts of KT1717, KT3007 15-40 by weight Part, 20-40 parts of auxiliary liming agent, 30-60 parts of nonionic degreasing agent, 60-100 parts of NaHS, 240-280 parts of vulcanized sodium；It stirs evenly, 3000-4000 parts of lime are slow added into, side edged stirs, and stirs evenly to obtain packet mortar；Packet mortar is applied to fur flesh noodles, ridge Line applying amount suitably increases, and the overlapping of meat meat stands and stacks 6-24 hours, this step does not have to liming enzyme and other alkaline enzymes, pushes away hair, into Enter silane-akali sulphide and ruins a mao liming；

(3) silane-akali sulphide ruins a mao liming step are as follows: be added normal-temperature water 10-30 parts, 0.1-0.3 parts of KT1717, it is non-from Sub- degreasing agent 0.3-0.5 parts, 0.3-0.5 parts of auxiliary liming agent, 0.5-0.8 parts of NaHS, 0.5-0.8 parts of vulcanized sodium, turn at a slow speed After dynamic 1 hour, turn 30 minutes/stop 30 minutes, turn to stop 2 hours；KT1717 0.5-1 parts of addition, 0.5-1.5 parts of akali sulphide, lime 1-3 parts, turn 30 minutes/stop 30 minutes, turn stop 2 hours；KT1717 0.5-1 parts of addition, 0.5-1.5 parts of akali sulphide, lime 1-3 Part, turn 30 minutes/stop 30 minutes, turn stop 2-12 hours；Look into and ruin a mao situation, ruin hair shaft it is net after, be added KT1717 1-5 part, rotate 2 hours, it is added normal-temperature water 30-50 part, 1-2 part of lime, 0.1-0.3 parts of auxiliary liming agent, turns 30 minutes/stop 30 minutes, it was small turn to stop 2 When；Add 50-150 parts of normal-temperature water, 1-2 parts of lime, 0.1-0.3 parts of auxiliary liming agent, turn 30 minutes/stop 30 minutes, turn that stop 2 small Shi Hou, turn 5 minutes/stop 55 minutes, turn to stop 10-24 hour, this step does not have to liming enzyme and other alkaline enzymes, out bulging split, waste liquid Reservation can be used as liming liquid or multiple lixivium is recycled, subsequently into the multiple ash of silica gel；

(4) the multiple grey step of the silica gel are as follows: weigh 100 parts of alkali skins by weight in rotary drum, a mao Lime Liquor 100-200 is ruined in addition Part, add 1-2 part of KT1717,0.3-0.5 parts of nonionic degreasing agent, 3-5 parts of lime, turn at a slow speed 30 minutes/stop 30 minutes, turn stop 4-12 hours, this step did not had to liming enzyme and other alkaline enzymes；Waste liquid reservation can be used as liming liquid or multiple lixivium is recycled, will be grey Severe edema due to hypofunction of the spleen wash clean, into the pre- deliming of silane-hydrogen peroxide (eliminating akali sulphide)；

(5) the pre- deliming of silane-hydrogen peroxide (the eliminating akali sulphide) step are as follows: be added normal-temperature water 50-100 parts, KT1717 1-2 Part, 0.3-0.5 parts of nonionic degreasing agent, slow rotation 2 hours；Add 3-5 parts of ammonium sulfate, 0.5-1 parts of deliming agent, slow rotation 2 Hour；Adding 1-2 parts of hydrogen peroxide, slow rotation 4 hours, this step did not had to the macerating enzymes such as pancreatin, 1398 alkaline enzymes, and washing is clean, into Enter the main deliming of silane-hydrogen peroxide (eliminating akali sulphide)；

(6) the main deliming of silane-hydrogen peroxide (the eliminating akali sulphide) step are as follows: be added normal-temperature water 30-50 parts, KT1717 2-4 Part, 0.3-0.5 parts of nonionic degreasing agent, slow rotation 2 hours；Add 5-8 parts of ammonium sulfate, 0.5-1 parts of deliming agent, slow rotation 2 Hour；Add 1-2 parts of hydrogen peroxide, slow rotation 4 hours, turn at a slow speed 30 minutes/stop 30 minutes, turn to stop 4-12 hours；This step does not have to The macerating enzymes such as pancreatin, 1398 alkaline enzymes are washed to pH value after 6.5-7.5, not have to carry out the macerating enzymes such as pancreatin, 1398 alkaline enzymes Processing is pre-processed into cationic silica；

(7) the cationic silica pre-treatment step are as follows: be added 35 DEG C 30-50 parts of hot water, 3-5 parts of KT1717, KT4031 3-5 Part, slow rotation 3 hours, into leaching salt；

(8) brining step are as follows: be added Nacl 8-10 parts, 8-10 parts of anhydrous sodium sulphate, 35 DEG C slow rotation 3 hours, into leaching Acid；

(9) acid soaking step are as follows: industrial 0.5-1.5 parts of formic acid is added, tune pH value range is 2.5-3, and slow rotation 8-12 is small When, first tan is combined into tan/silica gel-tannin extract at the beginning of silicon aldehyde；

(10) just tan/silica gel-tannin extract combines first tan step to the silicon aldehyde are as follows: KT2811 3-5 parts, acidproof oil 0.1-0.3 is added Part, 2-4 parts of KT2034, slow rotation 4-8 hours；Be added tannin extract 8-16 parts, acidproof 2-4 parts of oil, 4-6 parts of KT2034, 2-4 parts of KT5901, slow rotation 8-12 hours；Add acidproof 1-2 parts of oil, 2-4 parts of KT2034, temperature adjustment is to 45 DEG C, slow rotation 8-12 hours；Drum stands 48 hours out, and water squeezing, shaving ease back into cationic silica；

(11) cationic silica eases back step are as follows: weighing 100 parts by weight, just tanning is in rotary drum for shaving, washing two Secondary, temperature adjustment is to 45 DEG C；100-150 parts of water, 5-8 parts of KT4031,5-8 parts of KT1717,1-3 parts of KT2811 of 45 DEG C are added, in Speed rotation 4-6 hours adds 1-2 parts of sodium bicarbonate, and middling speed rotates 4-6 hours, this step is not required to use acid enzymatic treatment, into anion silicon Stuffing is filled in glue-tannin extract dyeing retanning；

(12) fatliquoring steps are filled in the anion silica gel-tannin extract dyeing retanning are as follows: with bath be added dyestuff X parts, 3-5 parts of tannin extract, 2-4 parts of KT5901,6-8 parts of KT2034,4-6 parts of KT2351, acidproof 3-5 parts of oil, grease 5-8 parts general, 45 DEG C of middling speed rotations It 8-12 hours, is fixed into cationic silica and mould proof processing；

(13) cationic silica is fixed and mould proof processing step are as follows: it is 3-3.5,45 DEG C of middling speeds that formic acid tune pH value, which is added, with bath Rotation 1 hour adds 1-3 parts of KT4031,0.3-0.5 parts of mould inhibitor, and 45 DEG C of middling speeds rotate 2 hours, and washing twice, is roused out, dry Arrange to obtain skin base.

2. water soluble polymer polyamines base silane coupling agent thoroughly replaces the water-saving of biological enzyme formulation to subtract according to claim 1 Arrange silane tanning process, it is characterised in that: the KT1717 is the displacement neutralization silane that eases back, and KT1717 is poly- for weak cation lotion The more ammonia alkyl polyhydroxy alkyl triethoxysilicane alkyl poly methyl silsesquioxane aqueous emulsions in the side of conjunction, also known as: water-soluble organic silicon Macromolecule silane coupling agent, low temperature are coupled self-cross linking type ammonia alkyl hydroxyl alkyl silicone oil, technical indicator are as follows: 20 DEG C of density 0.95g/ Ml, water solubles content 20 ± 1%, aqueous solvent, pH value 6.5 ± 0.2, viscosity 40-50mPa.s, appearance are light blue lotion.

3. water soluble polymer polyamines base silane coupling agent thoroughly replaces the water-saving of biological enzyme formulation to subtract according to claim 1 Arrange silane tanning process, it is characterised in that: the KT3007 is osmotic crosslink silane adjuvant, and KT3007 is multi-epoxy alcohol ether alkyl Polymethyl siloxane silane coupling agent isopropanol water solution, technical indicator are as follows: 20 DEG C of density 0.85g/ml, non-volatile component weight Percentage 36 ± 1%, aqueous solvent, pH value 6.5 ± 0.2, charge nonionic, viscosity 90-110mPa.s, appearance be it is light yellow extremely Colourless transparent liquid.

4. water soluble polymer polyamines base silane coupling agent thoroughly replaces the water-saving of biological enzyme formulation to subtract according to claim 1 Arrange silane tanning process, it is characterised in that: the KT4031 is cation polyurethane retanning silica gel, and KT4031 is to hand over coupling Join the water-soluble cationic polyurethane high molecule silane coupling agent of reactivity, while being also a kind of more alkoxies of strong cation type Siloxanes carbamate-grease-silicon based polymers；Technical indicator are as follows: 20 DEG C of density 0.95g/ml-1.05g/ml, the hydrotrope Content 18-22%, aqueous solvent, pH value 4.5 ± 0.3, viscosity 400-500mPa.s, appearance are milk yellow emulsion.

5. water soluble polymer polyamines base silane coupling agent thoroughly replaces the water-saving of biological enzyme formulation to subtract according to claim 1 Arrange silane tanning process, it is characterised in that: the KT2811 is amino silane modified fatty aldehyde；KT2811 is containing the water-soluble of aldehyde radical Property organosilicon polyethylene polyamine class macromolecule silane coupling agent, have good crosslinking hybrid modified and infiltration, peptizaiton；Technology Index are as follows: pH value 2-4, charge weak cation, appearance are light blue lotion.

6. according to claim 1 state water soluble polymer polyamines base silane coupling agent the water-saving of biological enzyme formulation thoroughly replaced to subtract Arrange silane tanning process, it is characterised in that: the KT2034 is continuous bubble voluptuousness filling gel, and KT2034 is lecithin and hydroxyl alkyl The modified secondary derivative of polymethyl siloxane of the more alkoxyl silicone alkyl of ammonia alkyl carboxylic alkyl, technical indicator are as follows: 20 DEG C of density 0.92g/ml, water solubles content 26-30%, aqueous solvent, pH value 3.8 ± 0.2, viscosity 150-180mPa.s, appearance are shallow yellow fraction The thick shape liquid of color.

7. water soluble polymer polyamines base silane coupling agent thoroughly replaces the water-saving of biological enzyme formulation to subtract according to claim 1 Arrange silane tanning process, it is characterised in that: the KT5901 is that silicon sulfone fills syntans, and KT5901 is that silicon sulfone bridge crosslinking structure is high The secondary hydrolysis of the naphtholsulfonic acid and SO2 organic derivative of mass charge performance, condensation polymer tanning agent, technical indicator are 20 DEG C close Degree: 1.10g/mL-1.25g/mL, water solubles content 46%-50%, aqueous solvent, pH value: 4.0 ± 0.2, viscosity: 120mPaS- 140mPaS, appearance are light brown translucent glop.

8. water soluble polymer polyamines base silane coupling agent thoroughly replaces the water-saving of biological enzyme formulation to subtract according to claim 1 Arrange silane tanning process, it is characterised in that: the KT2351 is the elastic stuffing silicone oil that foams, and KT2351 is modified poly type silicon The emulsion type copolymer of oil, modified-reaction type silicone oil and ethyleneamino class, carboxyl class monomer etc., technical indicator are as follows: 20 DEG C close Spend 1.10g/ml-1.25g/ml, water solubles content 28-33%, aqueous solvent, pH value 4.5-5.5, viscosity 24000- 26000mPa.s, appearance are the thicker shape liquid of milk yellow.

9. water soluble polymer polyamines base silane coupling agent thoroughly replaces the water-saving of biological enzyme formulation to subtract according to claim 1 Arrange silane tanning process, it is characterised in that: KT1717, KT3007, KT2811, KT4031, KT2034, KT5901, KT2351 etc. Industrial products, from Wenjiang district of Chengdu city, Ming Nida fluosilicic skin application study pilot plant is bought.