CN109097506B

CN109097506B - Manufacturing process of silane tanned leather by combining chromium-free ecological silica gel-tannin extract to tanned vegetable tanned leather

Info

Publication number: CN109097506B
Application number: CN201710723148.1A
Authority: CN
Inventors: 阳庆文; 陈磊; 帅晓强; 蓝华全; 徐沙; 卢宁沙
Original assignee: Chengdu Kate Organosilicon New Material Technology Co ltd
Current assignee: Chengdu Kate Organosilicon New Material Technology Co ltd
Priority date: 2017-06-21
Filing date: 2017-08-22
Publication date: 2021-07-27
Anticipated expiration: 2037-08-22
Also published as: CN109097506A

Abstract

The invention discloses a manufacturing process of silane tanning of chromium-free ecological silica gel-tannin extract combined vegetable tanning leather, which comprises the steps of fur silane soaking, silane ash-coating, fur pushing and fur destroying, and silica gel cross-linking liming; after the alkali skin is sliced, silica gel is relished, silica gel is delimed, salt is soaked, silica gel is pickled, cationic polyurethane silica gel is pretreated, silica aldehyde is pretanned, and silica gel-tannin extract is primarily tanned; after shaving evenly, the cationic polyurethane silica gel is subjected to softening pretreatment, silica gel-tannin extract dyeing retanning and cationic polyurethane silica gel fixing mildew prevention, so that the pollutant discharge amount and the consumption of water, electricity and human resources are obviously reduced. According to the invention, the tannin extract tanning is implanted in the process of forming organic silica gel by using a water-soluble high-molecular silane coupling agent under an alkaline condition, the defects of hardness and poor hand feeling of a traditional vegetable tanning leather plate are overcome, and the flexible vegetable tanning skin which is subjected to Q elastic flesh feel, compact and soft grain surface and no looseness and is tanned by combining the all-organic ecological silica gel and the tannin extract and has skin properties superior to those of chrome tanning is obtained, is in close contact with the skin of a human body, is comfortable in skin-friendly massage feeling and has no pollution to the human body.

Description

Manufacturing process of silane tanned leather by combining chromium-free ecological silica gel-tannin extract to tanned vegetable tanned leather

Technical Field

The invention relates to the field of leather, in particular to a manufacturing process of silane tanning of chromium-free ecological silica gel-tannin extract combined vegetable tanning leather.

Background

1. Traditional vegetable tanning, the first method used by man for leather manufacture, uses extracts of vegetable tannin extracts (mainly tannin) to tanne leather. The vegetable tanning leather is the only environment-friendly ecological leather in the tanning leather, toxic substances can not be released even if the vegetable tanning leather is burnt, and some current pet foods are made of the crushed leather. The leather is thick, hard and tough, can easily absorb liquid, is convenient for three-dimensional plasticity after absorbing water, and has light brown yellow color of tannin extract; after the tanning agent is used, factors such as oxidation, sunshine and absorption of liquid can be gradually deepened, and the vegetable tanning skins can be tanned into black brown color after long-time sunshine. The traditional vegetable tanning leather is mainly used for military products, mechanical accessories, basketballs, waistbands, soles, leather box boxes and sculpture leather, so the leather is called 'heavy leather'; because of the bitter and astringent taste of tannin used for tanning, the tannin is also commonly called astringent skin, ointment skin, tannin extract skin and the like.

2. The invention adopts water-soluble macromolecule silane coupling agent, namely water-soluble organic macromolecule bridging polysilsesquioxane precursor, to implant tanning extract leather in the process of forming organic silica gel under alkaline condition, such as breast augmentation and shaping, the organic silica gel is implanted into female breasts to obtain plump, soft and fine meat feeling, thus, the cognition of people on the hardness and poor hand feeling of the traditional vegetable tanning leather plate can be thoroughly changed, the brand new soft vegetable tanning leather which is combined with silica gel and tannin extract for tanning, has full and soft hand feeling, compact and loose grain surface and leather property reaching or even exceeding that of light leather such as chrome tanning and the like is obtained, the leather can be in close contact with the skin of a human body, is skin-friendly and comfortable, does not have any poison to the skin, can be used for manufacturing summer sleeping mats, can also be used for manufacturing close-fitting bras, underwear and underpants and the like, revolutionarily innovates the traditional leather making industry, and has immeasurable environmental protection and commercial value.

3. Water-soluble high-molecular silane coupling agent

3.1 silane coupling Agents

The silane coupling agent simultaneously contains an organophilic carbon functional group and an inotropic silicon functional group, and can form molecular bridging between an inorganic interface and an organic interface, thereby playing the roles of chemically tackifying, enhancing, increasing the volume and improving the performance of the composite material. The silane coupling agent can be represented by [ Q-R '-Si (R) nX (3-n) ], X being a silicon functional group which can be hydrolytically condensed, Q being an organic functional group (carbon functional group), R being an inert hydrocarbon group bonded to silicon-carbon, and R' being an inert linking group which bonds the silicon functional group X to the carbon functional group Q.

The main products in the current silane coupling agent market are small in molecular weight, mostly oil-soluble, and cannot be uniformly dispersed and stably exist in water, a large amount of alcohol is needed to inhibit hydrolysis and cure into macromolecules under an acidic condition before use, the process is easily influenced by various conditions such as environmental temperature, humidity, medium pH value, metal impurities and the like, the application experience is strong, and the control is difficult, so that the silane coupling agent market has certain limitations. The multifunctional macromolecular silane coupling agent does not need hydrolysis curing before use, but is still basically oil-soluble, is not environment-friendly enough and cannot directly use water as a reaction medium. With the continuous development of the technology for preparing functional hybrid materials by a sol-gel method in recent years, higher requirements are put forward on the aspects of reactivity, controllability and repeatability of reaction, convenience of operation, environmental friendliness and the like of the silane coupling agent, so that the small-molecule silane coupling agent needs to be functionalized, polymerized and water-soluble.

3.2 from oil-soluble, Small to Water-soluble, high molecular weight

The oil-soluble micromolecular silane coupling agent is characterized in that high polymerization, multiple functionalization and water-based polymerization are realized by directly connecting a hydrophilic group, a plurality of specific silicon functional groups, a carbon functional group and a macromolecule bridging group similar to a base material structure with a polysiloxane chain through hydrosilylation and acidic silane equilibrium reaction.

There are four methods for the polymerization of small-molecule silane coupling agents: (1) grafting a polyalkoxysilyl group on an organic carbon macromolecular chain; (2) grafting a polyalkoxysilyl group on an organic silicon polymer chain; (3) grafting a poly-alkoxy silicon base on a high molecular block copolymer chain of organic silicon and organic carbon; (4) and carrying out reactive modification on the obtained macromolecular or macromolecular silane coupling agent and a micromolecular silane coupling agent or a modified macromolecular silane coupling agent. The obtained molecular weight is generally more than 10000 and can even reach more than 30000.

In the process, a plurality of different silicon functional groups are introduced to simultaneously realize high polymerization and multiple functionalization. Starting from monomers such as D4/DMC, small molecular silane coupling agent, hydrogen-containing silicone oil, carbon organic monomer containing active functional groups and the like, the small molecular silane coupling agent is prepared by silicon organic high molecular, carbon organic high molecular, silicon-carbon organic hybrid high molecular and further functional group modification according to the application performance of a final product through silicon hydrogen addition, copolymerization/polycondensation/grafting and other modes.

Since both silicon functional groups and carbon functional groups are reactive and react with active hydrogen in water, to obtain a silane coupling agent which can be uniformly dispersed and stably present in water, the active functional groups must be protected properly so that the silane coupling agent does not undergo self-crosslinking or water-hydrolysis deactivation before reaching the surface of the substrate. The water-based reaction of the micromolecule silane coupling agent starts from hydrophilic prepolymerization of monomers to hydrophilic chain extension, and then acidic water is dispersed and chain extension is carried out, so that a hydrophilic covalent bonding system of macromolecules and macromolecules is formed step by step, and meanwhile, the multifunctionalization, the high-molecular reaction and the water-soluble self-emulsification of the silane coupling agent are realized.

The types, the number and the distribution of hydrophilic groups, carbon functional groups and silicon functional groups on the main and side chains of the water-soluble high-molecular silane coupling agent can be designed according to application requirements so as to obtain a unique novel environment-friendly functional material which has excellent wetting and penetrating properties and can be cured at normal temperature on the surfaces of different substrates.

Wherein n is 15-150, R1: alkylene oxide or triethoxysilyl or alkyl, R2: polyether 1 hydrocarbyl or epoxyhydrocarbyl or triethoxysilylhydrocarbyl or alkanyl, R3: alkyl or polyether 1 alkyl, R4: triethoxysilyl hydrocarbon group or isocyanate hydrocarbon group, R5: epoxy hydrocarbyl or trimethoxysilyl hydrocarbyl, R6: polyether 2 hydrocarbyl, R7: polyether 3 hydrocarbyl or triethoxysilyl hydrocarbyl, R8: polyether 4 hydrocarbyl, R9: polyene polyamino hydrocarbon group or isocyanate hydrocarbon group, except sulfur-containing hydrocarbon group, fluorine-containing hydrocarbon group, etc. The bridging group- [ Bridge ] -may be: polymethylsiloxane, acrylic resin, polyurethane resin, epoxy resin, polyamino acid, and the like.

In order to improve the service performance, the water-soluble high-molecular silane coupling agent needs to be considered during synthesis design: (1) the varieties and the number of the silicon functional groups and the carbon functional groups are increased according to the needs: the number of silicon functional groups of the water-soluble macromolecular silane coupling agent can reach six, nine, twelve or even a plurality of silicon functional groups, so that the number of available precursors is huge, the variety and the number of materials with different properties which can be hybridized are almost unlimited by coupling and crosslinking, after sol-gel reaction, the molecular characterization can be regarded as bridged polysilsesquioxane with a body structure, and the application adaptability of the silane coupling agent precursor network can be improved by introducing a plurality of carbon functional groups such as hydroxyl group, mercapto group, amino group, carboxyl group, alkylene group, epoxy group, isocyanate group and fluorine alkyl group; (2) correspondingly extending the-R arm connected with the functional group and the main chain to fully expose the functional group to the outside as much as possible and avoid shielding due to steric hindrance; (3) introducing a group, a side chain or a macromolecular bridging structure similar to the surface of the base material to improve the similarity of the water-soluble macromolecular silane coupling agent and the surface of the material base material, so that the water-soluble macromolecular silane coupling agent and the base material with different characteristics can form network-shaped or body-shaped polysiloxane sol-gel together.

The water-soluble high-molecular silane coupling agent can be flexibly designed into a specific functional group combination according to specific application occasions, so that the limitation that the functional group of the small-molecular silane coupling agent is single and insoluble in water can be broken through, the silane coupling agent is expanded from the existing application field to the fields of organic-inorganic, organic-biological-inorganic and other substrate surface coupling hybrid modification and similar compatibility improvement, and particularly the occasions using water as a reaction medium are as follows: leather making, synthetic leather and textile finishing; washing leather, fur and wool textile products to prevent shrinkage and smooth nursing; metal surfaces of automobiles, machinery and the like are lubricated and subjected to rust-proof and corrosion-proof treatment; the adhesive force and the water-based waterproof ink of the water-based paint and the water-based waterproof ink are improved; the surfaces of nano powder, hollow glass beads and the like are organically modified and subjected to water-resistant treatment; modifying stone-plastic, wood-plastic, plastic-steel and other composite materials; preparing a biosol-gel hybrid material; LEDs, medical body implant materials, biomedical engineering, and the like.

Disclosure of Invention

1. Silane tanned leather

"silane tanned leather" is a new word created by Chengdu Kate organosilicon new materials science and technology limited. In the professional field, the meaning of a new word is not only a new combination of characters but also a new thing from a new material to a new application. Due to good wettability, permeability, dispersibility and flexibility, the organic silicon product is always considered as a development trend by the tanning industry for more than twenty years, and can bring a progress and a change.

The organic silicon system is introduced into the process from raw leather to finished leather, the defects of the traditional leather making are solved, the concept of a leather making expert is already entered in the last century, but the organic silicon system is bitter in large professional span, the professional knowledge in four aspects of polymer synthetic chemistry, water-soluble organic polymer bridging polysilsesquioxane precursor synthetic chemistry, leather making chemical engineering material chemistry, leather making process chemistry and the like needs to be fused, no operable ready-made material exists, no reference using method exists, and the organic silicon system is not different from the cloud end climbing in the realization difficulty.

At present, the development of a third generation silane modified leather material system with silicon-based reaction activity produced by Minneda silicon fluoride application research laboratory in Wenjiang district of metropolis and a related application system 'silane tanning' of the invention enables the scientific research conception of old and elder experts to be finally moved from a laboratory to the market and land stably. The silane tanning is a silane sol-gel tanning technical system which adopts a nonhazardous and pollution-free water-soluble polymethylsiloxane bridging polysilsesquioxane precursor high-molecular silane coupling agent as a main frame and is characterized by quality improvement, cost reduction, water saving, energy saving and emission reduction. In the silane tanning system, tanning is regarded as preparation of organic-biological-inorganic hybrid materials, and according to the market and the specific conditions of raw leather, traditional chemical materials are combined to different degrees to perform inorganic, semi-inorganic and organic sol-gel modification on natural biopolymer leather collagen fibers so as to obtain expected service performance. The invention advances the application of organosilicon materials in the leather-making field from the prior coating and fatliquoring working section to the water-field pre-tanning preparation and tanning retanning working section, fills the technical blank at home and abroad, basically establishes a water-saving emission-reducing low-carbon environment-friendly simple technical system of silane tanning on the basis of taking a water-soluble high-molecular silane coupling agent as a main leather-making material, develops a brand-new way for water saving and emission reduction for the traditional tanning for many years, stands up the clean production of ecological leather, strives to achieve the environment-friendly ecology of a terminal product, always emphasizes the environment-friendly ecology in the production process of the product, controls pollution from materials and process sources, improves the high energy consumption, high water consumption and high pollution conditions of the traditional leather-making industry, promotes the simplification, the scientization and the artistry of the leather-making process, and promotes the development of tanning practice and modernization.

2. Selection of silane tanning agent

From the chemical point of view, the tanning process is essentially to adopt polybase coupling agent such as inorganic, semi-inorganic and organic polybase coupling agent to carry out inorganic, semi-inorganic and organic coupling hybridization modification on natural organic polymer leather collagen fiber, namely, to adopt condensation crosslinking OR addition crosslinking reaction of transition metal ion hydroxyl complex containing 3d, 4d OR 5d empty orbitals OR alkoxide thereof (namely-OH is substituted by-OR group) OR organic compound containing hydroxyl unit (OR hydroxyl unit can be reduced in water) OR other active carbon functional group and active hydrogen on the leather collagen fiber.

Traditional tanning is predominantly based on basic trivalent chromium. In acidic aqueous environments, trivalent chromium is usually the central ion as d²sp³The hybrid form and three electron-rich ligands form a coordination compound, and the R-O-Cr formed by dehydration and crosslinking with active hydrogen on the collagen fibers can be regarded as polychlorinated siloxane, and the collagen fibers are endowed with good stability and rigidity after being modified by chromium due to the stable and hard structure of the chromium. Theoretically, the maximum of chromium ions can form an octahedral coordination structure with six ligands, but due to the mismatch of the electron orbital energy levels and symmetry of chromium atoms and carbon atoms, electron cloud flowing, i.e. covalent bonds, are difficult to form between chromium and carbon, so that six coordinated trivalent chromium ions (d) are difficult to form²sp³) The three empty coordination positions left after coordination with the three electron-rich ligands can not accept hydrocarbon groups, namely Cr-C bonds can not be formed, so that the organic property of chromium is insufficient, the chromium can better permeate into skin collagen fibers in a low-pH value aqueous solution state during use, the flexibility of the prepared polychrominated siloxane chrome tanned skin, namely blue wet skin, is also insufficient, a large amount of grease needs to be filled in the post-process to increase the flexibility and lubrication, and the grease is lost if the skin blank is placed for a long time, so that the plate is hard and aged easily, and the quality is influenced. Although trivalent chromium is still the leading material of the traditional tanning system at present, because of the toxicity of hexavalent state ions, the trivalent chromium is harmful to the environment and human bodies, and the earth chromium resource is gradually deficient, the search for a more ideal alternative tanning agent is not stopped all the time. Theoretically, it is said that all transition metal or semimetal elements capable of forming three or more hydroxyl or alkoxy alkoxide coordination compounds, i.e. having 3d, 4d or 5d empty orbitals, may have a tanning function, and it is preferable that the transition metal or semimetal elements are capable of being directly connected to carbon, i.e. -R, and it is also required to have good stability, rigidity and flexibility, safety and non-toxicity.

On the periodic table, an element capable of bonding to three or more hydroxyl groups or alkoxy groups and also capable of bonding directly to-R is silicon having a 3d vacant orbital. The nano-sized inorganic silica can be used as a hydrogen bond filler for tanning, but is not active enough to be used as a tanning agent. In the organosilicon, the silane coupling agent is R-Si (OR')₃The structure is that the oil-soluble micromolecular silane coupling agent on the market is not dissolved in water, and the-R is short and small, and the variety and the number of functional groups are limited, so the oil-soluble micromolecular silane coupling agent is not suitable for being used as a tanning agent. The application of the water-soluble polymer silane coupling agent with a plurality of active silicon functional groups and carbon functional groups to leather making is a great idea, and the water-soluble organic polymer bridged polysilsesquioxane precursor specially used for a leather making water field has the characteristics of an inorganic tanning agent and an organic tanning agent, is non-toxic and pollution-free, has quite abundant silicon reserves on the earth, and therefore can be a suitable choice for the tanning agent.

3. Comparison of silane tanning agent with chrome tanning agent

Silicon functional group of silane coupling agent-Si (OR')₃Upper Si atom halfLarger diameter, 3d orbit being empty, electron deficient, - (OR)₃The 2p orbital of the medium oxygen atom is rich in electrons, the energy levels of the two orbitals are close and symmetrically matched, and the two orbitals are opposite and uniform in the same molecule and are opposite.

Delocalized alcoholysis to form multi-base structure

Similar to the formation of 3-OH coordination compounds in an acidic water environment by trivalent chromium, the trivalent chromium can also perform dehydration (or dealcoholization) crosslinking reaction with active hydrogen on the collagen fibers. The water-soluble high-molecular silane coupling agent has a plurality of silicon functional groups on the main chain and the side chain, so that the water-soluble high-molecular silane coupling agent can react with active hydrogen on the collagen fibers to form a network-shaped polysiloxane sol-gel precursor framework. In a polysiloxane sol-gel system, tanning crosslinking of each layer of the leather is relatively homogeneous, so that the loose surface problem of the chrome tanning leather, such as loose core, rough surface, grabbing surface and separation of a grain surface layer and a net layer due to uneven tanning can be well avoided.

The quadrivalent Si atom of the water-soluble macromolecular silane coupling agent is sp³Hybridization is carried out, the covalent bond is directly connected with carbon atoms to form Si-R covalent bonds, so the organic property is obviously superior to trivalent chromium, the similar compatibility with biological base materials such as leather collagen fibers is greatly increased, the use at a low pH value strictly as chrome tanning is not needed, meanwhile, macromolecule bridging-R groups of the water-soluble macromolecule silane coupling agent can be flexibly and changeably used as required, such as polysiloxane, polyurethane, polyacrylic resin, polypeptide, grease and the like, and correspondingly, different characteristics are endowed to adapt to the functions of different base material surfaces and application occasions. Chrome tanning agents and other metal tanning agents such as zirconium, titanium, aluminum, etc. cannot be directly linked to carbon atoms to form M-R organometallic covalent bonds. The "metal organic compound" such as organic chromium coupling agent, titanate coupling agent, aluminum alkoxide and the like, the hydrocarbon group of which is indirectly connected with chromium, titanium and aluminum only through oxygen. Thus, in contrast, silane is more easily combined with the collagen fibers by reaction, and the molecular structure is more flexible, thereby being more easily endowed with different functions.

In addition, the water-soluble high-molecular silane coupling agent has unique stability and flexibility, and the skin collagen fiber modified by the polysiloxane sol-gel hybridization has unique stability, flexibility, bending and compression resistance elasticity, delicate, soft and soft texture of the silica gel and the like and the durability of the qualities correspondingly. These properties are difficult to achieve with the chromoxane-modified collagen fibers.

4. Comparison of silane tanning agent with organic tanning agent

The organic tanning agent has active units on carbon atoms (OR can be reduced in water) capable of crosslinking with active hydrogen on the surface of a substrate, such as hydroxyl-OH capable of being dehydrated and crosslinked, alkoxy-OR capable of being dealcoholized and crosslinked, isocyanate-N-C-O capable of being added and crosslinked, and the like. The organic tanning agent is SP in the molecule³The hybridized carbon atom can not be simultaneously and stably connected with three hydroxyl groups or alkoxy groups like the silicon atom on the silane coupling agent, one-OH on the carbon atom is connected with one-OH to form alcohol, two-OH is connected with the carbon atom to form aldehyde, three-OH is connected with the carbon atom to form carboxylic acid, and four-OH is connected with the carbon atom to form carbon dioxide. Therefore, a hydroxyalkyl structure (phenolic resin of phenolic hydroxyl group, tetramethylolphosphonate, cyanamide resin, etc.) and a structure which can be reduced to a single or plural hydroxyl units in water, such as an epoxy structure (epoxy resin), an aldehyde structure (aldehyde tanning agent), a carboxyl structure (acrylic resin tanning agent), an oxazolidine structure (prepared by aldehyde synthesis and releasing aldehyde in water), an isocyanate structure (urethane resin tanning agent, which can be regarded as containing a dialdehyde unit in which a hydroxyl group is substituted by an amino group) have a certain tanning property.

Characteristic of water-soluble high-molecular silane coupling agent

The structure can be provided with a plurality of active silicon functional groups X and a plurality of different active carbon functional groups Q. Theoretically, all the activated carbon functional groups which play a role in cross-linking and tanning in the organic tanning agent and the water-soluble high-molecular silane coupling agent can be connected, can also play a role in the organic tanning agent on the skin collagen fibers, and can cooperatively participate in forming a sol-gel hybrid modified network together with the silicon functional groups.

Because the organic tanning agent only depends on carbon functional groups to act, and the carbon atomic radius of the organic tanning agent is smaller than that of silicon atomic radius, the crosslinking hybridization modification of the leather collagen fibers is difficult to form uniform network sol-gel with certain pores like a macromolecular silane coupling agent simultaneously having the silicon functional groups and the carbon functional groups, so the tanning agent is not good at the tanning uniformity and the packaging capacity of other tanning materials.

5. Use of silane tanning agents in tanning leather

In summary, the water-soluble high molecular silane coupling agent plays a main role in tanning: (1) through the cross-linking combination of the active silicon functional group and the carbon functional group with the leather collagen fiber, a sol-gel precursor network framework system of polysiloxane-leather collagen fiber is built, and the leather is endowed with unique, fine, soft and elastic silica gel texture; (2) the excellent permeability, dispersibility and special opposite phase forming performance of the leather retanning agent play a unique one-bath regulating role in the permeation absorption, emulsification and dispersion of various materials in bath liquid, such as acid, alkali, chrome tanning agent, grease, filler, dye, spice and the like in leather collagen fibers, so that a water-saving emission-reducing environment-friendly scheme without water washing in a retanning dyeing section can be realized; (3) the sol-gel precursor network of the silane-leather collagen fiber still has precursor activity, and still has cross-linking and combining capacity for other materials in bath liquid, such as tanning agent, dye, grease, filler, spice and the like, so that the materials can jointly penetrate into the fiber and are packaged and fixed in a wide polysiloxane sol-gel network system in a reactive way, and the quality of the obtained leather can be maintained for a long time.

6. Technical route of silane tanning

In fact, the whole leather manufacturing process, from water field to coating, from fur to leather blank to finished product, the upgrading and reusing of the abnormal loose surface leather in each stage and the later washing and nursing of leather and fur products can all use the water-soluble high molecular silane coupling agent.

In recent years, silane tanning accumulates a large amount of first-hand application data from countless small-scale tanning tests to middle-scale tanning tests to small-scale external leather processing, a silane retanning dyeing technology without washing in midway is mature, and the large-pine-blue wet leather can be upgraded to manufacture dual-purpose leather for plain vamps and cases through silane sol-gel modification. By adopting the silane sol-gel tanning method, the alkali leather, the nitro leather or the acid leather can be directly tanned into leather blanks without a wet blue leather working section, and the tanning modes of low pH value chrome tanning, high pH value high temperature fatliquoring and repeated water washing for more than one hundred years are thoroughly changed. The user experience brought by silane tanning is incomparable with the traditional carbon leather tanning no matter in the aspects of finished leather quality, quality controllability, convenience and easiness in operation, water conservation, emission reduction, low carbon, environmental protection and the like.

In addition, the silane tanning system has very good inclusion property, not only can well contain trivalent chromium, organic tanning agents and other first-line traditional tanning materials, but also can contain other metals or mineral tanning agents such as zirconium, titanium, aluminum, iron, silicate and the like, even calcium, magnesium, zinc and the like which are not used as tanning agents usually are possibly well blended into the silane tanning system after silanization, and organic-biological-inorganic hybrid co-modification is carried out on leather collagen fibers, so that the hybrid modification has greater adjustability. On the other hand, the full-organic silane tanned leather without adding any metal tanning agent can replace the tedious traditional oil tanning method for tanning, and the polysiloxane silica gel leather which is soft, delicate, skin-friendly and environment-friendly and can be used as the underwear fabric is obtained, the fiber of the silica gel leather is in a cotton shape, has the memory function similar to memory alloy, can automatically recover the shape and the hand feeling before deformation once the fiber is recovered to normal temperature even after being contracted and deformed at high temperature, has better humidity-heat resistance stability and mechanical strength than the traditional oil tanned leather, and has short production period and simple and convenient process.

Therefore, the water-soluble high-molecular silane coupling agent with good water solubility, no toxicity and no pollution is applied to the field of leather making, is not only used as a superior auxiliary agent to be introduced into each working section of the traditional leather making process, but also used as a material with a leading effect, can be used for building a brand-new water-saving energy-saving emission-reduction silane sol-gel tanning technical system, is combined with other traditional tanning agents to different degrees according to the raw leather conditions and market requirements, and contains and screens the carbon leather chemical materials.

7. Silane tanning process scheme for tanning vegetable leather by combining chromium-free ecological silica gel-tannin extract

In order to overcome the defects of the traditional vegetable tanned leather, the invention provides the water-saving emission-reduction silane tanning manufacturing process for the environment-friendly silica gel-tannin extract combined tanning close-skin ecological flexible vegetable tanned leather, which can eliminate the hardness, the death and the softness of a vegetable tanned leather plate and has poor hand feeling, can improve the quality of finished leather, is simple and convenient in process operation, saves more than 50 percent of time and more than 40 percent of water and has wide application range. In order to achieve the purpose, the invention is realized by the following technical scheme:

the water-saving emission-reducing silane tanning manufacturing process of the environment-friendly silica gel-tannin extract combined tanning close-skin ecological flexible vegetable tanning leather comprises fur silane soaking, silica gel ash-wrapping wool pushing, silane-alkali sulfide fur soaking, silica gel re-ashing, silane-hydrogen peroxide pre-deliming (alkali sulfide elimination), silane-hydrogen peroxide main deliming (alkali sulfide elimination), cationic silica gel pretreatment, salt leaching, pickling, silicon aldehyde primary tanning/silica gel-tannin extract combined primary tanning, cationic silica gel softening, anionic silica gel-tannin extract dyeing re-tanning filling and fat adding, cationic silica gel fixing and mildew-proof treatment and the like, can save more than 50% of time, save more than 40% of water, and remarkably reduce pollutant discharge and water, electricity and manpower resource consumption.

The fur silane soaking step comprises the following steps: weighing 100 parts of fur by weight in a rotary drum, washing for 10 minutes, adding 150 parts of normal-temperature water, KT 17170.1-1 part, KT 30070.05-0.3 part, 0.2-0.5 part of non-ionic degreasing agent, 0.1-0.3 part of bactericide, 0.3-1 part of sodium carbonate and 0.1-0.3 part of sodium sulfide, rotating for 3 hours at a slow speed, rotating for 30 minutes/stopping for 30 minutes, rotating for 8-10 hours, discharging from the drum, removing meat, entering silica gel package ash and pushing hair;

the step of pushing wool by wrapping ash with silica gel comprises the following steps: weighing 5000 parts of water, 171730-60 parts of KT, 300715-40 parts of liming auxiliary agent, 30-60 parts of nonionic degreasing agent, 60-100 parts of sodium hydrosulfide and 280 parts of sodium sulfide; stirring evenly, then adding 3000-4000 parts of lime slowly while stirring to obtain mortar. Coating mortar on the surface of rabbit skin, properly increasing the coating amount of the ridge line, overlapping meat and meat, standing and stacking for 6-12 hours, pushing hair, blowing, and then, entering silane-sodium sulfide for hair destruction and liming.

The steps of destroying and liming the silane-sodium sulfide comprise: adding 10-30 parts of normal temperature water, 0.3-0.3 part of KT 17170.1, 0.3-0.5 part of non-ionic degreasing agent, 0.3-0.5 part of liming auxiliary agent, 0.5-0.8 part of sodium hydrosulfide and 0.5-0.8 part of sodium sulfide, slowly rotating for 1 hour, then rotating for 30 minutes/stopping for 30 minutes, and rotating for 2 hours; adding KT 17170.5-1 part, sodium sulfide 0.5-1.5 parts and lime 1-3 parts, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2 hours; adding KT 17170.5-1 part, sodium sulfide 0.5-1.5 parts, lime 1-3 parts, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2-12 hours; checking the condition of broken wool, after the broken wool is clean, adding KT 17171-5 parts, rotating for 2 hours, adding normal temperature water 30-50 parts, lime 1-2 parts and liming auxiliary agent 0.1-0.3 part, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2 hours; adding 50-80 parts of normal temperature water, 1-2 parts of lime and 0.1-0.3 part of liming auxiliary agent, rotating for 30 minutes/stopping for 30 minutes, rotating for 2 hours, rotating for 5 minutes/stopping for 55 minutes, rotating for 10-24 hours, discharging the drum sheet, reserving waste liquid which can be used as liming liquid or liming liquid for recycling, and then adding silica gel for liming;

the silica gel ash recovery step is as follows: weighing 100 parts of alkali leather by weight into a rotary drum, adding 100-200 parts of the waste liquid of the hair destruction and liming, adding KT 17171-2 parts, 0.3-0.5 part of the non-ionic degreasing agent and 3-5 parts of lime, slowly rotating for 30 minutes/stopping for 30 minutes, and stopping for 4-12 hours; the waste liquid can be reserved as ash dipping liquid or ash recovery liquid for recycling, and the ash bark is washed clean by water and enters silane-hydrogen peroxide for pre-deliming (removing sodium sulfide):

the silane-hydrogen peroxide pre-deashing (eliminating sodium sulfide) step comprises the following steps: adding normal temperature water 50-100 parts, KT 17171-2 parts, and non-ionic degreasing agent 0.3-0.5 parts, and rotating slowly for 2 hours; adding 3-5 parts of ammonium sulfate and 0.5-1 part of deliming agent, and slowly rotating for 2 hours; adding 1-2 parts of hydrogen peroxide, slowly rotating for 4 hours, washing with water, and performing main deliming (sodium sulfide elimination) on silane-hydrogen peroxide;

the silane-hydrogen peroxide main deashing (eliminating sodium sulfide) steps are as follows: adding normal temperature water 30-50 parts, KT 17172-4 parts, and non-ionic degreasing agent 0.3-0.5 part, slowly rotating for 2 hours: adding 5-8 parts of ammonium sulfate and 0.5-1 part of deliming agent, and slowly rotating for 2 hours; adding 1-2 parts of hydrogen peroxide, slowly rotating for 4 hours, slowly rotating for 30 minutes/stopping for 30 minutes, and stopping for 4-12 hours; washing with water until the pH value is 6.5-7.5, and then performing cationic silica gel pretreatment;

the pretreatment steps of the cationic silica gel are as follows: adding 30-50 parts of 35 ℃ hot water, KT 17173-5 parts and KT 40313-5 parts, slowly rotating for 3 hours, and performing salt leaching;

the salt leaching step comprises the following steps: adding 8-10 parts of industrial salt and 8-10 parts of anhydrous sodium sulphate, slowly rotating at 35 ℃ for 3 hours, and performing pickling;

the pickling step comprises the following steps: adding 0.5-1.5 parts of industrial formic acid, adjusting the pH value range to 2.5-3, slowly rotating for 8-12 hours, and performing combined primary tanning of the silica aldehyde primary tanning/silica gel-tannin extract;

the step of the combined initial tanning of the silicon aldehyde initial tanning/the silica gel-tannin extract comprises the following steps: adding KT 28113-5 parts, acid-resistant oil 0.1-0.3 part and KT 20342-4 parts, and slowly rotating for 4-8 hours; adding 8-16 parts of tannin extract, 2-4 parts of acid-resistant oil, 2-6 parts of KT 20344 and 4 parts of KT 59012-4 parts, and slowly rotating for 8-12 hours; adding 1-2 parts of acid-resistant oil and KT 20342-4 parts, adjusting the temperature to 45 ℃, and slowly rotating for 8-12 hours; standing for 48 hours after the materials are discharged from the drum, squeezing water, uniformly shaving, and softening by entering cationic silica gel;

the softening step of the cationic silica gel is as follows: weighing 100 parts by weight of the shaved primary tanned leather in a rotary drum, washing with water twice, and adjusting the temperature to 45 ℃; adding 150 parts of water with the temperature of 45 ℃, 100-8 parts of KT 40315-8 parts of KT 17175-8 parts of KT 28111-3 parts of KT, rotating for 4-6 hours at medium speed, adding 1-2 parts of baking soda, rotating for 4-6 hours at medium speed, and entering anionic silane-tannin extract dyeing retanning, filling and fatliquoring;

the anionic silane-tannin extract dyeing retanning filling fatliquoring step comprises the following steps: adding X parts of dye, 3-5 parts of tannin extract, 3-4 parts of KT 59012-4 parts, KT 20346-8 parts, KT 23514-6 parts, 3-5 parts of acid-resistant oil and 5-8 parts of common grease into the mixture in one bath, rotating the mixture at a medium speed of 45 ℃ for 8-12 hours, and performing cationic silica gel fixation and mildew-proof treatment;

the cationic silica gel fixing and mildew-proof treatment steps are as follows: adding formic acid into the mixture in one bath to adjust the pH value to 3-3.5, rotating the mixture at the temperature of 45 ℃ for 1 hour at medium speed, adding KT 40311-3 parts and the mildew preventive 0.3-0.5 part, rotating the mixture at the temperature of 45 ℃ for 2 hours at medium speed, washing the mixture twice, discharging the mixture out of a drum, and drying and finishing the mixture to obtain a leather blank.

Preferably, the KT1717 is a softening-replacement neutralizing silane, and the KT1717 is a side polyamino hydrocarbon polyhydroxy hydrocarbon triethoxy silane polymethyl silsesquioxane aqueous emulsion polymerized by weak cation emulsion, also known as: the water-soluble organic silicon high-molecular silane coupling agent and the low-temperature coupling self-crosslinking amino-hydrocarbon hydroxyl silicone oil have the technical indexes that: the density is 0.95g/ml at 20 ℃, the content of water-soluble substances is 20 +/-1%, the pH value of solvent water is 6.5 +/-0.2, the viscosity is 40-50mPa.s, and the appearance is light blue emulsion;

preferably, the KT3007 is a penetrating crosslinking silane assistant, the KT3007 is an isopropanol aqueous solution of a polyepoxy alcohol ether alkyl polymethylsiloxane silane coupling agent, and the technical indexes are as follows: the density is 0.85g/ml at 20 ℃, the weight percentage of non-volatile components is 36 +/-1%, the solvent is water, the pH value is 6.5 +/-0.2, the charge is non-ionic, the viscosity is 90-110mPa.s, and the appearance is light yellow to colorless transparent liquid.

Preferably, the KT4031 is cationic polyurethane retanning silica gel, the KT4031 is a water-soluble cationic polyurethane high-molecular silane coupling agent with coupling and crosslinking reaction activity, and is a strong cationic poly-alkoxy siloxane carbamate-grease-silica gel polymer; the technical indexes are as follows: the density is 0.95g/ml to 1.05g/ml at 20 ℃, the content of water soluble matters is 18 percent to 22 percent, the pH value of solvent water is 4.5 +/-0.3, the viscosity is 400-500mPa.s, and the appearance is milky yellow emulsion.

Preferably, the KT2811 is amino silane modified fatty aldehyde, and the KT2811 is a water-soluble organic silicon polyethylene polyamine alkaline high molecular silane coupling agent, so that the crosslinking hybridization modification, permeation and dispersion effects are good. The technical indexes are as follows: the pH value is 2-4, the charge is weak cationic, and the appearance is light blue emulsion.

Preferably, the KT2034 is cotton-bubble meat-feeling filled silica gel, the KT2034 is a secondary derivative of lecithin and hydroxyalkyl aminoalkyl carboxyalkyl carboxyalkoxysilicon-based modified polymethylsiloxane, and the technical indexes are as follows: the density is 0.92g/ml at 20 ℃, the content of water soluble substances is 26-30%, the pH value of solvent water is 3.8 +/-0.2, the viscosity is 150-180mPa.s, and the appearance is light cream yellow thick liquid;

preferably, the KT5901 is a silicon sulfone filled synthetic tanning agent, the KT5901 is a polymer tanning agent formed by secondary hydrolysis and condensation of naphthol sulfonic acid and SO2 organic derivatives with a silicon sulfone bridged structure and high filling performance, and the technical indexes are that the density at 20 ℃: 1.10g/mL-1.25g/mL, water soluble substance content 46% -50%, solvent water, pH value: 4.0 ± 0.2, viscosity: 120 mPa.S-140 mPa.S, the appearance is light brown semitransparent thick liquid.

Preferably, the KT2351 is foaming elastic greasing silicone oil, the KT2351 is modified polymerization type silicone oil, and the modified reaction type silicone oil is an aqueous emulsion type copolymer of vinyl amino monomers, carboxyl monomers and the like, and the technical indexes are as follows: the density is 1.10g/ml-1.25g/ml at 20 ℃, the water soluble substance content is 28-33%, the pH value of the solvent water is 4.5-5.5, the viscosity is 24000-26000mPa.s, and the appearance is creamy yellow thicker liquid.

The invention relates to a water-saving emission-reduction silane tanning manufacturing process for environment-friendly silica gel-tannin extract combined tanning close-skin ecological flexible vegetable tanning leather, which has the beneficial effects that: the operation mode is simple, and the working procedures are popular and easy to understand. In the conventional vegetable tanning process, dozens of processes are usually carried out from fur to leather blank, the operation is complicated, and instability of vegetable tanning leather surface can occur in the process of multiple processes, such as: skin surface scratch, color difference, loose surface and the like. According to the situation, the inventor researches a one-pot boiling fast tanning method of a silica gel-tannin extract combined tanning rotary drum by groping for many years, adopts fast intermittent rotation and tanning from low temperature to high temperature, and the organosilicon material can effectively help leather to absorb tannin extract under the mechanical action of the rotary drum, and compared with the traditional tanning method (pool tanning and hanging tanning), the operation is simple and stable, the blank discharging time of the leather blank is short, the time is saved by more than 50%, the water is saved by more than 40%, the production period can be greatly shortened, and the pollutant discharge amount and the resource consumption of water, electricity, manpower and the like are obviously reduced.

Drawings

FIG. 1 is a schematic structural formula of a water-soluble polymer silane coupling agent.

FIG. 2 is a technical route diagram of the application of water-soluble polymer silane coupling agent in the leather making field.

Detailed Description

The present invention will be described in further detail with reference to the following examples.

Example 1: the invention discloses an environment-friendly silica gel-tannin extract combined tanning skin-next-to-skin ecological flexible buffalo hide vegetable tanning mat leather manufactured by the method, which comprises fur silane soaking, silane-alkali sulfide fur destroying soaking ash, silica gel redrying, silane-hydrogen peroxide pre-deliming (removing alkali sulfide), silane-hydrogen peroxide main deliming (removing alkali sulfide), cation silica gel pretreatment, salt leaching, pickling, silicon aldehyde primary tanning/silica gel-tannin extract combined primary tanning, cation silica gel softening, anion silica gel-tannin extract dyeing and retanning filling fatting, cation silica gel fixing and mildew-proof treatment. The method comprises the following specific steps:

(1) soaking fur in silane: weighing 100 parts of buffalo fur by weight in a rotary drum, washing for 10 minutes, adding 150 parts of normal-temperature water, KT 17170.5 parts, KT 30070.1 parts, 0.3 part of nonionic degreasing agent, 0.1 part of bactericide, 0.5 part of soda ash and 0.3 part of sodium sulfide, slowly rotating for 3 hours, then rotating for 30 minutes/stopping for 30 minutes, stopping for 10 hours, discharging, removing meat, trimming, entering the drum, and entering silane-sodium sulfide to destroy hairs and soak ash;

(2) silane-sodium sulfide wool destruction and liming: adding normal-temperature water 20 parts, KT 17170.3 parts, non-ionic degreasing agent 0.3 part, liming auxiliary agent 0.5 part, sodium hydrosulfide 0.6 part and sodium sulfide 0.6 part, slowly rotating for 1 hour, then rotating for 30 minutes/stopping for 30 minutes, and rotating for 2 hours; adding KT 17170.5 parts, sodium sulfide 0.6 parts and lime 2 parts, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2 hours; adding KT 17170.5 parts, sodium sulfide 0.6 parts and lime 2 parts, rotating for 30 minutes/stopping for 30 minutes, and rotating for 10 hours; checking the condition of broken wool, after the broken wool is clean, adding KT 17173 parts, rotating for 2 hours, adding normal-temperature water 30 parts, lime 1 part and liming auxiliary agent 0.2 part, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2 hours; adding 80 parts of normal temperature water, 2 parts of lime and 0.3 part of liming auxiliary agent, rotating for 30 minutes/stopping for 30 minutes, rotating for 2 hours, rotating for 5 minutes/stopping for 55 minutes, rotating for 24 hours, discharging the drum sheet skin, reserving waste liquid which can be used as liming liquid or liming liquid for recycling, and then adding silica gel for liming;

(3) silica gel ash coating: weighing 100 parts of alkali leather by weight into a rotary drum, adding 200 parts of hair-destroying liming waste liquid, adding KT 17171 parts, 0.5 part of nonionic degreasing agent and 3 parts of lime, slowly rotating for 30 minutes/stopping for 30 minutes, and stopping for 10 hours; the waste liquid can be used as ash leaching liquid or ash recovery liquid for recycling, the ash bark is washed clean by water and enters silane-hydrogen peroxide for pre-deliming (eliminating sodium sulfide);

(4) silane-hydrogen peroxide pre-deliming (elimination of sodium sulfide): adding 50 parts of normal temperature water, KT 17171 parts and 0.3 part of nonionic degreasing agent, and slowly rotating for 2 hours; adding 3 parts of ammonium sulfate and 0.5 part of deliming agent, and slowly rotating for 2 hours; adding 1 part of hydrogen peroxide, slowly rotating for 4 hours, washing with water, and performing main deliming (sodium sulfide elimination) on silane-hydrogen peroxide;

(5) silane-hydrogen peroxide main deliming (elimination of sodium sulfide): adding 30 parts of normal temperature water, KT 17172 parts and 0.3 part of nonionic degreasing agent, and slowly rotating for 2 hours; adding 8 parts of ammonium sulfate and 0.5 part of deliming agent, and slowly rotating for 2 hours; adding 1 part of hydrogen peroxide, slowly rotating for 4 hours, slowly rotating for 30 minutes/stopping for 30 minutes, and stopping for 10 hours; washing with water until the pH value is 6.5-7.5, and then performing cationic silica gel pretreatment;

(6) pretreatment of cationic silica gel: adding 30 parts of 35 ℃ hot water, 17173 parts of KT and 40313 parts of KT, slowly rotating for 3 hours, and carrying out salt leaching;

(7) salt leaching: adding 8 parts of industrial salt and 8 parts of anhydrous sodium sulphate, slowly rotating for 3 hours at 35 ℃, and performing pickling;

(8) pickling: adding 1.5 parts of industrial formic acid, adjusting the pH value range to 2.5-3, slowly rotating for 8 hours, and entering the initial tanning of silicon aldehyde/silica gel-tannin extract combination:

(9) initial tanning of silicon aldehyde/silica gel-tannin extract combination: adding KT 28114 parts, acid-resistant oil 0.3 part and KT 20344 parts, and slowly rotating for 6 hours; adding 12 parts of tannin extract, 4 parts of acid-resistant oil, KT 20346 parts and KT 59013 parts, and slowly rotating for 10 hours at 35 ℃; adding 2 parts of acid-resistant oil and 2 parts of KT 20344, adjusting the temperature to 45 ℃, and slowly rotating for 10 hours; standing for 48 hours after the materials are discharged from the drum, squeezing water, uniformly shaving, and softening by entering cationic silica gel;

(10) softening the cationic silica gel: weighing 100 parts by weight of the shaved primary tanned leather in a rotary drum, washing with water twice, and adjusting the temperature to 45 ℃; adding 100 parts of water with the temperature of 45 ℃, KT 40316 parts, KT 17176 parts and KT 28112 parts, rotating for 4 hours at medium speed, adding 2 parts of baking soda, rotating for 4 hours at medium speed, and entering anionic silane-tannin extract dyeing retanning, filling and fatliquoring;

(11) anionic silane-tannin extract dyeing retanning filling fatliquoring: adding X parts of dye, 5 parts of tannin extract, 5 parts of KT 59012 parts, KT 20345 parts, KT 23515 parts, 3 parts of acid-resistant oil and 8 parts of fatting agent into the mixture in one bath, rotating the mixture at a medium speed of 45 ℃ for 6 hours, and performing cationic silane fixation and mildew-proof treatment;

(12) fixing cationic silane and performing mildew-proof treatment: adding formic acid into the mixture in one bath to adjust the pH value to 3-3.5, rotating at 45 ℃ for 1 hour at medium speed, adding KT 40312 parts and mildew preventive 0.3 parts, rotating at 45 ℃ for 2 hours at medium speed, washing twice, discharging from a drum, and drying and finishing to obtain a leather blank.

The industrial products of KT1717, KT3007, KT2811, KT4031, KT2034, KT5901, KT2351 and the like are purchased from Minninida silicofluoride application research and test factories in Wenjiang river district of metropolis. The environment-friendly silica gel-tannin extract combined tanning close-skin ecological flexible buffalo hide vegetable tanning summer sleeping mat manufactured by the invention is cool but not ice, mild and exquisite, cool and comfortable without stimulation discomfort of ice when being in close contact with human skin, has the fine and smooth feeling of real silk and the roughness and the stiffness of cotton and hemp.

Example 2: the invention discloses an inner-layer skin-friendly leather of an environment-friendly silica gel-tannin extract combined tanning skin-next ecological flexible rabbit skin bra, which comprises fur silane immersion, silica gel ash-wrapping wool pushing, silane-alkali sulfide fur immersion, silane-hydrogen peroxide pre-deliming (alkali sulfide elimination), silane-hydrogen peroxide main deliming (alkali sulfide elimination), cationic silica gel pretreatment, salt immersion, pickling, silicon aldehyde primary tanning/silica gel-tannin extract combined primary tanning, cationic silica gel softening, anionic silica gel-tannin extract dyeing and retanning filling fatting, cationic silica gel fixing and mildew prevention, and specifically comprises the following steps:

(1) soaking fur in silane: weighing 100 parts of rabbit fur by weight in a rotary drum, washing for 10 minutes, adding 150 parts of normal temperature water, KT 17170.5 parts, KT 30070.1 parts, 0.3 part of nonionic degreasing agent, 0.1 part of bactericide, 0.5 part of soda ash and 0.3 part of sodium sulfide, slowly rotating for 3 hours, then rotating for 30 minutes/stopping for 30 minutes, rotating for 10 hours, taking out of the drum, cutting off the head, tail and limbs, draining water and preserving moisture, and putting the rabbit fur into silica gel coated ash to push the fur.

(2) And (3) wrapping ash with silica gel and pushing wool: the mortar coating formula comprises: weighing 5000 parts of water, 171740 parts of KT, 300720 parts of liming auxiliary agent, 50 parts of nonionic degreasing agent, 80 parts of sodium hydrosulfide and 250 parts of sodium sulfide by weight; stirring evenly, then slowly adding 3000 parts of lime while stirring, and stirring evenly to obtain mortar. Coating mortar on the surface of rabbit skin, properly increasing the coating amount of the ridge line, overlapping meat and meat, standing and stacking for 6-12 hours, pushing hair, blowing, and then, entering silane-sodium sulfide for hair destruction and liming.

(3) Silane-sodium sulfide wool destruction and liming: adding normal-temperature water 20 parts, KT 17170.3 parts, non-ionic degreasing agent 0.3 part, liming auxiliary agent 0.5 part, sodium hydrosulfide 0.6 part and sodium sulfide 0.6 part, slowly rotating for 1 hour, then rotating for 30 minutes/stopping for 30 minutes, and rotating for 4 hours; checking the condition of broken wool, after the broken wool is clean, adding KT 17173 parts, rotating for 2 hours, adding normal-temperature water 30 parts, lime 1 part and liming auxiliary agent 0.2 part, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2 hours; and then adding 80 parts of normal temperature water, 2 parts of lime and 0.3 part of liming auxiliary agent, rotating for 30 minutes/stopping for 30 minutes, rotating for 5 minutes/stopping for 55 minutes after rotating for 2 hours, and rotating for 24 hours. The waste liquid can be reserved as ash leaching liquid or ash recovery liquid for recycling, and then enters silane-hydrogen peroxide for pre-deliming (eliminating sodium sulfide).

(4) Silane-hydrogen peroxide pre-deliming (elimination of sodium sulfide): adding 50 parts of normal temperature water, KT 17171 parts and 0.3 part of nonionic degreasing agent, and slowly rotating for 2 hours; adding 3 parts of ammonium sulfate and 0.5 part of deliming agent, and slowly rotating for 2 hours; adding 1 part of hydrogen peroxide, slowly rotating for 4 hours, washing with water, and performing main deliming (sodium sulfide elimination) on silane-hydrogen peroxide.

(5) Silane-hydrogen peroxide main deliming (elimination of sodium sulfide): adding 30 parts of normal temperature water, KT 17172 parts and 0.3 part of nonionic degreasing agent, and slowly rotating for 2 hours; adding 8 parts of ammonium sulfate and 0.5 part of deliming agent, and slowly rotating for 2 hours; adding 1 part of hydrogen peroxide, slowly rotating for 4 hours, slowly rotating for 30 minutes/stopping for 30 minutes, and stopping for 10 hours; washing with water until the pH value is 6.5-7.5, and then performing cationic silica gel pretreatment.

(6) Pretreatment of cationic silica gel: adding 30 parts of 35 ℃ hot water, 17173 parts of KT and 40313 parts of KT, slowly rotating for 3 hours, and carrying out salt leaching.

(7) Salt leaching: adding 8 parts of industrial salt and 8 parts of anhydrous sodium sulphate, slowly rotating for 3 hours at 35 ℃, and then pickling.

(8) Pickling: adding 1.5 parts of industrial formic acid, adjusting the pH value range to 2.5-3, slowly rotating for 8 hours, and entering the initial tanning of the silicon aldehyde/silica gel-tannin extract combination.

(9) Initial tanning of silicon aldehyde/silica gel-tannin extract combination: adding KT 28114 parts, acid-resistant oil 0.3 part and KT 20344 parts, and slowly rotating for 6 hours; adding 12 parts of tannin extract, 4 parts of acid-resistant oil, KT 20346 parts and KT 59013 parts, and slowly rotating for 10 hours at 35 ℃; adding 2 parts of acid-resistant oil and 2 parts of KT 20344, adjusting the temperature to 45 ℃, and slowly rotating for 10 hours; and (5) taking out the materials from the drum, standing for 48 hours, squeezing water, uniformly shaving, and softening by entering cationic silica gel.

(10) Softening the cationic silica gel: weighing 100 parts by weight of the shaved primary tanned leather in a rotary drum, washing with water twice, and adjusting the temperature to 45 ℃; adding 100 parts of water with the temperature of 45 ℃, KT 40316 parts, KT 17176 parts and KT 28112 parts, rotating for 4 hours at medium speed, adding 2 parts of baking soda, rotating for 4 hours at medium speed, and entering anionic silane-tannin extract dyeing retanning, filling and fatliquoring.

(11) Anionic silane-tannin extract dyeing retanning filling fatliquoring: adding X parts of dye, 5 parts of tannin extract, 5 parts of KT 59012 parts, KT 20345 parts, KT 23515 parts, 3 parts of acid-resistant oil and 8 parts of fatting agent into the mixture in one bath, rotating the mixture at a medium speed of 45 ℃ for 6 hours, and entering cationic silica gel for fixation and mildew prevention.

(12) Fixing and mildew prevention by cationic silica gel: adding formic acid into the mixture in one bath to adjust the pH value to 3-3.5, rotating at 45 ℃ for 1 hour at medium speed, adding KT 40312 parts and mildew preventive 0.3 parts, rotating at 45 ℃ for 2 hours at medium speed, washing twice, discharging from a drum, and drying and finishing to obtain a leather blank.

The industrial products of KT1717, KT3007, KT2811, KT4031, KT2034, KT5901, KT2351 and the like are purchased from Minninida silicofluoride application research and test factories in Wenjiang river district of metropolis. The environment-friendly silica gel-tannin extract combined tanning close-skin ecological flexible smooth rabbit skin bra leather manufactured by the invention is soft and exquisite, moisture permeable and breathable, free and transparent, mildew-proof and sterilization when being in close contact with breast nipples, namely has good skin physiological respiration function, and has the fine and smooth of real silk without the roughness and stiffness of cotton and hemp.

Example 3: the invention discloses an outer layer lining leather of an environment-friendly silica gel-tannin extract combined tanning skin-next ecological flexible sheepskin bra, which comprises fur silane soaking water, silica gel ash-coating wool pushing, silane-alkali sulfide fur soaking ash, silica gel reliming, silane-hydrogen peroxide pre-deliming (alkali sulfide elimination), silane-hydrogen peroxide main deliming (alkali sulfide elimination), cationic silica gel pretreatment, salt leaching, pickling, silicon aldehyde primary tanning/silica gel-tannin extract combined primary tanning, cationic silica gel softening, anionic silane-tannin extract dyeing, retanning filling and greasing, cationic silane fixing and mildew proofing, and specifically comprises the following steps:

(1) soaking fur in silane: weighing 100 parts of sheep fur by weight in a rotary drum, washing for 10 minutes, adding 150 parts of normal temperature water, KT 17170.5 parts, KT 30070.1 parts, 0.3 part of nonionic degreasing agent, 0.1 part of bactericide, 0.5 part of soda ash and 0.3 part of sodium sulfide, slowly rotating for 3 hours, then rotating for 30 minutes/stopping for 30 minutes, rotating for 10 hours, discharging from the drum, cutting the head, tail and limbs, draining water and preserving moisture, and then feeding the wool into silica gel coated ash to push the wool.

(2) And (3) wrapping ash with silica gel and pushing wool: weighing 5000 parts of water, 171740 parts of KT, 300720 parts of liming auxiliary agent, 50 parts of nonionic degreasing agent, 80 parts of sodium hydrosulfide and 250 parts of sodium sulfide by weight; stirring evenly, then slowly adding 3000 parts of lime while stirring to obtain mortar. Coating mortar on the surface of sheep skin, properly increasing the coating amount of the ridge line, overlapping meat and meat, standing and stacking for 12-24 hours, pushing hair, entering a drum, and then entering silane-sodium sulfide for hair destruction and liming.

(3) Silane-sodium sulfide wool destruction and liming: adding normal-temperature water 20 parts, KT 17170.3 parts, non-ionic degreasing agent 0.3 part, liming auxiliary agent 0.5 part, sodium hydrosulfide 0.6 part and sodium sulfide 0.6 part, slowly rotating for 1 hour, then rotating for 30 minutes/stopping for 30 minutes, and rotating for 4 hours; checking the condition of broken wool, after the broken wool is clean, adding KT 17173 parts, rotating for 2 hours, adding normal-temperature water 30 parts, lime 1 part and liming auxiliary agent 0.2 part, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2 hours; and then adding 80 parts of normal temperature water, 2 parts of lime and 0.3 part of liming auxiliary agent, rotating for 30 minutes/stopping for 30 minutes, rotating for 5 minutes/stopping for 55 minutes after rotating for 2 hours, and rotating for 24 hours. The waste liquid can be reserved as ash leaching liquid or ash compounding liquid for recycling, and then enters silica gel for ash compounding.

(4) Silica gel ash coating: adding 200 parts of hair destroying liming waste liquid, adding KT 17171 parts, 0.5 part of nonionic degreasing agent and 3 parts of lime, slowly rotating for 30 minutes/stopping for 30 minutes, and stopping for 10 hours; the waste liquid can be used as ash dipping liquid or ash compounding liquid for recycling, and the ash skin is washed clean by water and enters silane-hydrogen peroxide for pre-deliming (eliminating sodium sulfide).

(5) Silane-hydrogen peroxide pre-deliming (elimination of sodium sulfide): adding 50 parts of normal temperature water, KT 17171 parts and 0.3 part of nonionic degreasing agent, and slowly rotating for 2 hours; adding 3 parts of ammonium sulfate and 0.5 part of deliming agent, and slowly rotating for 2 hours; adding 1 part of hydrogen peroxide, slowly rotating for 4 hours, washing with water, and performing main deliming (sodium sulfide elimination) on silane-hydrogen peroxide.

(6) Silane-hydrogen peroxide main deliming (elimination of sodium sulfide): adding 30 parts of normal temperature water, KT 17172 parts and 0.3 part of nonionic degreasing agent, and slowly rotating for 2 hours; adding 8 parts of ammonium sulfate and 0.5 part of deliming agent, and slowly rotating for 2 hours; adding 1 part of hydrogen peroxide, slowly rotating for 4 hours, slowly rotating for 30 minutes/stopping for 30 minutes, and stopping for 10 hours; washing with water until the pH value is 6.5-7.5, and then performing cationic silica gel pretreatment.

(7) Pretreatment of cationic silica gel: adding 30 parts of 35 ℃ hot water, 17173 parts of KT and 40313 parts of KT, slowly rotating for 3 hours, and carrying out salt leaching.

(8) Salt leaching: adding 8 parts of industrial salt and 8 parts of anhydrous sodium sulphate, slowly rotating for 3 hours at 35 ℃, and then pickling.

(9) Pickling: adding 1.5 parts of industrial formic acid, adjusting the pH value range to 2.5-3, slowly rotating for 8 hours, and entering the initial tanning of the silicon aldehyde/silica gel-tannin extract combination.

(10) Initial tanning of silicon aldehyde/silica gel-tannin extract combination: adding KT 28114 parts, acid-resistant oil 0.3 part and KT 20344 parts, and slowly rotating for 6 hours; adding 12 parts of tannin extract, 4 parts of acid-resistant oil, KT 20346 parts and KT 59013 parts, and slowly rotating for 10 hours at 35 ℃; adding 2 parts of acid-resistant oil and 2 parts of KT 20344, adjusting the temperature to 45 ℃, and slowly rotating for 10 hours; and (5) taking out the materials from the drum, standing for 48 hours, squeezing water, uniformly shaving, and softening by entering cationic silica gel.

(11) Softening the cationic silica gel: weighing 100 parts by weight of the shaved primary tanned leather in a rotary drum, washing with water twice, and adjusting the temperature to 45 ℃; adding 100 parts of water with the temperature of 45 ℃, KT 40316 parts, KT 17176 parts and KT 28112 parts, rotating for 4 hours at medium speed, adding 2 parts of baking soda, rotating for 4 hours at medium speed, and entering anionic silica-tannin extract dyeing retanning, filling and fatliquoring.

(12) Anionic silicone gum-tannin extract dyeing retanning filling fatliquoring: adding X parts of dye, 5 parts of tannin extract, 5 parts of KT 59012 parts, KT 20345 parts, KT 23515 parts, 3 parts of acid-resistant oil and 8 parts of fatting agent into the mixture in one bath, rotating the mixture at a medium speed of 45 ℃ for 6 hours, and then entering cationic silane for fixation and mildew prevention.

(13) Fixing and mildew prevention by cationic silica gel: adding formic acid into the mixture in one bath to adjust the pH value to 3-3.5, rotating at 45 ℃ for 1 hour at medium speed, adding KT 40312 parts and mildew preventive 0.3 parts, rotating at 45 ℃ for 2 hours at medium speed, washing twice, discharging from a drum, and drying and finishing to obtain a leather blank.

The industrial products of KT1717, KT3007, KT2811, KT4031, KT2034, KT5901, KT2351 and the like are purchased from Minninida silicofluoride application research and test factories in Wenjiang river district of metropolis. The outer layer lining leather of the environment-friendly silica gel-tannin extract combined tanning close-skin ecological flexible smooth sheepskin bra manufactured by the invention has soft texture, high elasticity, stiffness, smoothness, easy shaping, fine hand feeling and free and transparent performance; particularly, the design that a special-effect breast health care and nursing traditional Chinese medicine bag can be placed in an interlayer between the skin-friendly rabbit skin on the inner layer of the bra and the supporting sheep skin on the outer layer of the bra, and the bra has special nursing effects on dredging the channels and collaterals of breasts and preventing hyperplasia of mammary glands and breast cancer; meanwhile, the bra has the functions of supporting and gathering breast tissues, making the breast tissues stiff and plump, and avoiding the adverse stimulation and even damage of traditional toxic and harmful bra fillers such as sponge, plastic foam and the like to the breasts; in addition, the material has stronger functions than similar materials in the aspects of sweat absorption, difficult deformation, easy management and storage, self-cleaning and the like.

The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the embodiments are only used to help understanding the principles of the embodiments of the present invention; meanwhile, for a person skilled in the art, according to the embodiments of the present invention, there may be variations in the specific implementation and application ranges, and in summary, the content of the present description should not be construed as a limitation to the present invention.

Claims

1. A manufacturing process of silane tanning of chromium-free ecological silica gel-tannin extract combined tanning vegetable leather comprises the steps of fur silane soaking, silica gel ash-coating hair pushing, silane-alkali sulfide hair destroying soaking, silica gel redrying, silane-hydrogen peroxide pre-deliming, silane-hydrogen peroxide main deliming, cationic silica gel pretreatment, salt leaching, pickling, silicon aldehyde primary tanning/silica gel-tannin extract combined primary tanning, cationic silica gel softening, anionic silica gel-tannin extract dyeing and retanning filling and fatliquoring, cationic silica gel fixing and mildew-proof treatment, and is characterized in that:

(1) the fur silane soaking step comprises the following steps: weighing 100 parts of fur by weight in a rotary drum, washing for 10 minutes, adding 150 parts of normal-temperature water, KT 17170.1-1 part, KT 30070.05-0.3 part, 0.2-0.5 part of non-ionic degreasing agent, 0.1-0.3 part of bactericide, 0.3-1 part of sodium carbonate and 0.1-0.3 part of sodium sulfide, rotating for 3 hours at a slow speed, rotating for 30 minutes/stopping for 30 minutes, rotating for 8-10 hours, discharging from the drum, removing meat, entering silica gel package ash and pushing hair;

(2) the step of pushing wool by wrapping ash with silica gel comprises the following steps: weighing 5000 parts of water, 171730-60 parts of KT, 300715-40 parts of liming auxiliary agent, 30-60 parts of nonionic degreasing agent, 60-100 parts of sodium hydrosulfide and 280 parts of sodium sulfide; stirring, slowly adding 3000-4000 parts of lime, stirring while adding to obtain mortar, coating the mortar on the flesh side of the fur, properly increasing the coating amount of the back line, overlapping the flesh and the flesh, standing and stacking for 6-12 hours, pushing the fur, entering a drum, and then, entering silane-sodium sulfide to destroy the fur and ash;

(3) the steps of destroying and liming the silane-sodium sulfide comprise: adding normal temperature water 10-30 parts, KT 17170.1-0.3 part, non-ionic degreasing agent 0.3-0.5 part, liming auxiliary agent 0.3-0.5 part, sodium hydrosulfide 0.5-0.8 part and sodium sulfide 0.5-0.8 part, slowly rotating for 1 hour, then rotating for 30 minutes/stopping for 30 minutes, and rotating for 2-4 hours; adding KT 17170.5-1 part, sodium sulfide 0.5-1.5 parts, lime 1-3 parts, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2-4 hours; adding KT 17170.5-1 part, sodium sulfide 0.5-1.5 parts, lime 1-3 parts, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2-12 hours; checking the condition of broken wool, after the broken wool is clean, adding KT 17171-5 parts, rotating for 2-4 hours, adding normal temperature water 30-50 parts, lime 1-2 parts and liming auxiliary agent 0.1-0.3 part, rotating for 30 minutes/stopping for 30 minutes, and rotating for 2-4 hours; adding 50-80 parts of normal temperature water, 1-2 parts of lime and 0.1-0.3 part of liming auxiliary agent, rotating for 30 minutes/stopping for 30 minutes, rotating for 2-4 hours, rotating for 5 minutes/stopping for 55 minutes, rotating for 10-24 hours, discharging the drum sheet, and keeping the waste liquid as liming liquid or liming liquid for recycling, and then entering silica gel for liming;

(4) the silica gel ash recovery step is as follows: weighing 100 parts by weight of calcined soda flakes into a rotary drum, adding 200 parts by weight of waste liquid of hair destruction and liming, adding KT 17171-2 parts by weight, 0.3-0.5 part by weight of non-ionic degreasing agent and 3-5 parts by weight of lime, slowly rotating for 30 minutes/stopping for 30 minutes, and stopping for 4-12 hours; the waste liquid is reserved as liming liquid or liming liquid for recycling, the ash bark is washed clean and enters silane-hydrogen peroxide for pre-deliming;

(5) the silane-hydrogen peroxide pre-deliming step comprises the following steps: adding normal temperature water 50-100 parts, KT 17171-2 parts, and non-ionic degreasing agent 0.3-0.5 parts, and rotating slowly for 2 hours; adding 3-5 parts of ammonium sulfate and 0.5-1 part of deliming agent, and slowly rotating for 2 hours; adding 1-2 parts of hydrogen peroxide, slowly rotating for 4 hours, washing with water, and performing main deliming by using silane-hydrogen peroxide;

(6) the silane-hydrogen peroxide main deashing step comprises the following steps: adding normal temperature water 30-50 parts, KT 17172-4 parts, and non-ionic degreasing agent 0.3-0.5 parts, and slowly rotating for 2 hours; adding 5-8 parts of ammonium sulfate and 0.5-1 part of deliming agent, and slowly rotating for 2 hours; adding 1-2 parts of hydrogen peroxide, slowly rotating for 4 hours, slowly rotating for 30 minutes/stopping for 30 minutes, and stopping for 4-12 hours; washing with water until the pH value is 6.5-7.5, and then performing cationic silica gel pretreatment;

(7) the pretreatment steps of the cationic silica gel are as follows: adding 30-50 parts of 35 ℃ hot water, KT 17173-5 parts and KT 40313-5 parts, slowly rotating for 3 hours, and performing salt leaching;

(8) the salt leaching step comprises the following steps: adding 8-10 parts of industrial salt and 8-10 parts of anhydrous sodium sulphate, slowly rotating for 3-8 hours at 35 ℃, and performing pickling;

(9) the pickling step comprises the following steps: adding 0.5-1.5 parts of industrial formic acid, adjusting the pH value range to 2.5-3, slowly rotating for 8-12 hours, and performing combined primary tanning of the silica aldehyde primary tanning/silica gel-tannin extract;

(10) the step of the combined initial tanning of the silicon aldehyde initial tanning/the silica gel-tannin extract comprises the following steps: adding KT 28113-5 parts, acid-resistant oil 0.1-0.3 part and KT 20342-4 parts, and slowly rotating for 4-8 hours; adding 8-16 parts of tannin extract, 2-4 parts of acid-resistant oil, 2-6 parts of KT 20344 and 4 parts of KT 59012-4 parts, and slowly rotating for 8-12 hours; adding 1-2 parts of acid-resistant oil and KT 20342-4 parts, adjusting the temperature to 45 ℃, and slowly rotating for 8-12 hours; standing for 48 hours after the materials are discharged from the drum, squeezing water, uniformly shaving, and softening by entering cationic silica gel;

(11) the softening step of the cationic silica gel is as follows: weighing 100 parts by weight of the shaved primary tanned leather in a rotary drum, washing with water twice, and adjusting the temperature to 45 ℃; adding 150 parts of water with the temperature of 45 ℃, 100-8 parts of KT 40315-8 parts of KT 17175-8 parts of KT 28111-3 parts of KT, rotating for 4-6 hours at medium speed, adding 1-2 parts of baking soda, rotating for 4-6 hours at medium speed, and entering into anionic silica-tannin extract dyeing and retanning;

(12) the anionic silicon gum-tannin extract dyeing retanning step comprises the following steps: adding appropriate amount of dye, 3-5 parts of tannin extract, 3-4 parts of KT 59012-4 parts, KT 20346-8 parts, KT 23514-6 parts, 3-5 parts of acid-resistant oil and 5-8 parts of common grease in one bath, rotating at medium speed of 45 ℃ for 8-12 hours, and performing cationic silica gel fixation and mildew-proof treatment;

(13) the cationic silica gel fixing and mildew-proof treatment steps are as follows: adding formic acid into the mixture in one bath to adjust the pH value to 3-3.5, rotating the mixture at the temperature of 45 ℃ for 1 hour at medium speed, adding KT 40311-3 parts and the mildew preventive 0.3-0.5 part, rotating the mixture at the temperature of 45 ℃ for 2 hours at medium speed, washing the mixture twice, discharging the mixture out of a drum, and drying and finishing the mixture to obtain a leather blank.

2. The process of manufacturing silane tanned hides of the chrome-free ecotype silica gel-tannin extract combination tanned hides of claim 1, characterized in that: KT1717 is soft-return replacement neutralization silane, KT1717 is side polyamino hydrocarbyl polyhydroxy hydrocarbyl triethoxy silyl polymethylsilsesquioxane aqueous emulsion polymerized by weak cation emulsion, and is also named as: the water-soluble organic silicon high-molecular silane coupling agent and the low-temperature coupling self-crosslinking amino-hydrocarbon hydroxyl silicone oil have the technical indexes that: the density is 0.95g/ml at 20 ℃, the content of water soluble substances is 20 +/-1%, the pH value of solvent water is 6.5 +/-0.2, the viscosity is 40-50mPa.s, and the appearance is light blue emulsion.

3. The process of manufacturing silane tanned hides of the chrome-free ecotype silica gel-tannin extract combination tanned hides of claim 1, characterized in that: KT3007 is a penetrating crosslinking silane auxiliary agent, KT3007 is a polyepoxyoxyalcoholic ether alkyl polymethylsiloxane silane coupling agent isopropanol water solution, and the technical indexes are as follows: the density is 0.85g/ml at 20 ℃, the weight percentage of non-volatile components is 36 +/-1%, the solvent is water, the pH value is 6.5 +/-0.2, the charge is non-ionic, the viscosity is 90-110mPa.s, and the appearance is light yellow to colorless transparent liquid.

4. The process of manufacturing silane tanned hides of the chrome-free ecotype silica gel-tannin extract combination tanned hides of claim 1, characterized in that: the KT4031 is cationic polyurethane retanning silica gel, the KT4031 is a water-soluble cationic polyurethane high-molecular silane coupling agent with coupling and crosslinking reaction activity, and is a strong cationic poly-alkoxy siloxane carbamate-grease-silica gel polymer; the technical indexes are as follows: the density is 0.95g/ml to 1.05g/ml at 20 ℃, the content of water soluble matters is 18 percent to 22 percent, the pH value of solvent water is 4.5 +/-0.3, the viscosity is 400-500mPa.s, and the appearance is milky yellow emulsion.

5. The process of manufacturing silane tanned hides of the chrome-free ecotype silica gel-tannin extract combination tanned hides of claim 1, characterized in that: KT2811 is amino silane modified fatty aldehyde, KT2811 is water-soluble organic silicon polyethylene polyamine alkaline high molecular silane coupling agent, has good crosslinking hybridization modification, permeation and dispersion effects, and has the following technical indexes: the pH value is 2-4, the charge is weak cationic, and the appearance is light blue emulsion.

6. The process of manufacturing silane tanned hides of the chrome-free ecotype silica gel-tannin extract combination tanned hides of claim 1, characterized in that: the KT2034 is cotton-bubble meat-feeling filled silica gel, the KT2034 is lecithin and hydroxyalkyl aminoalkyl carboxyalkyl carboxyalkoxysilicane radical modified polymethylsiloxane secondary derivative, and the technical indexes are as follows: the density is 0.92g/ml at 20 ℃, the content of water soluble substances is 26-30%, the pH value of solvent water is 3.8 +/-0.2, the viscosity is 150-180mPa.s, and the appearance is light cream yellow thick liquid.

7. The process of manufacturing silane tanned hides of the chrome-free ecotype silica gel-tannin extract combination tanned hides of claim 1, characterized in that: KT5901 is a silicon sulfone filled synthetic tanning agent, and KT5901 is naphthol sulfonic acid and SO with a silicon sulfone bridged structure and high quality filling performance₂The organic derivative secondary hydrolysis and condensation polymer tanning agent has the technical indexes of 20 ℃ density: 1.10g/mL-1.25g/mL, 46% -50% of water soluble substance,solvent water, pH: 4.0 ± 0.2, viscosity: 120 mPa.S-140 mPa.S, the appearance is light brown semitransparent thick liquid.

8. The process of manufacturing silane tanned hides of the chrome-free ecotype silica gel-tannin extract combination tanned hides of claim 1, characterized in that: the KT2351 is foaming elastic fat-liquoring silicone oil, the KT2351 is modified polymerization type silicone oil, and the modified reaction type silicone oil is an aqueous emulsion type copolymer of vinyl amino monomers and carboxyl monomers, and the technical indexes are as follows: the density is 1.10g/ml-1.25g/ml at 20 ℃, the water soluble substance content is 28-33%, the pH value of the solvent water is 4.5-5.5, the viscosity is 24000-26000mPa.s, and the appearance is creamy yellow thicker liquid.