CN101613963A - Utilize the continuous leather staining method of ultrasonic wave and microwave radiation - Google Patents
Utilize the continuous leather staining method of ultrasonic wave and microwave radiation Download PDFInfo
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Abstract
The continuous leather staining method that utilizes ultrasonic wave and microwave radiation disclosed by the invention, be to moisture≤60% with retanning stuffing leather base mechanical presses, 1min then at least dyes its dyeing bath that contains surface reactive material in the ultrasonic wave sound field that places frequency≤100kHz, mechanical presses is to dye liquor content 〉=50% again, with microwave irradiation 1min at least, or dyeing that will be behind microwave irradiation leather is at the fixation liquid fixation that contains the fixation material of the ultrasonic wave sound field that places frequency≤100kHz 1min at least, again with fixation dyeing leather mechanical presses to fixation liquid hold-up 〉=50%, operation carries out drying and covers with paint, lacquer, colour wash, etc. processing getting final product routinely again.The inventive method is skillfully constructed, technology and simple to operate, can make the length of penetration of dyestuff reach 0.5～2mm, the color depth no significant difference of surface and otch color, satisfy the dyeing requirement of conventional soft leather fully, and dyeing leather surface color is anti-ly done, the wet rubbing fastness reaches 4～5 grades of color staining fastnesses and 〉=3 grades.
Description
Technical field
The invention belongs to the leather coloring technical field, be specifically related to continuous leather staining method a kind of high-efficiency environment friendly, that utilize ultrasonic wave and microwave radiation.
Background technology
Dyeing is an important procedure of tanning production, its objective is and gives leather certain color.Can improve the outward appearance of leather by dyeing, make it to adapt to popular style, and increase the surcharge of its commodity.
The main method of leather coloring is water-bath dyeing in rotary drum at present.This colouring method is big because of every drum head operation amount, the dyeing relative fixed, and designs and varieties are single, are difficult to adapt to the fast transition of popular designs and varieties on the market, and can produce a large amount of high chromas and unmanageable leather-making waste water.Continuous reinforcement along with people's environmental consciousness, the method that the process hides worker develops is used to reduce the dyeing discharging of waste liquid has: the leather dyeing method (Zhang Fangzhong of 1. low liquor ratio or aneroid ratio, pasty state dyeing and fat-liquoring method is one of effective way that solves in suede leather look flower, Chinese leather, 1984,13 (6): 25～27; Dye stuff polymerzation bathless dry dyeing method for leather dyeing, Chinese invention patent, the patent No.: 90104028.2.), yet this class colouring method easily makes dyeing leather surface color inhomogeneous or masstone occurs, can not satisfy the dyeing requirement of conventional monochromatic leather.2. non-aqueous media leather coloring.As, leather coloring in the solvent medium (Rafidinarivo, H., New process of leatherdyeing in solvent medium, JSLTC, 1996,80 (1): 6-10.), leather coloring (Liao Longli in the supercritical CO 2 medium, Feng Yuchuan, Chen Min, etc., CO
2Pollution-free tanning technical research (III) CO in the supercritical fluid media
2Leather coloring research in the supercritical fluid media, leather science and engineering, 1999,9 (4): 6-12.).Exhaust the rate of using though this class colouring method has high dyestuff, and dyeing medium reclaims easily.But because the cost height, corollary equipment lacks, and this class colouring method is difficult to realize industrialization promotion at present.3. new and high technology leather coloring, as, electrochemistry leather coloring (Zhao Xin, Cao Xiangyu, Feng Yunsheng, the electrochemistry dyeing pre-test of leather, Qiqihar University's journal, 1998,14 (3): 67-71.).This class staining technique is faced with the problem that allied industry equipment lacks equally, is difficult to realize industrialization promotion at present.
In recent years, as a kind of staining technique fast, the ultrasonic wave leather coloring has obtained broad research.Because ultrasonic wave has cavitation, can produce the microenvironment of moment high temperature, high pressure, high energy, thereby can promote dyestuff penetration, (stone is green for He Youjie, Zhang Zhaosheng to improve the dyestuff dye-uptake, Deng, ultrasonic wave is to the influence [J] of dye diffusion coefficient and dye-uptake in the leather coloring, Sichuan University's journal (engineering science version), 2001 (33): 74-77; VenktasasubramanianSivakumar, Studies on the use of power ultrasound in leather dyeing, UltrasoundSonochemistry, 2003 (19): 85-94; Venktasasubramanian Sivakumar, Influence of ultrasoundon diffusion through skin/leather matrix, Chemical Engineering and Processing:ProcessIntensification, 2008,47 (12): 2076-2083.).These researchs all are that the wet blue leather with common process production is the raw material skin, have studied the certain law in the interior ultrasonic wave leather coloring of longer dyeing time (30min) process.But its: 1. dyeing time is longer, is unfavorable for suitability for industrialized production; 2. because of mainly being to be the raw material skin with the wet blue leather, do not consider to combine (actual leather-making technology is that the leather base after retanning, neutralization is carried out stuffing and dyeing again) with actual leather-making technology; 3. because of being breadboard exploitative experiment, and still there is problem, promotes so be difficult to directly these research conclusions to be used for the industry of ultrasonic wave leather coloring to environmental emission dyeing waste liquid.
Microwave has obtained Preliminary Applications as a kind of high-new physically activated technology in the dyeing and finishing field, but mainly concentrate in the dyeing and fixation of textiles (Wu Lianghua thanks to Kong Liang, Wang Wei etc., the microwave dyeing technique pre-test (on), dyeing and finishing technique, 2008,30 (12): 1-5; Jiangsu Shenghong Chemical Fiber Co., Ltd., a kind of energy-saving high-efficiency environment-friendly staining technique, Chinese invention patent, application number: 200710134041.X; The Yongtong Dyeing Technology Development Center, Shaoxing City, the microwave dyeing method of fabric, Chinese invention patent, the patent No.: 99116982.4; Paik Bo Hyun utilizes the low temperature of microwave, low immersion rate, no tension force and short-term decoration method and device, Chinese invention patent, the patent No.: 98101687.1).Though microwave dyeing method has efficiently, environmental protection and advantage such as energy-conservation, yet, because it is different with fiber plane knitting mode in the textiles, leather coloring leather base is to have a certain thickness natural macromolecular material by what the collagenous fibres 3 D weaving formed, separately during applied microwave irradiation, short time effect (＜10min) after, it is dark and be evenly distributed along the thickness direction infiltration that dyestuff is difficult in dyeing leather otch, thereby can not satisfy the basic demand of high-quality leather for dye coloring.
Summary of the invention
The objective of the invention is problem, a kind of continuous leather staining method that utilizes ultrasonic wave and microwave radiation is provided at the prior art existence.
To achieve the object of the present invention, the inventor is on the basis of existing ultrasonic wave leather coloring and the disclosed method of microwave textile dyeing, furtherd investigate the influence for leather coloring of ultrasonic wave and microwave irradiation, can promote the infiltration of dyestuff though find ultrasonic wave, speed is slower; But microwave is assisted staining also, but adopt separately ultrasonic wave or microwave irradiation be difficult in the short time (＜10min) reach saturated, the uniform requirement of otch color in the dyeing leather; Microwave not only can be removed from office in dry dyeing, also can play tint retention to color, and can improve dyeing leather surface uniformity and dense property.In order to accelerate dyeing kinetics and to make the otch in the dyeing leather reach saturated, the uniform requirement of color, the inventor has explored again after leather base moisture is reduced, relend and help ultrasonic wave and drying, fixation, the level dyeing of the effect of certain acceleration dyeing and microwave arranged and make color increase dark effect, find that finally this process combination can make dense, the height of the anti-rubbing fastness the (xerotripsis: 4～5 grades of surface color of dyeing leather; Wet rubbing: 〉=3 grades), the otch color is saturated and be evenly distributed.In order further to explore the feasible process conditions and the inherent mechanism of action, the inventor also studies the histology of the wet leather that is squeezed to different conditions and the dyeing leather produced when ultrasonic wave and microwave irradiation are auxiliary thereof, find because the mechanical presses preliminary treatment has been removed in the leather collagen fiber interfascicular crack behind the part moisture, can make capillary pipeline between the leather collagen fiber bundle be in the vacuum state of microenvironment, this is for the rubber-like leather, in the process of state, the air of trace can enter into leather inside before it is extremely pushed by extruding back recovering state.When such leather when placing the dyeing bath of ultrasonic wave sound field, the air and the collagenous fibres gap of the inner trace of leather will cause ultrasonic cavitation threshold value acoustic pressure to descend, thereby promote the generation of cavitation phenomenon.Cavitation effect of ultrasonic waves can promote dyestuff to the leather diffusion inside.Simultaneously, the inner micro-vacuum environment of the leather that forms in the mechanical presses process also helps taking place based on the diffusion of dye strength difference.That is, when promoting dyestuff penetration, cavitation effect of ultrasonic waves has cooperative effect when before the dyeing leather base being carried out the mechanical presses preliminary treatment with dyeing.In addition, in order to reclaim dye liquor and fixation liquid, avoid its discharging that environment is polluted, and also for reduce cost, energy consumption, economize on resources, the inventor has also explored on the basis that does not influence leather dyeing of base and fixation, to the mechanical force extruding degree of leather base, and makes the dye liquor that squeezes out and fixation liquid retrieval system again.
On the basis of above exploratory development, if follow-up covering with paint operation is for less demanding (the xerotripsis staining fastness:＜4 grades of the anti-rubbing fastness of color of dyeing leather; Wet rubbing staining fastness:＜3 grades) time, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation provided by the invention is to moisture≤60% with retanning stuffing leather base mechanical presses, leather base after will pushing then is at the dyeing bath that contains surface reactive material of the ultrasonic wave sound field that the places frequency≤100kHz 1min at least that dyes, the leather mechanical presses will dye again to dye liquor content 〉=50%, with frequency is the microwave irradiation 1min at least of 2450MHz, and subsequent handling routinely carries out drying and cover with paint, lacquer, colour wash, etc. to handle getting final product subsequently.This not only can reduce the use of fixation material, can also directly utilize microwave irradiation that the dyeing leather is carried out drying, fixation and hyperchromic.The dye liquor retrieval system that wherein squeezes out.
(the xerotripsis staining fastness: 〉=4 grades if the anti-rubbing fastness of color that follow-up covering with paint operation is removed from office for dyeing is had relatively high expectations; Wet rubbing staining fastness: 〉=3 grades) time, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation provided by the invention is to moisture≤60% with retanning stuffing leather base mechanical presses, leather base after will pushing then is at the dyeing bath that contains surface reactive material of the ultrasonic wave sound field that the places frequency≤100kHz 1min at least that dyes, the leather mechanical presses will dye again to dye liquor content 〉=50%, with frequency is the microwave irradiation 1min at least of 2450MHz, dyeing leather that subsequently will be behind microwave irradiation is at the fixation liquid fixation that contains the fixation material of the ultrasonic wave sound field that places frequency≤100kHz 1min at least, at last with fixation dyeing leather mechanical presses to fixation liquid hold-up 〉=50%, subsequent handling routinely carries out drying and covers with paint, lacquer, colour wash, etc. processing getting final product again.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
The preferred version of each operation is in the said method: before dyeing, be 45～60% to retanning stuffing leather base mechanical presses to moisture, and more preferably 50～55%; The ultrasonic frequency that adopts during to dyeing of leather base and dyeing leather fixation is 20～100kHz, and 20～40kHz more preferably, and ultrasonic wave radiation intensity is 0.5～6W/cm
2, 1～2W/cm more preferably
2The mass percent of dyestuff is 0.5～6% in the dyeing bath, and the dyestuff mass percent is preferably 0.5～1.5% in the dyeing bath when dying the light color leather, and the dyestuff mass percent is preferably 4～5% in the dyeing bath when dying dark leather; The mass percent of surface reactive material is 0.2～2%, more preferably 0.5～1%; Dyeing temperature is 25～45 ℃, and more preferably 30～40 ℃, dyeing time is 1～3min, more preferably 1～1.5min; To leather base dye liquor content after the dyeing leather mechanical presses is 50～70%, more preferably 60～65%; Microwave radiation is 0.1～3W/cm
3, 0.5～1W/cm more preferably
3, microwave irradiation time is 1～3min, more preferably 1～2min; The mass concentration of fixation liquid is 0.5～2%, more preferably 1～1.5%, and color fixing temperature is 25～45 ℃, more preferably 30～40 ℃, the fixation time is 1～3min, more preferably 1～1.5min; Be 50～70% to dyeing leather mechanical presses to fixation liquid hold-up after the fixation, more preferably 60～65%.
Used dyestuff is conventional leather coloring dyestuff when dyeing in the above method, be specifically as follows ACID DYES, direct dyestuff and premetallized dye, preferred permeability is black, the direct fast black of leather black, leather, infiltration, reactive red, reactive yellow, 1: 1 premetallized dye, 1: 2 premetallized dye preferably.The surface reactive material that adds in the dye liquor during dyeing can be in anionic surfactant, nonionic surface active agent and the alcohols material at least a.Wherein anionic surfactant can be succinate sodium sulfonate, alkyl phenol ether sulfosuccinate sodium, lauryl sodium sulfate and neopelex, preferred succinate sodium sulfonate and alkyl phenol ether sulfosuccinate sodium; Nonionic surface active agent can be wetting agent jfc, paregal O-25, paregal O-15 and polysiloxane-based wetting agent, preferred wetting agent jfc and polysiloxane-based wetting agent; Alcohols material can be isopropyl alcohol, ethanol, butanols and propyl alcohol, preferred isopropyl alcohol and ethanol.Used fixation material can be at least a in the molysite of positive divalent, aluminium salt, organic acid and the cation type resin that chemical valence is positive 3 valencys for chemical valence during fixation.At least a in preferred alchlor, aluminum sulfate, frerrous chloride, ferrous succinate, formic acid, acetic acid, cationic amino resins and the cation type polyurethane resin.
The above-mentioned continuous leather staining method that utilizes ultrasonic wave and microwave radiation provided by the invention, utilize micro-vacuum environment in the retanning stuffing leather after the mechanical presses dexterously, the moment high temperature that produces by cavitation effect of ultrasonic waves at first, high pressure, the high energy microenvironment, promoted the infiltration of dyestuff to leather inside, secondly the high speed polarization by microwave has promoted the migration of dyeing leather surface dye and painted, utilize the positive electricity character in the color-fixing agent further to promote the set of dyestuff in the dyeing leather at last, make the length of penetration of dyestuff in dyeing finished product leather can reach 0.5～2mm, can satisfy conventional in the market soft leather fully, as upper leather, shoe lining leather, clothing leathers etc. are for the requirement of the dyestuff penetration degree of depth, and make the surface of dyeing leather and the color depth no significant difference of otch color, and the surface color of dyeing leather is anti-dried, the wet rubbing fastness can reach 4～5 grades of color staining fastnesses and 〉=3 grades respectively.
Because the leather base is done in the retanning stuffing and the wet leather of the pretreated retanning stuffing of mechanical presses base has approximate charge property and leather structure of fibrous tissue feature, therefore, colouring method provided by the invention also is applicable to the dyeing of the dried leather of retanning stuffing base, and the surface color and the otch color color depth of dyeing leather are approaching, surface color is anti-to be done, the wet rubbing fastness also can reach 4～5 grades of color staining fastnesses respectively and 〉=3 grades.
The present invention also has the following advantages:
1, method provided by the invention is skillfully constructed, technology and simple to operate, its used capital equipment is the mechanical presses device, have the staining trough of ultrasonic generator and the microwave cavity of soaper and sealing, it is soluble that these are not only the existing equipment technology, and can be that lace curtaining connects (seeing accompanying drawing) to these technique units by conveyer belt, can realize leather is carried out that serialization dyes one by one etc., the mechanization degree height, work load is low.In conjunction with advanced mechanical presses equipment, can finish accurate control for moisture in the leather base.
2, carry out dye fixing with method provided by the invention, can realize dyeing and the zero-emission of fixation waste liquid, therefore not only environmental protection, and also can reduce cost, economize on resources.
3, because the dyeing temperature of method provided by the invention is lower than normal dyeing temperature (50～60 ℃), and this dyeing temperature can be kept by the fuel factor of ultrasonic wave itself, do not need additionally to provide heat to keep the temperature of dyeing bath, therefore not only energy-conservation, and can further reduce cost.
4, dyeing and the required total time of fixation owing to method provided by the invention only is 3～10min, thereby dyeing efficient height, power consumption are few, and can also obtain the dyeing leather of multi-color kind by the conversion of dyeing bath, can make in time and effecting reaction the variation of outward appearance demands such as leather color in the market to guarantee dyeing.
5, because method provided by the invention uses material dyestuff, surface reactive material and fixation material to be conventional usedization of leather-making technology material, thereby wide material sources.
6, with method provided by the invention retanning stuffing leather is dyeed, all can not produce obvious influence to the operation of subsequent handling and the mechanical property of finished leather (comprising tensile strength, tearing strength) and apparent property (comprising surface color intensity, color uniformity, fullness, flexibility etc.), and all can not detect Cr VI in the finished leather, therefore, this method safety, reliable.
7, method provided by the invention not only can or be done leather and dye in tannery the wet leather of retanning stuffing, also can change colour for the surface color of dyeing leather in leather goods processing sites such as Shoes Factory or clothing factories, and therefore, this method is applied widely.
Description of drawings
Accompanying drawing is that the serialization that the inventive method was suitable for is dyed, the schematic diagram of color-fixing device, 1-conveyer belt wherein, 2-compression roller, 3-staining trough, 4-ultrasonic transducer, 5-microwave cavity, 6-transfer roller, 7-soaper.
The specific embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field still belongs to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention makes.
In addition, what deserves to be explained is that the content of dyestuff and surface reactive material is mass percent, the concentration of fixation liquid is mass concentration.
Embodiment 1
Will be through chrome tanning agent retanning, sulfated castor oil and the stuffing of polymer class fatting agent, thickness be 1.4mm the first machinery of the wet leather of sheepskin upper leather to be squeezed to moisture be 50～55%, be that 20kHz, radiation intensity are 0.5W/cm in ultrasonic frequency then
2, temperature is 25 ℃, contain the 1min that dyes in the dyeing bath of the black and 0.5% polysiloxane-based wetting agent of 4% infiltration; After leather mechanical presses to the dye liquor content that will dye is 60～65%, be that 2450MHz, radiation intensity are 1W/cm with frequency
3Microwave irradiation 1min; Is that 20kHz, radiation intensity are 0.5W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 25 ℃, concentration is fixation 3min in 1% the aluminum trichloride solution; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 60～65% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Will be through the retanning of amino resins retanning agent, sulphation neat's foot oil and the stuffing of lecithin class fatting agent, thickness be the first machinery of the wet leather of the goat shoe upper leather of 1.6mm to be squeezed to moisture be 45～50%, be that 40kHz, radiation intensity are 1.5W/cm in ultrasonic frequency then
2, temperature is 45 ℃, contain the 2min that dyes in the dyeing bath of 0.5% reactive yellow and 0.2% alkyl phenol ether sulfosuccinate sodium; After leather mechanical presses to the dye liquor content that will dye is 50～55%, be that 2450MHz, radiation intensity are 0.1W/cm with frequency
3Microwave irradiation 3min.Then, carrying out processing such as drying and covering with paint according to the subsequent handling of routine gets final product.The dye liquor retrieval system that wherein squeezes out.
Will be through chrome tanning agent and acrylic resin retanning agent retanning, the stuffing of synthetic neat's foot oil fatting agent, thickness be the first machinery of the wet leather of the lining leather of pigskin shoes of 1.6mm to be squeezed to moisture be 55～60%, be that 70kHz, radiation intensity are 3W/cm in ultrasonic frequency then
2, temperature is 40 ℃, contain the 3min that dyes in the dyeing bath of 1% reactive red and 1% poly-succinate sodium sulfonate; After leather mechanical presses to the dye liquor content that will dye is 65～70%, be that 2450MHz, radiation intensity are 3W/cm with frequency
3Microwave irradiation 1min; Is that 70kHz, radiation intensity are 3W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 40 ℃, concentration is fixation 1min in 1% alchlor and aluminum sulfate (mass ratio is 1: the 1) solution; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 65～70% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Will be through chrome tanning agent and the retanning of phenols syntans, atoleine and the stuffing of siliceous class fatting agent, thickness be the first machinery of the wet leather of the ox-hide shoe lining leather of 1.4mm to be squeezed to moisture be 50～55%, be that 100kHz, radiation intensity are 6W/cm in ultrasonic frequency then
2, temperature is 25 ℃, contain the 1.5min that dyes in the dyeing bath of 6% leather black and 2% isopropyl alcohol; After leather mechanical presses to the dye liquor content that will dye is 50～55%, be that 2450MHz, radiation intensity are 1.5W/cm with frequency
3Microwave irradiation 2min; Is that 100kHz, radiation intensity are 6W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 25 ℃, concentration is fixation 2min in 2% formic acid and lactic acid (mass ratio is 1: the 1) solution; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 50～55% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Will be through chrome tanning agent and wattle extract retanning, atoleine and the stuffing of fluorinated fatting agent, thickness be the first machinery of the wet leather of the sheepskin clothing leather of 1.4mm to be squeezed to moisture be 55～60%, be that 80kHz, radiation intensity are 4W/cm in ultrasonic frequency then
2, temperature is 30 ℃, contain the 1.5min that dyes in the dyeing bath of 4% leather and 0.5% wetting agent jfc; After leather mechanical presses to the dye liquor content that will dye is 60～65%, be that 2450MHz, radiation intensity are 3W/cm with frequency
3Microwave irradiation 1min; Is that 80kHz, radiation intensity are 4W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 30 ℃, concentration is fixation 2min in 1.5% the acetum; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 60～65% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Embodiment 6
Will be through chrome tanning agent retanning, sulfated castor oil and the stuffing of synthetic neat's foot oil fatting agent, thickness be the first machinery of the wet leather of the pig leather for making garment of 1.2mm to be squeezed to moisture be 50～55%, be that 28kHz, radiation intensity are 2W/cm in ultrasonic frequency then
2, temperature is 35 ℃, contain the 1.5min that dyes in the dyeing bath of 2%1: 1 bronze medal complex dyes and 1% neopelex; After leather mechanical presses to the dye liquor content that will dye is 55～60%, be that 2450MHz, radiation intensity are 1W/cm with frequency
3Microwave irradiation 2min; Is that 28kHz, radiation intensity are 2W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 35 ℃, concentration is fixation 1.5min in 1% the cation type polyurethane resin solution; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 55～60% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Will be through chrome tanning agent and modified glutaraldehyde retanning, sulfated castor oil and the stuffing of polymer class fatting agent, thickness be the first machinery of the wet leather of the goat shoe upper leather of 1.8mm to be squeezed to moisture be 50～55%, be that 35kHz, radiation intensity are 1.5W/cm in ultrasonic frequency then
2, temperature is 30 ℃, contain the 1.2min that dyes in the dyeing bath of 1.2%1: 2 aluminium complex dyes and 0.8% lauryl sodium sulfate; After leather mechanical presses to the dye liquor content that will dye is 60～65%, be that 2450MHz, radiation intensity are 0.8W/cm with frequency
3Microwave irradiation 1.5min; Is that 35kHz, radiation intensity are 1.5W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 30 ℃, concentration is fixation 3min in 0.5% the aluminum trichloride solution; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 60～65% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Embodiment 8
Will be through chrome tanning agent retanning, sulphation neat's foot oil and the stuffing of lecithin class fatting agent, thickness be 1.4mm the first machinery of the wet leather of lining leather of pigskin shoes to be squeezed to moisture be 50～55%, be that 45kHz, radiation intensity are 1W/cm in ultrasonic frequency then
2, temperature is 25 ℃, contain the 1min that dyes in the dyeing bath of black and 0.5% the surface reactive material (mass ratio is 1: 1 isopropyl alcohol and a wetting agent jfc) of 3% infiltration; After leather mechanical presses to the dye liquor content that will dye is 60～65%, be that 2450MHz, radiation intensity are 1W/cm with frequency
3Microwave irradiation 1min; Is that 45kHz, radiation intensity are 1W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 35 ℃, concentration is fixation 1min in 1.5% the cation type polyurethane resin solution; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 60～65% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Embodiment 9
Will be through chrome tanning agent retanning, the stuffing of sulfated castor oil fatting agent, thickness be the first machinery of the wet leather of the pig leather for making garment of 1.4mm to be squeezed to moisture be 50～55%, be that 35kHz, radiation intensity are 1.5W/cm in ultrasonic frequency then
2, temperature is 35 ℃, contain the 1.5min that dyes in the dyeing bath of 4.5% leather black and 0.8% alkyl phenol ether sulfosuccinate sodium; After leather mechanical presses to the dye liquor content that will dye is 60～65%, be that 2450MHz, radiation intensity are 0.5W/cm with frequency
3Microwave irradiation 2min; Is that 35kHz, radiation intensity are 1.5W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 40 ℃, concentration is fixation 3min in 1.5% the cationic amino resins solution; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 65～70% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Embodiment 10
Will be through chrome tanning agent, amino resins retanning agent and acrylic resin retanning agent retanning, sulfated castor oil, synthetic neat's foot oil and the stuffing of atoleine fatting agent, thickness be the first machinery of the wet leather of the cow leather upper leather of 3.0mm to be squeezed to moisture be 50～55%, be that 30kHz, radiation intensity are 1.5W/cm in ultrasonic frequency then
2, temperature is 25 ℃, contain the 1min that dyes in the dyeing bath of black and 1% the surface reactive material (mass ratio is 2: 1 ethanol and a propyl alcohol) of 4% infiltration; After leather mechanical presses to the dye liquor content that will dye is 60～65%, be that 2450MHz, radiation intensity are 1W/cm with frequency
3Microwave irradiation 1min; Is that 30kHz, radiation intensity are 1.5W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 35 ℃, concentration is fixation 1.5min in 1% the solution of ferrous chloride; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 60～65% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Embodiment 11
Will be through chrome tanning agent, amino resins retanning agent and the retanning of myrica extract retanning agent, polymer class fatting agent and the stuffing of lecithin class fatting agent, thickness is that the cow leather upper revolutionary cadre of 1.3mm removes from office is that 20kHz, radiation intensity are 1.5W/cm in ultrasonic frequency earlier
2, temperature is 30 ℃, contain the 1.5min that dyes in the dyeing bath of the surface reactive material of 1.5% reactive blue and 0.9% (mass ratio is 1: 2 butanols and a wetting agent jfc); After leather mechanical presses to the dye liquor content that will dye is 60～65%, be that 2450MHz, radiation intensity are 0.8W/cm with frequency
3Microwave irradiation 1.5min; Is that 20kHz, radiation intensity are 1.5W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 30 ℃, concentration is fixation 1.5min in 1% organic acid (mass ratio is 1: 1 formic acid and an acetic acid) solution; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 60～65% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
Embodiment 12
Will be through chrome tanning agent, valonea extract, the retanning of modified glutaraldehyde retanning agent, sulfated castor oil and the stuffing of synthetic neat's foot oil fatting agent, thickness is that the sheepskin clothes revolutionary cadre of 0.6mm removes from office is that 30kHz, radiation intensity are 1W/cm in ultrasonic frequency earlier
2, 1min dyes in the dyeing bath of temperature is 35 ℃, contain 1.5% dyestuff (mass ratio is that 1: 2 direct fast black and infiltration is black) and 0.5% polysiloxane-based wetting agent; After leather mechanical presses to the dye liquor content that will dye is 60～65%, be that 2450MHz, radiation intensity are 1W/cm with frequency
3Microwave irradiation 1min.Then, carrying out processing such as drying and covering with paint according to the subsequent handling of routine gets final product.The dye liquor retrieval system that wherein squeezes out.
Embodiment 13
Will be through amino resins retanning agent, phenols syntans and wattle extract retanning, siliceous class fatting agent and the stuffing of fluorinated fatting agent, thickness is that the cow leather upper revolutionary cadre of 1.7mm removes from office is that 40kHz, radiation intensity are 2W/cm in ultrasonic frequency earlier
2, temperature is 30 ℃, contain the 1.5min that dyes in the dyeing bath of the surface reactive material of 5% leather and 1% (mass ratio is 1: 1 paregal O-25 and peregal O-15); After leather mechanical presses to the dye liquor content that will dye is 60～65%, be that 2450MHz, radiation intensity are 1W/cm with frequency
3Microwave irradiation 1.5min; Is that 40kHz, radiation intensity are 2W/cm with the leather of the dyeing behind the microwave irradiation in ultrasonic frequency
2, temperature be 35 ℃, concentration is fixation 2min in 1.5% fixation material (mass ratio is 1: 1 frerrous chloride and a ferrous succinate) solution; With fixation dyeing leather mechanical presses to fixation liquid hold-up be 60～65% after, carry out drying and cover with paint, lacquer, colour wash, etc. and wait processing to get final product according to the subsequent handling of routine.Dye liquor that wherein squeezes out and fixation liquid retrieval system.
In order to investigate the present invention's dyeing, the performance of the physical and mechanical properties of leather and the anti-rubbing fastness of color after the fixation, the dyeing leather of the above embodiment preparation of picked at random of the present invention, and through conventional subsequent technique drying, cover with paint, lacquer, colour wash, etc., fall the soft finished product leather of handling that waits, according to QB/T 2710-2005, QB/T 2711-2005 standard test leather tensile strength and percentage elongation and tearing strength, and with test result and QB/T 1872-2004 clothes leather standard, QB/T 1873-2004 vamp compares (seeing Table) with leather standard and QB/T 2680-2004 shoe lining with the leather standard.Data show in the table, dye according to method of the present invention, and carry out processing such as drying and covering with paint according to the subsequent technique of routine, and the finished product that obtains leather all can satisfy the mechanical property technical indicator of national Specification.In addition, also according to QB/T 2537-2001 standard test the finished product that obtains through processing such as conventional subsequent technique drying, coverings with paint of the dyeing leather colour fastness test of removing from office, wherein anti-xerotripsis fastness is 4～5 grades of color staining fastnesses, the moisture-proof rubbing fastness can reach 3 grades of color staining fastnesses (the dyeing leather is through processing such as conventional subsequent technique drying, coverings with paint among the embodiment 8, and the color moisture-proof rubbing fastness of the finished product that obtains leather is 3～4 grades).That is, dye according to method of the present invention, and carry out processing such as drying and covering with paint according to the subsequent technique of routine, the finished product that obtains leather all can satisfy the colour fastness test technical indicator of national Specification.The apparent property of the finished product leather that dyeing leather of assessing by the sense organ mode and processing obtain: flexibility and fullness and conventional retanning, dyeing, stuffing technology gained leather are suitable.
Table
Claims (10)
1, a kind of continuous leather staining method that utilizes ultrasonic wave and microwave radiation, this method is to moisture≤60% with retanning stuffing leather base mechanical presses, leather base after will pushing then is at the dyeing bath that contains surface reactive material of the ultrasonic wave sound field that the places frequency≤100kHz 1min at least that dyes, the leather mechanical presses will dye again to dye liquor content 〉=50%, with frequency is the microwave irradiation 1min at least of 2450MHz, subsequent handling routinely carries out drying and covers with paint, lacquer, colour wash, etc. to handle getting final product subsequently, or dyeing that will be behind microwave irradiation leather is at the fixation liquid fixation that contains the fixation material of the ultrasonic wave sound field that places frequency≤100kHz 1min at least, at last with fixation dyeing leather mechanical presses to fixation liquid hold-up 〉=50%, subsequent handling routinely carries out drying and covers with paint, lacquer, colour wash, etc. to handle getting final product dye liquor that wherein squeezes out and fixation liquid retrieval system again.
2, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation according to claim 1, this method are removed from office base mechanical presses to moisture to the retanning stuffing before dyeing be 45～60%; The ultrasonic frequency that adopts during to dyeing of leather base and dyeing leather fixation is 20～100kHz, and the ultrasonic wave radiation intensity is 0.5～6W/cm
2The mass percent of dyestuff is 0.5～6% in the dyeing bath, and the mass percent of surface reactive material is 0.2～2%; Dyeing temperature is 25～45 ℃, and dyeing time is 1～3min; To leather base dye liquor content after the dyeing leather mechanical presses is 50～70%; Microwave radiation is 0.1～3W/cm
3, microwave irradiation time is 1～3min; The mass concentration of fixation liquid is 0.5～2%, and color fixing temperature is 25～45 ℃, and the fixation time is 1～3min; After the fixation mechanical presses to fixation liquid hold-up being removed from office in dyeing is 50～70%.
3, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation according to claim 1 and 2, this method is removed from office base mechanical presses to moisture to the retanning stuffing before dyeing be 50～55%, is 60～65% to the leather of the dyeing after dyeing mechanical presses to dye liquor content; After the fixation mechanical presses to fixation liquid hold-up being removed from office in dyeing is 60～65%.
4, the ultrasonic frequency that the continuous leather staining method that utilizes ultrasonic wave and microwave radiation according to claim 1 and 2, this method adopt when the leather base is dyeed and dye the leather fixation is 20～40kHz, and the ultrasonic wave radiation intensity is 1～2W/cm
2
5, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation according to claim 1 and 2, this method dyestuff mass percent in the dyeing bath that dyes the light color leather is 0.5～1.5%, and the dyestuff mass percent is 4～5% in the dyeing bath that dyes dark leather; The surface reactive material mass percent is 0.5～1%; Dyeing temperature is 30～40 ℃, and the time is 1～1.5min.
6, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation according to claim 1 and 2, it is 0.5～1W/cm that this method is carried out microwave radiation to the dyeing leather after dyeing
3, microwave irradiation time is 1～2min.
7, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation according to claim 1 and 2, this method is 1～1.5% to the mass concentration of the fixation liquid of dyeing leather fixation; Color fixing temperature is 30～40 ℃, and the fixation time is 1～1.5min.
8, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation according to claim 1 and 2, the used surface reactive material of this method are at least a in anionic surfactant, nonionic surface active agent and the alcohols material; The fixation material is that chemical valence is at least a in the molysite of positive divalent, aluminium salt, organic acid and the cation type resin that chemical valence is positive 3 valencys.
9, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation according to claim 8, the used surface reactive material of this method are at least a in succinate sodium sulfonate, alkyl phenol ether sulfosuccinate sodium, wetting agent jfc, polysiloxane-based wetting agent, isopropyl alcohol and the ethanol.
10, the continuous leather staining method that utilizes ultrasonic wave and microwave radiation according to claim 8, the used fixation material of this method are at least a in alchlor, aluminum sulfate, frerrous chloride, ferrous succinate, formic acid, acetic acid, cationic amino resins and the cation type polyurethane resin.
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| CN102080315A (en) * | 2011-01-14 | 2011-06-01 | 盐城纺织职业技术学院 | Method and device for dyeing by utilizing ultrasonic wave and microwave |
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