CN101570940A - Method for modification, dyeing and multifunctional composite finishing of aramid fiber - Google Patents
Method for modification, dyeing and multifunctional composite finishing of aramid fiber Download PDFInfo
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- CN101570940A CN101570940A CNA2009100276881A CN200910027688A CN101570940A CN 101570940 A CN101570940 A CN 101570940A CN A2009100276881 A CNA2009100276881 A CN A2009100276881A CN 200910027688 A CN200910027688 A CN 200910027688A CN 101570940 A CN101570940 A CN 101570940A
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Abstract
The invention discloses a method for modification, dyeing and multifunctional composite finishing of aramid fiber, and belongs to the technical field of textile chemical industry. Through surface physical and chemical modification for the aramid fiber, the method improves the physical and chemical states of the aramid fiber surface and is favorable for the dyeing and after finishing of the aramid fiber. The specific process flow comprises the following steps of cleaning before the dyeing of the aramid fiber, pretreatment of the aramid fiber, dyeing of the aramid fiber, and multifunctional composite finishing of the aramid fiber. Not only the dyeing property of the aramid fiber treated by the method is remarkably improved, but also the dyeing fastness is good, the aramid fiber has good moisture permeability particularly, and simultaneously the aramid fiber is endued with good anti-ultraviolet ageing function. Moreover, the aramid fiber is subjected to composite finishing by adopting a nano composite sol, and the method has wide applicability, simple process, relatively low treatment cost, and low requirements on the applied technology and equipment.
Description
Technical field
The method of a kind of modification of aramid fiber, dyeing and multifunctional composite finishing belongs to technical field of textile chemical engineering.
Background technology
Kevlar promptly gathers terephthalate p-phenylenediamine (PPD) fiber, calls to be aramid fiber resin, aramid fiber, claims the Kevlar that again, belongs to aromatic polyamide, is at first succeeded in developing in the sixties in 20th century by du pont company.Because its structure is special, aramid fiber has good heat-resisting quantity and anti-flammability, therefore be widely used in fire-entry suit, the army's protective clothing, and be a kind of strategic materials.Yet as the clothes of special industries such as fire-fighting, require to have special sign, color, so that in urgent, chaotic scene identification, searching.But because the upright and outspoken macromolecular chain of aramid fiber has highly crystalline and surperficial non-activity group, and its vitrification point is up to 270 ℃, can't dye with the method for routine, even indivedual dyestuff dyes on reluctantly, but COLOR FASTNESS is very poor.At present, the colouring method of this fibrid of report mainly contains dyeing of superhigh-temperature and-pressure method and carrier dyeing process both at home and abroad, but color fastness to washing and crock fastness are also all not ideal enough.A thinking that solves its colouring problem is exactly to pass through some physics, chemistry or physicochemical method to the aramid fiber pre-treatment, improves the physics and the chemical state of fiber surface, and then the interaction of reinforcing fibre and matrix, improves its dyeability.A kind of method that improves aramid fiber 1313 stock-dye fastness is disclosed among the patent CN101029457A.Comprise high pressure pre-treatment and high-temperature pressure dyeing two procedures in this method.Because the processing of high pressure can better be adsorbed on the fiber carrier, dyes on the fiber thereby be beneficial on the dyestuff.Found that the color fastness to washing of the aramid fiber after the processing and colorfastness to rubbing etc. have all obtained improving preferably.Mention a kind of colouring method of aryl fiber cloth among the patent CN1888183A, comprised shrinking processes and dyeing process.The fiber colour of handling is bright-coloured, feel is soft, good permeability and wear comfortable.
Though kevlar fabric has excellent chemical stability,, still have the characteristics of wettability difference as a kind of synthetic fiber.Simultaneously, aramid fiber is a kind of light activated macromolecular material, issue third contact of a total solar or lunar eclipse degradation with aging in the ultraviolet ray irradiation easily, particularly the ultraviolet light in 280～320nm scope is the strongest to the aramid fiber photodegradation, should not be directly exposed under the daylight and use, therefore need it is carried out the ultraviolet screener arrangement to improve its serviceability and range of application.Patent CN101215782A has invented a kind of light ageing resisting finishing method of aromatic polyamide fabric.The intensity of kevlar fabric behind ultraviolet ageing after this method is handled can well be kept, the not loss of mechanical performance of arrangement back fabric.But its processing time is longer, can't satisfy industrialized continuous production.Patent CN 200610025829 has invented a kind of TiO
2Anti UV finishing liquid and to the anti UV finishing method of aramid fiber, aramid fiber is after this anti UV finishing method is handled, the anti-ultraviolet ageing performance of aramid fiber, yarn or fabric is significantly strengthened, but titanium dioxide is easy to generate the phenomenon of blueing in application process.And aramid fiber also will possess good moisture permeability as the lining of fire-entry suit, but as a kind of synthetic fiber, the wettability of aramid fiber is very poor.Therefore, these performances must obtain by the back arrangement.Sol-gel process is a kind of new technology of loomage surface modification.Adopting sol-gel technique is the method preferably of giving one or more functions of aramid fiber to the method that fiber carries out top finish.This method is exactly to add an amount of finishing agent in complex sol, carries out coating by method such as padding at fabric face, and drying and necessary heat treatment then forms thin film at fabric face.These class methods are wide to the applicability of kinds of fibers, and processing cost is low, and are less demanding to the technology and equipment of using.
Summary of the invention
The object of the present invention is to provide a kind of method of modification, dyeing and multifunctional composite finishing of aramid fiber, improve the aramid fiber value-added content of product, product is developed towards profound and superior direction.
Technical scheme of the present invention:
By aramid fiber is carried out surface physics, chemical modification, improve the physics and the chemical state of aramid fiber surface, and then the interaction between reinforcing fibre and dyestuff and the finishing agent, be beneficial to the dyeing and the multifunctional composite finishing of aramid fiber.Technological process comprises: the multifunctional composite finishing of the cleaning before the aramid fiber dyeing, aramid fiber preliminary treatment, aramid fiber dyeing and aramid fiber, and stand-by.
(1) cleaning before the aramid fiber dyeing
Some slurries and greasy dirt are all contained in the surface of commodity aramid fiber, and these slurries and greasy dirt will directly influence the dyeing and finishing following process of aramid fiber.Therefore, the removal to aramid fiber fabric face slurry and greasy dirt is the first step of aramid fiber dyeing and back arrangement.
Cleaning is: alkali cleaning (NaOH 5-10g/L, degreaser DO 2-5g/L, bath raio 1: 20-40, temperature 95-100 ℃, time 0.5-1h), flushing with clean water is dried stand-by.
(2) aramid fiber preliminary treatment
Because the aramid fiber macromolecular structure closely, degree of crystallinity is big, vitrification point is very high, do not have affinity groups, if directly to its dyeing, dyestuff dyes on not substantially, and it is very difficult to dye.Therefore before dyeing, must carry out surface modification to it, introduce some on the aramid fiber surface and have the polar group of reactivity, the reaction of increase and dyestuff improves aramid fiber dyeability and finishing effect.The selected pretreating scheme of the present invention can be:
1. plasma preliminary treatment: the aramid fiber after will cleaning places the reative cell normal temperature of plasma generator to handle: power 25-150W, processing time 1-10min, pressure 1-50Pa.
Or 2. phosphoric acid preliminary treatment: the aramid fiber after will cleaning places mass concentration 10%-85% phosphoric acid solution, takes out behind the 40-100 ℃ of processing 30-90min, clean repeatedly to neutrality with distilled water, and oven dry, standby;
(3) aramid fiber dyeing: select for use:
1. High Temperature High Pressure carrier dyeing process: pretreated aramid fiber input is contained in the water of dyeing carrier, dyeing carrier concentration is 60-70mL/L, making water temperature is 30-60 ℃, aramid fiber and dye bath mass ratio are 1: 20-40, to bathe temperature rise to 70-100 ℃ with the speed of 1-3 ℃/min, the DISPERSE DYES and the concentration of progressively adding mass concentration and be 1%-7% in dye bath are the accelerant of 10-80g/L, the adjusting dye liquor pH value is 2-5, speed with 1-3 ℃/min rises to 130-135 ℃ with the dye bath temperature, insulation 60-80min, insulation finishes the back and with the speed of 1-2 ℃/min the dye bath temperature is reduced to 60-80 ℃, discharge dye liquor, with concentration is the soap lye cleaning of 3-6g/L, after the cleaning fiber is taken out oven dry;
Or 2. preliminary treatment-dyeing: pretreated aramid fiber input is contained in the water of dyeing carrier, dyeing carrier concentration is 60-70mL/L, making water temperature is 30-60 ℃, aramid fiber and dye bath mass ratio are 1: 20-40, to bathe temperature rise to 70-80 ℃ with the speed of 1.5-2 ℃/min, the cation dyes and the concentration of progressively adding mass concentration and be 1%-7% in dye bath are the accelerant of 10-70g/L, the adjusting dye liquor pH value is 2-5, just dye bath temperature of speed with 1-1.5 ℃/min rises to 100-120 ℃, insulation 40-60min, insulation finishes the back and with the speed of 1-2 ℃/min the dye bath temperature is reduced to 60-80 ℃, discharge dye liquor, with concentration is the soap lye cleaning of 3-6g/L, after the cleaning fiber is taken out oven dry;
(4) multifunctional composite finishing of aramid fiber:
Sol-gel technique is a kind of new technology of fiber surface coating.Utilize the nano combined colloidal sol dressing liquid of sol-gel technology preparing fiber to be flooded or pads processing; again through Overheating Treatment; complex sol in the dressing liquid forms thin film at fiber surface; having the titania nanoparticles of anti-ultraviolet effect or zinc oxide nano particle and some to have the ventilative finishing agent of moisture absorption some is anchored in the gel mould, makes aramid fiber also possess advantages of good waterproof property when having good resistance ultraviolet ageing function.
Aramid fiber after the dyeing is put into arrangement bathes, it is 1 that aramid fiber is bathed mass ratio with arrangement: 20-40, arrangement bathe for contain moisture absorption poromeric finishing agent 2-10g/L, concentration is the complex sol of 0.5-2.5mol/L, by the dipping or the mode of padding it is put in order on the aramid fiber, dry, bake, stand-by.
Aramid fiber: this technology is fit to various types of aramid fiber bulk fibres, yarn or fabric.
Low temperature plasma atmosphere is the mixed atmosphere of one or more gases in the air, nitrogen, oxygen, ammonia, inert gas of concentration≤2%.
Described dyeing carrier is selected one or both in aromatic alcohol, aromatic ketone or the aromatic ether for use.
Accelerant during dyeing is a kind of in sodium nitrate, sodium sulphate, Boratex or the sodium chloride or two kinds.
Dyestuff during dyeing is DISPERSE DYES or cation dyes.
Described complex sol is selected TiO for use
2Colloidal sol, ZnO colloidal sol, SiO
2The complex sol of two or three in the colloidal sol.
Described moisture absorption poromeric finishing agent is selected silicone based hydrophilic finishing agent, epoxide resin type hydrophilic finishing agent, polyester and polyether block copolymer for use.
Beneficial effect of the present invention: compare with afterfinish method with the dyeing of routine, advantage of the present invention is:
1. using plasma or phosphoric acid come the preliminary treatment aramid fiber, introduce or produce some active groups at fiber surface, as-COOH ,-OH ,-OOH,＞C=O ,-NH
2Deng, improve the interaction between aramid fiber and dyestuff and the finishing agent, simultaneously, less to physical and mechanical propertiess such as the brute force influence of aramid fiber.In addition-COO
-Deng increasing of anionic group, also help cation dyes on dye.
2. aramid fiber is used cationic dyeing again through after the preliminary treatment, compares traditional High Temperature High Pressure disperse dyeing, and the fabric COLOR FASTNESS is higher, and is bright-colored, and feel is soft, and dyeing time is shorter, and dyeing temperature is lower, helps reducing production costs.
3. adopt nano combined colloidal sol that fiber is carried out composite finishing, applicability is wide, and technology is simple, and processing cost is relatively low, less demanding to the technology and equipment of using, when giving aramid fiber good resistance ultraviolet ageing function, also possess good moisture permeability.
The specific embodiment
Embodiment 1: the selected sample of present embodiment is the aramid fiber yarn, and selected pretreatment mode is the low temperature plasma preliminary treatment, and selected dyeing carrier is an acetophenone, and selected dressing liquid is titanium/zinc complex sol, and selected moisture absorption poromeric finishing agent is silicone based.
Get 20g aramid fiber yarn by the pre-treatment of dyeing of following technology: alkali cleaning (NaOH 6g/L, degreaser DO5g/L; bath raio 1: 20; 100 ℃ of temperature, time 45min), flushing with clean water, oven dry, plasma preliminary treatment (2% air; 25 ℃ of temperature; power 100W, processing time 5min, pressure 25Pa).
Aramid fiber dyeing: above-mentioned pretreated aramid fiber input is contained in the water of acetophenone 60mL/L, and water temperature is 40 ℃, and bath raio is 1: 20.Speed with 1 ℃/min rises to 70 ℃ with temperature, and progressively adding cation dyes and the concentration that concentration is about 6% (owf) in dye bath is the Na of 50g/L
2SO
4, regulating dye liquor pH value is 3.Speed with 1 ℃/min rises to 120 ℃ with temperature, insulation 45min.Speed with 1 ℃/min after insulation finishes cools the temperature to 70 ℃, discharges dye liquor, adds water concentration and cleans for the 4g/L soap lye, fiber is taken out oven dry.
Aramid fiber multifunctional composite finishing: get the aramid fiber yarn after the dyeing, it is immersed concentration is 0.6mol/L, bath raio 1: 20, and the proportioning that contains finishing agent 5g/L is to handle 40min in 1: 1 titanium/zinc complex sol, take out 60 ℃ of oven dry, under 140 ℃, bake 3min again.
Sample by the arrangement of above-mentioned technology has carried out the test of following performance respectively, as following table:
Annotate: uvioresistant performance test, uviol lamp power 400W, irradiation time 30h.
Embodiment 2: the selected sample of present embodiment is a kevlar fabric, and selected pretreatment mode is the plasma preliminary treatment, and selected dyeing carrier is a phenmethylol, and selected dressing liquid is silicon/titanium complex sol, and selected moisture absorption poromeric finishing agent is the epoxide resin type hydrophilic finishing agent.
Get the 20g kevlar fabric by the pre-treatment of dyeing of following technology: alkali cleaning (NaOH 5g/L, degreaser DO4g/L, bath raio 1: 30,100 ℃ of temperature, time 40min), flushing with clean water, 80 ℃ of oven dry, plasma preliminary treatment (2% oxygen, 25 ℃ of temperature, power 75W, processing time 10min, pressure 5Pa).
Kevlar fabric dyeing: above-mentioned pretreated kevlar fabric input is contained in the water of phenmethylol 70mL/L, and water temperature is 50 ℃, and bath raio is 1: 30.Speed with 1 ℃/min rises to 75 ℃ with temperature, and progressively adding cation dyes and the concentration that concentration is about 6% (owf) in dye bath is the NaCI of 50g/L, and regulating dye liquor pH value is 4.Speed with 1 ℃/min rises to 115 ℃ with temperature, insulation 50min.Speed with 1 ℃/min after insulation finishes cools the temperature to 65 ℃, discharges dye liquor, and adding water concentration is the soap lye cleaning of 5g/L, fabric is taken out oven dry.
The kevlar fabric multifunctional composite finishing: get the kevlar fabric after the dyeing, it is immersed concentration is 1mol/L, contains finishing agent 4g/L, and proportioning is after handling 3s in silicon/titanium complex sol of 4: 1, takes out two and soaks two and roll, and pick-up 75% bakes 3min again under 140 ℃.
Sample by the arrangement of above-mentioned technology has carried out the test of following performance respectively, as following table:
Annotate: uvioresistant performance test, uviol lamp power 400W, irradiation time 30h.
Embodiment 3: the selected sample of present embodiment is a kevlar fabric, and selected pretreatment mode is the phosphoric acid preliminary treatment, and selected dyeing carrier is an acetophenone, and selected dressing liquid is silicon/titanium/zinc complex sol, and selected moisture absorption poromeric finishing agent is polyester and polyether block copolymer.
Get the 20g kevlar fabric by the pre-treatment of dyeing of following technology: alkali cleaning (NaOH 5g/L, degreaser DO5g/L, bath raio 1: 40,90 ℃ of temperature, time 50min), flushing with clean water, 70 ℃ of oven dry, phosphoric acid preliminary treatment (phosphoric acid 20%, 100 ℃ of temperature, processing time 50min), flushing with clean water, oven dry.
Kevlar fabric dyeing: above-mentioned pretreated kevlar fabric input is contained in the water of acetophenone 70mL/L, and 55 ℃ of water temperatures, bath raio are 1: 25.Speed with 1 ℃/min rises to 70 ℃ with temperature, and progressively adding cation dyes and the concentration that concentration is about 5% (owf) in dye bath is the NaNO of 40g/L
3, regulating dye liquor pH value is 3.5.Speed with 1 ℃/min rises to 120 ℃ with temperature, insulation 70min.Speed with 1 ℃/min after insulation finishes cools the temperature to 60 ℃, discharges dye liquor, and adding water concentration is the soap lye cleaning of 3g/L, fabric is taken out oven dry.
The kevlar fabric multifunctional composite finishing: get the kevlar fabric after the dyeing, it is immersed concentration is 1mol/L, contains finishing agent 3g/L, proportioning is after handling 5s in silicon/titanium/zinc complex sol of 2: 1: 1, taking-up two is soaked two and is rolled, and pick-up 70% bakes 3min again under 140 ℃.
Sample by the arrangement of above-mentioned technology has carried out the test of following performance respectively, as following table:
Annotate: uvioresistant performance test, uviol lamp power 400W, irradiation time 30h.
Embodiment 4: the selected sample of present embodiment is a kevlar fabric, and selected staining method is a high-temperature and high pressure dyeing process, and selected dyeing carrier is a phenmethylol, and selected dressing liquid is silicon/titanium/zinc complex sol, and selected moisture absorption poromeric finishing agent is polyester and polyether block copolymer.
Get 20g aramid fiber fabric by the pre-treatment of dyeing of following technology: alkali cleaning (NaOH 5g/L, degreaser DO 4g/L, bath raio 1: 35,100 ℃ of temperature, time 60min), flushing with clean water, 70 ℃ of oven dry, standby.
The aramid fiber textile dyeing: the kevlar fabric input of above-mentioned processing is contained in the water of phenmethylol 70mL/L, and water temperature is 65 ℃, and bath raio is 1: 20.Speed with 1 ℃/min rises to 60 ℃ with temperature, and progressively adding DISPERSE DYES and the concentration that concentration is about 6% (owf) in dye bath is the Na of 50g/L
2SO
4, regulating dye liquor pH value is 3.5.Speed with 1 ℃/min rises to 130 ℃ with temperature, insulation 60min.Speed with 1 ℃/min after insulation finishes cools the temperature to 60 ℃, discharges dye liquor, and adding water concentration is the soap lye cleaning of 4g/L, fabric is taken out oven dry.
Aramid fiber fabric multifunctional composite finishing: get the kevlar fabric after the dyeing, it is immersed concentration is 1mol/L, contains finishing agent 3g/L, proportioning is after handling 7s in silicon/titanium/zinc complex sol of 2: 2: 1, taking-up two is soaked two and is rolled, and pick-up 70% bakes 3min again under 140 ℃.
Sample with the arrangement of above-mentioned technology has carried out the test of following performance respectively, as following table:
Annotate: uvioresistant performance test, uviol lamp power 400W, irradiation time 30h.
Claims (8)
1, the method for a kind of modification of aramid fiber, dyeing and multifunctional composite finishing is characterized in that technological process is: the cleaning before the aramid fiber dyeing, aramid fiber preliminary treatment, aramid fiber dyeing, the multifunctional composite finishing of aramid fiber;
(1) cleaning before the aramid fiber dyeing: alkali cleaning: the NaOH 5-10g/L and the degreaser DO 2-5g/L aqueous solution are that alkali cleaning is bathed, and it is 1 that mass ratio is bathed in aramid fiber and alkali cleaning: 20-40, temperature 95-100 ℃, time 0.5-1h; Flushing with clean water is dried stand-by;
(2) aramid fiber preliminary treatment: pretreating process is selected for use:
1. plasma preliminary treatment: the aramid fiber after will cleaning places the reative cell normal temperature of plasma generator to handle: power 25-150W, processing time 1-10min, pressure 1-50Pa;
Or 2. phosphoric acid preliminary treatment: the aramid fiber after will cleaning places mass concentration 10%-85% phosphoric acid solution, takes out behind the 40-100 ℃ of processing 30-90min, clean repeatedly to neutrality with distilled water, and oven dry, standby;
(3) aramid fiber dyeing: select for use:
1. High Temperature High Pressure carrier dyeing process: pretreated aramid fiber input is contained in the water of dyeing carrier, dyeing carrier concentration is 60-70mL/L, making water temperature is 30-60 ℃, aramid fiber and dye bath mass ratio are 1: 20-40, to bathe temperature rise to 70-100 ℃ with the speed of 1-3 ℃/min, the DISPERSE DYES and the concentration of progressively adding mass concentration and be 1%-7% in dye bath are the accelerant of 10-80g/L, the adjusting dye liquor pH value is 2-5, speed with 1-3 ℃/min rises to 130-135 ℃ with the dye bath temperature, insulation 60-80min, insulation finishes the back and with the speed of 1-2 ℃/min the dye bath temperature is reduced to 60-80 ℃, discharge dye liquor, with concentration is the soap lye cleaning of 3-6g/L, after the cleaning fiber is taken out oven dry;
Or 2. preliminary treatment-dyeing: pretreated aramid fiber input is contained in the water of dyeing carrier, dyeing carrier concentration is 60-70mL/L, making water temperature is 30-60 ℃, aramid fiber and dye bath mass ratio are 1: 20-40, to bathe temperature rise to 70-80 ℃ with the speed of 1.5-2 ℃/min, the cation dyes and the concentration of progressively adding mass concentration and be 1%-7% in dye bath are the accelerant of 10-70g/L, the adjusting dye liquor pH value is 2-5, just dye bath temperature of speed with 1-1.5 ℃/min rises to 100-120 ℃, insulation 40-60min, insulation finishes the back and with the speed of 1-2 ℃/min the dye bath temperature is reduced to 60-80 ℃, discharge dye liquor, with concentration is the soap lye cleaning of 3-6g/L, after the cleaning fiber is taken out oven dry;
(4) multifunctional composite finishing of aramid fiber: the aramid fiber after will dyeing is put into arrangement and is bathed, it is 1 that aramid fiber is bathed mass ratio with arrangement: 20-40, arrangement bathe for contain moisture absorption poromeric finishing agent 2-10g/L, concentration is the complex sol of 0.5-2.5mol/L, by the dipping or the mode of padding it is put in order on the aramid fiber, dry, bake, stand-by.
2, the method for the modification of aramid fiber according to claim 1, dyeing and multifunctional composite finishing is characterized in that being fit to various types of aramid fiber bulk fibres, yarn or fabric.
3, the method for the modification of aramid fiber according to claim 1, dyeing and multifunctional composite finishing is characterized in that plasma atmosphere is the mixed atmosphere of one or more gases in the air, nitrogen, oxygen, ammonia, inert gas of concentration≤2%.
4, the method for the modification of aramid fiber according to claim 1, dyeing and multifunctional composite finishing is characterized in that dyeing carrier selects one or both in aromatic alcohol, aromatic ketone or the aromatic ether for use.
5, the method for the modification of aramid fiber according to claim 1, dyeing and multifunctional composite finishing, the accelerant when it is characterized in that dyeing are a kind of in sodium nitrate, sodium sulphate, Boratex or the sodium chloride or two kinds.
6, the method for the modification of aramid fiber according to claim 1, dyeing and multifunctional composite finishing, the dyestuff when it is characterized in that dyeing are cation dyes or DISPERSE DYES.
7, the method for the modification of aramid fiber according to claim 1, dyeing and multifunctional composite finishing is characterized in that described complex sol selects TiO for use
2Colloidal sol, ZnO colloidal sol, SiO
2The complex sol of two or three in the colloidal sol.
8, the method for the modification of aramid fiber according to claim 1, dyeing and multifunctional composite finishing is characterized in that described moisture absorption poromeric finishing agent selects silicone based hydrophilic finishing agent, epoxide resin type hydrophilic finishing agent or polyester and polyether block copolymer for use.
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2009
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