CN106592204B - It is a kind of free-floride water repellent fabric and fabric floride-free water-repellent finishing method - Google Patents

It is a kind of free-floride water repellent fabric and fabric floride-free water-repellent finishing method Download PDF

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CN106592204B
CN106592204B CN201611135837.2A CN201611135837A CN106592204B CN 106592204 B CN106592204 B CN 106592204B CN 201611135837 A CN201611135837 A CN 201611135837A CN 106592204 B CN106592204 B CN 106592204B
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fabric
solution
floride
water
temperature
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CN106592204A (en
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江红
徐柏青
贺昌城
田俊莹
董猛
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JIANGXI CHANGSHUO OUTDOOR LEISURE PRODUCTS CO Ltd
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JIANGXI CHANGSHUO OUTDOOR LEISURE PRODUCTS CO Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
    • D—TEXTILES; PAPER
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
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    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The floride-free water-repellent finishing method of a kind of free-floride water repellent fabric and fabric, it belongs to technical field of textile afterfinish, and method includes following step：Sol solution A is prepared using conventional method；The graphene oxide of single layer structure is dispersed in water, the solution B that mass percent concentration is 0.1~0.5% is made；Solution B and solution A are mixed to get composite finishing liquid C according to B: A=1: 10 volume ratio or mass ratio；Base fabric is placed in dressing liquid C, is handled 10~1000 minutes under conditions of temperature is room temperature~90 DEG C, 3~30min of front baking in being 50~90 DEG C in temperature after carrying out reduction treatment after rolling surplus liquid and being washed with deionized；10~100min is dried after being in 95~130 DEG C in temperature, the above-mentioned processing step by the present invention can be obtained the floride-free water repellent fabric that surface water contact angle is 110 °~152 °.

Description

It is a kind of free-floride water repellent fabric and fabric floride-free water-repellent finishing method
Technical field：
The present invention relates to a kind of floride-free water repellent fabric and the floride-free water-repellent finishing method of fabric, it belongs to whole after textile Manage technical field.
Background technology：
Water repellent waterproof fabric is widely used in the production and life of the mankind.Water repellent finish is carried out to fabric, is to obtain Obtain the important channel of waterproof fabric.Since the 1950s so far, waterproof water repellent finishing agent used in industrial production with Based on fluorochemical.Since fluorochemical can will produce harmful shadow during its production and use to human body and environment It rings, then people begin one's study and the floride-free fabric waterproof water repellent finishing agent of exploitation.A variety of fluorine-free compounds be used to fabric into Row water repellent finish e.g. arranges cotton and polyester-cotton blend textile fabric using pyridine quaternary ammonium salt, obtains the preferable water repellent of durability and knits Object；After fabric being impregnated using the aqueous dispersion of paraffin wax emulsions and metal salt, then drying and heat treatment, so that fabric is obtained waterproof Property；Water-proof finish, etc. is carried out to the fabric of various material using organo-silicon compound.
Fabric water repellency is assigned by the method for introducing the material composition of low-surface-energy in fabric surface, there are durabilities not Good disadvantage, with the increase of washing times, water repellency is gradually deteriorated, and its method tends not to make fabric with super-hydrophobic Property.
Except through fabric surface introduce low-surface-energy material composition except, in recent years, people attempt to imitate again The micro character of lotus leaf surface, by constructing specific micro-nano structure in fabric surface to assign fabric good water repellency, this And the technical foundation of the technical solution of the new issue and the application of current this field.
Invention content：
The purpose of the present invention is to provide a kind of using graphene as the attachment material of fabric surface, to realize water repellent A kind of floride-free water repellent fabric of more good water repellent effect and the floride-free water-repellent finishing method of fabric.
The object of the present invention is achieved like this：
A kind of floride-free water-repellent finishing method of fabric, it includes following step：
A, colloidal sol is prepared：
Colloidal sol is prepared using conventional method, obtains solution A, the solution A is：Silicon dioxide gel or titanium dioxide are molten Glue or alumina sol or magnesia colloidal sol or one or more of other metals or nonmetal oxide colloidal sol；
B, graphene oxide is dispersed in water, the graphene oxide be single layer structure, average radial size be 5~ 40um, obtained solution B；The mass percent concentration of solution B is 0.1~0.5%；
C, by solution B made from step b with to volume ratio or mass ratio of the solution A according to B: A=1: 10 made from step a It is mixed and stirred for uniformly, obtaining composite finishing liquid C；
D, base fabric is placed in dressing liquid C made from step c, 10 is handled under conditions of temperature is room temperature~90 DEG C It~1000 minutes, then takes out and rolls surplus liquid, obtain single treatment fabric；
E, the single treatment fabric D made from step d is made into reduction treatment, so that graphene oxide is reduced to graphene, so After be washed with deionized three times, after-treatment fabric is made；
F, the after-treatment fabric made from step e carries out front baking, and pre-bake temperature is 50~90 DEG C, 3~30min；So It is dried after carrying out again afterwards, rear temperature of drying is 95~130 DEG C, and 10~100min of criteria thus the drying time obtains final process fabric.
Colloidal sol described in step a is silicon dioxide gel or TiO 2 sol.
The average radial size of the graphene oxide of single layer structure is 5~8um in stepb.
The average radial size of the graphene oxide of single layer structure is 20~30um in stepb.
The average radial size of the graphene oxide of single layer structure is 30~40um in stepb.
In step d, fabric is placed in dressing liquid C made from step c, adds concussion field, is room temperature~70 DEG C in temperature Under conditions of handle 20~100 minutes, then take out and roll surplus liquid, obtain single treatment fabric.
Pre-bake temperature is 70~85 DEG C in step f, and criteria thus the drying time is 8~18min；It is 95~130 DEG C to dry temperature afterwards, is dried The dry time is 30~70min.
Base fabric described in step d is highdensity cotton fabric or linen or wool fabric or viscose fiber fabric or washs Synthetic fibre fabric or nylon fabric or blended fabric.
The floride-free water repellent fabric is 110 ° to pass through surface water contact angle made of the above method in base fabric ~152 ° of fabric.
The base fabric is highdensity cotton fabric or linen or wool fabric or viscose fiber fabric or dacron Or nylon fabric or blended fabric.
The method provided by the invention for carrying out water repellent finish to fabric, overall process does not use fluorochemical, and can reach To super-hydrophobic level, the water contact angle of treated fabric becomes fabric surface reaches 110 °~152 °, and with good The floride-free water repellent fabric of water repellency.
Specific implementation mode：
Below by embodiment and experimental example, the present invention is described in more detail.
Before enumerating embodiment, conventional colloidal sol preparation method and routine involved in the present invention is explained first Graphene oxide restoring method.
It is conventional colloidal sol preparation method first, by taking silicon dioxide gel and TiO 2 sol as an example：
The preparation of silicon dioxide gel：Esters of silicon acis Hydrolyze method may be used, such as select ethyl orthosilicate as precursor, profit Its hydrolysis is set to be made for catalyst with hydrochloric acid or nitric acid；Ion-exchange can also be used, is such as starting with sodium silicate solution Object removes sodium ion using cation exchange resin, is then made through alkalization concentration；Or use pasc reaction method, i.e., with silica flour Simple substance is raw material, reacts and is made with water under the catalytic action of a certain amount of alkali.It is preferred that esters of silicon acis Hydrolyze method, more preferably with positive silicon Acetoacetic ester is as precursor.
The preparation of TiO 2 sol：Titanate esters Hydrolyze method may be used.It is precursor such as to select tetra-n-butyl titanate, with Ethyl alcohol is solvent, so that its hydrolysis is made as catalyst using hydrochloric acid or nitric acid；Or using water as solvent, it is made with second acid as catalyst It hydrolyzes and is made；The method reacted with ammonium hydroxide with titanium tetrachloride aqueous solution can also be used to prepare TiO 2 sol.It is preferred that titanium Sour four butyl ester Hydrolyze methods, more preferably using water as solvent, with the reaction system of second acid as catalyst.
Graphene oxide is reduced to graphene：
Graphene oxide is set to be reduced to graphene, the used method to graphene oxide reduction includes chemical reducing agent The methods of reduction, electrochemical reduction, catalysis or photo catalytic reduction and microwave treatment and high-temperature heating reduction；It can also be by two kinds Or a variety of restoring method are used cooperatively.Preferably chemical reducing agent reduction and two kinds of restoring method are used cooperatively.
The adoptable chemical reducing agent have hydrazine (including hydrazine, hydrazine hydrate, dimethylhydrazine, phenylhydrazine, to sulfonyloxy methyl Hydrazine etc.), metal hydride (including sodium borohydride, lithium aluminium hydride reduction, the derivative sodium cyanoborohydride and triacetyl oxygen of sodium borohydride Base sodium borohydride etc.), active metal (including aluminium powder, iron powder, zinc powder etc.), reproducibility acid or phenol (such as ascorbic acid, pyrogallol, Hydroquinone, tea polyphenols) etc. and other reducing agents (such as sodium citrate, sodium hydrogensulfite salt, such as sodium hydroxide, hydrogen-oxygen Change the reducing sugars such as alkaline matters and glucose, fructose, sucrose, also hydroiodic acid etc. such as potassium, ammonium hydroxide) it is preferably hydrazine, gold Belong to hydride and sodium hydrogensulfite.Hydrazine is more preferably hydrazine hydrate, and metal hydride is more preferably sodium borohydride, other are more preferably For sodium hydrogensulfite.
The method that can be used cooperatively with use above two restoring method, including sodium hydrogensulfite and heat treatment cooperation Method, the method for sodium borohydride and heat treatment cooperation, hydrazine and the method for heat treatment cooperation, the method for glucose and heat treatment cooperation Deng the method that preferably sodium hydrogensulfite and heat treatment coordinate.
Embodiment
Embodiment 1,
A, solution A：The preparation of silicon dioxide gel measures ethyl orthosilicate 40mL and ethyl alcohol respectively in the present embodiment It is first placed in the round-bottomed flask of the same 250mL volumes by 32mL；Measure again a concentration of 37.2% hydrochloric acid 1mL and go Ionized water 15mL is poured into beaker in above-mentioned round-bottomed flask after mixing.By the mixture in flask in magnetic agitation Under be heated to reflux 90 minutes, reflux temperature be 60 DEG C.After reflux, room temperature is cooled to get solution A.
B, the preparation of solution B：The graphene oxide of single layer rate >=99.5%, average radial size 5-8um is scattered in In ionized water, the solution 8.8mL of mass percent concentration 0.33% is obtained to get solution B.
C, the preparation of composite finishing liquid C：Solution B is mixed with solution A, and stir process 15 is divided under magneton stirring action Clock obtains composite finishing liquid C.
D, the preparation of single treatment fabric：By the fabric for the suitable dimension cut out, selection in the present embodiment uses The pure spring Asia spinning bleached cotton fabrics of washing of 75D/190T66 are a piece of, immerse in composite finishing liquid C, take out, roll more after handling 20min at 85 DEG C Extraction raffinate body obtains single treatment fabric.
E, the preparation of after-treatment fabric：NaHSO by single treatment fabric 2%3It is restored in solution and at 90 DEG C 60min is handled, takes out, then be washed with deionized three times, obtains after-treatment fabric.
F, by after-treatment fabric in 55 DEG C of baking oven front baking 30min, be then warming up to 95 DEG C continue after dry 90min, Final process free-floride water repellent fabric is obtained, the free-floride water repellent fabric.
Embodiment 2
A, solution A, the preparation of silicon dioxide gel：Ethyl orthosilicate 40mL and ethyl alcohol 32mL is measured respectively, by its priority Person is placed in the round-bottomed flask of the same 250mL volumes；A concentration of 37.2% hydrochloric acid 1mL and deionized water 15mL are measured again, It is poured into after mixing in above-mentioned round-bottomed flask in beaker.Mixture in flask is heated to reflux 90 under magnetic stirring Minute, reflux temperature is 60 DEG C.After reflux, room temperature is cooled to get solution A.
B, the preparation of solution B：Graphene oxide (single layer rate >=99.5%, average radial size 20-30um) is scattered in In deionized water, the solution 8.8mL of mass percent concentration 0.20%, ie in solution B are obtained.
C, the preparation of composite finishing liquid C：Solution B is mixed with solution A and stir process 15 is divided under magneton stirring action Clock obtains composite finishing liquid C.
D, the preparation of single treatment fabric：By the fabric for the suitable dimension cut out, (75D/190T66 spins drift in pure spring Asia of washing Calico) it is a piece of, it immerses in dressing liquid C, is taken out after handling 400min at 50 DEG C, roll surplus liquid, obtain single treatment fabric.
E, the preparation of after-treatment fabric：Single treatment fabric is immersed to 2% NaHSO3In solution, original place is gone back at 90 DEG C 60min is managed, is taken out, is washed with deionized three times, obtains after-treatment fabric.
F, by after-treatment fabric in 75 DEG C of baking oven front baking 15min, be then warming up to 110 DEG C continue after dry 50min, Obtain final process free-floride water repellent fabric.
Embodiment 3
A, solution A, the preparation of silicon dioxide gel：Ethyl orthosilicate 40mL and ethyl alcohol 32mL is measured respectively, by its priority Person is placed in the round-bottomed flask of the same 250mL volumes；A concentration of 37.2% hydrochloric acid 1mL and deionized water 15mL are measured again, It is poured into after mixing in above-mentioned round-bottomed flask in beaker.Mixture in flask is heated to reflux 90 under magnetic stirring Minute, reflux temperature is 60 DEG C.After reflux, room temperature is cooled to get solution A.
B, the preparation of solution B：Graphene oxide (single layer rate >=99.5%, average radial size 30-40um) is scattered in In deionized water, the solution 8.8mL of mass percent concentration 0.40%, ie in solution B are obtained.
C, the preparation of composite finishing liquid C：Solution B is mixed with solution A and stir process 15 is divided under magneton stirring action Clock obtains composite finishing liquid C.
D, the preparation of single treatment fabric：The fabric (136T/C polyester-cotton blend (65/35)) for the suitable dimension cut out is blackish green Painting cloth) it is a piece of, it immerses in dressing liquid C, is taken out after room temperature processing 900min, roll surplus liquid, obtain single treatment fabric.
E, the preparation of after-treatment fabric：Single treatment fabric is immersed to 2% NaHSO3In solution, in isothermal vibration machine Reduction treatment 60min at 90 DEG C takes out, is washed with deionized three times, obtains after-treatment fabric.
F, by after-treatment fabric in 90 DEG C of baking oven front baking 5min, be then warming up to 130 DEG C continue after dry 15min, Obtain final process free-floride water repellent fabric.
Embodiment 4
A, solution A, the preparation of TiO 2 sol：Butyl titanate 17g is measured respectively, acetic acid 15g is weighed, by its priority It is placed in the round-bottomed flask of the same 100mL volumes, magneton stirs 30min, obtains solution I；Acetic acid 5g is weighed, is dissolved in In 85g deionized waters, solution II is obtained.I solution is slowly dropped in II solution under magnetic agitation, rate of addition is about 35 Drop/min, the reaction was continued after being added dropwise a period of time, obtains solution A.
B, the preparation of solution B：Graphene oxide (single layer rate >=99.5%, average radial size 5-8um) is scattered in In ionized water, the solution 12.2g of mass percent concentration 0.33%, ie in solution B are obtained.
C, the preparation of composite finishing liquid C：Solution B is mixed with solution A and stir process 15 is divided under magneton stirring action Clock obtains composite finishing liquid C.
D, the preparation of single treatment fabric：The fabric (136T/C polyester-cotton blend (65/35)) for the suitable dimension cut out is blackish green Painting cloth) it is a piece of, it immerses in dressing liquid C, is taken out after handling 20min at 85 DEG C, roll surplus liquid, obtain single treatment fabric.
E, the preparation of after-treatment fabric：NaHSO by single treatment fabric 2.5%3Original place is gone back in solution at 80 DEG C 120min is managed, is taken out, is washed with deionized three times, obtains after-treatment fabric.
F, by after-treatment fabric in 55 DEG C of baking oven front baking 30min, be then warming up to 95 DEG C continue after dry 90min, Obtain final process free-floride water repellent fabric.
Embodiment 5
A, solution A, the preparation of TiO 2 sol：Butyl titanate 17g is measured respectively, acetic acid 15g is weighed, by its priority It is placed in the round-bottomed flask of the same 100mL volumes, magneton stirs 30min, obtains solution I；Acetic acid 5g is weighed, is dissolved in In 85g deionized waters, solution II is obtained.I solution is slowly dropped in II solution under magnetic agitation, rate of addition is about 35 Drop/min, the reaction was continued after being added dropwise a period of time, obtains solution A.
B, the preparation of solution B：Graphene oxide (single layer rate >=99.5%, average radial size 20-30um) is scattered in In deionized water, the solution 12.2g of mass percent concentration 0.20%, ie in solution B are obtained.
C, the preparation of composite finishing liquid C：Solution B is mixed with solution A and stir process 15 is divided under magneton stirring action Clock obtains composite finishing liquid C.
D, the preparation of single treatment fabric：By the fabric (the pure nylon royal blue cloths of 75D/190T) for the suitable dimension cut out It is a piece of, it immerses in dressing liquid C, is taken out after handling 450min at 50 DEG C, roll surplus liquid, obtain single treatment fabric.
E, the preparation of after-treatment fabric：NaHSO by single treatment fabric 2.5%3Original place is gone back in solution at 80 DEG C 120min is managed, is taken out, is washed with deionized three times, obtains after-treatment fabric.
F, by after-treatment fabric in 75 DEG C of baking oven front baking 15min, be then warming up to 110 DEG C continue after dry 50min, Obtain final process free-floride water repellent fabric.
Embodiment 6
A, solution A, the preparation of TiO 2 sol：Butyl titanate 17g is measured respectively, acetic acid 15g is weighed, by its priority It is placed in the round-bottomed flask of the same 100mL volumes, magneton stirs 30min, obtains solution I；Acetic acid 5g is weighed, is dissolved in In 85g deionized waters, solution II is obtained.Solution I is slowly dropped in solution II under magnetic agitation, rate of addition is about 35 Drop/min, the reaction was continued after being added dropwise a period of time, obtains solution A.
B, the preparation of solution B：Graphene oxide (single layer rate >=99.5%, average radial size 30-40um) is scattered in In deionized water, the solution 12.2g of mass percent concentration 0.40%, ie in solution B are obtained.
C, the preparation of composite finishing liquid C：Solution B is mixed with solution A and stir process 15 is divided under magneton stirring action Clock obtains composite finishing liquid C.
D, the preparation of single treatment fabric：By the fabric (the pure nylon royal blue cloths of 75D/190T) for the suitable dimension cut out It is a piece of, it immerses in dressing liquid C, is taken out after room temperature processing 900min, roll surplus liquid, obtain single treatment fabric.
E, the preparation of after-treatment fabric：NaBH by single treatment fabric 2.5%4Reduction treatment at 80 DEG C in solution 120min takes out, is washed with deionized three times, obtains after-treatment fabric.
F, by after-treatment fabric in 90 DEG C of baking oven front baking 5min, be then warming up to 130 DEG C continue after dry 15min, Obtain final process free-floride water repellent fabric.
Experimental example
Water repellency parameter, predominantly water contact angle data made from Examples 1 to 6 are measured respectively, as a result such as 1 institute of table Show：
The water repellency parameter of 1. fabric of table
Contact angle (°)
Embodiment 1 147
Embodiment 2 145
Embodiment 3 121
Embodiment 4 152
Embodiment 5 119
Embodiment 6 112

Claims (7)

1. a kind of floride-free water-repellent finishing method of fabric, it is characterised in that it includes following step：
A, colloidal sol is prepared：
Colloidal sol is prepared using conventional method, obtains solution A, the solution A is：Silicon dioxide gel, specific preparation method are： Ethyl orthosilicate 40mL and ethyl alcohol 32mL is measured respectively, it is first placed in the round-bottomed flask of the same 250mL volumes；It measures again The hydrochloric acid 1mL and deionized water 15mL for taking a concentration of 37.2%, pour into beaker in above-mentioned round-bottomed flask after mixing, Mixture in flask is heated to reflux 90 minutes under magnetic stirring, reflux temperature is 60 DEG C, after reflux, is cooled to room Temperature is to get solution A；
B, graphene oxide is dispersed in water, the graphene oxide be single layer structure, average radial size be 5~ 40um, obtained solution B；The mass percent concentration of solution B is 0.1~0.5%；
C, by solution A made from solution B made from step b and step a according to B:A=1:10 volume ratio or mass ratio mixing is simultaneously It stirs evenly, obtains composite finishing liquid C；
D, base fabric is placed in dressing liquid C made from step c, temperature be room temperature~90 DEG C under conditions of processing 10~ It 1000 minutes, then takes out and rolls surplus liquid, obtain single treatment fabric D；
E, the single treatment fabric D made from step d is made into reduction treatment, so that graphene oxide is reduced to graphene, then uses Deionized water is washed three times, and after-treatment fabric is made；
F, the after-treatment fabric made from step e carries out front baking, and pre-bake temperature is 50~90 DEG C, 3~30min；Then again It is dried after progress, rear temperature of drying is 95~130 DEG C, and 10~100min of criteria thus the drying time obtains final process fabric.
2. the floride-free water-repellent finishing method of fabric as described in claim 1, it is characterised in that the oxygen of single layer structure in stepb The average radial size of graphite alkene is 5~8um.
3. the floride-free water-repellent finishing method of fabric as described in claim 1, it is characterised in that the oxygen of single layer structure in stepb The average radial size of graphite alkene is 20~30um.
4. the floride-free water-repellent finishing method of fabric as described in claim 1, it is characterised in that the oxygen of single layer structure in stepb The average radial size of graphite alkene is 30~40um.
5. the floride-free water-repellent finishing method of fabric as described in claim 1, it is characterised in that in step d, fabric is placed in In dressing liquid C made from step c, add concussion field, processing 20~100 minutes under conditions of temperature is room temperature~70 DEG C, then Surplus liquid is rolled in taking-up, obtains single treatment fabric.
6. the floride-free water-repellent finishing method of fabric as described in claim 1, it is characterised in that pre-bake temperature is 70 in step f ~85 DEG C, criteria thus the drying time is 8~18min；It is 95~130 DEG C to dry temperature afterwards, and criteria thus the drying time is 30~70min.
7. the floride-free water-repellent finishing method of the fabric as described in claims 1 or 2 or 3 or 4 or 5 or 6, it is characterised in that step Base fabric described in d is highdensity cotton fabric or linen or wool fabric or viscose fiber fabric or dacron or polyamide fibre Fabric or blended fabric.
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