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

Info

Publication number
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
Authority
CN
China
Prior art keywords
fabric
solution
floride
water
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201611135837.2A
Other languages
Chinese (zh)
Other versions
CN106592204A (en
Inventor
江红
徐柏青
贺昌城
田俊莹
董猛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JIANGXI CHANGSHUO OUTDOOR LEISURE PRODUCTS CO Ltd
Original Assignee
JIANGXI CHANGSHUO OUTDOOR LEISURE PRODUCTS CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JIANGXI CHANGSHUO OUTDOOR LEISURE PRODUCTS CO Ltd filed Critical JIANGXI CHANGSHUO OUTDOOR LEISURE PRODUCTS CO Ltd
Priority to CN201611135837.2A priority Critical patent/CN106592204B/en
Publication of CN106592204A publication Critical patent/CN106592204A/en
Application granted granted Critical
Publication of CN106592204B publication Critical patent/CN106592204B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • 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
    • D06M11/73—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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • D06M2101/34—Polyamides
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Landscapes

  • Engineering & Computer Science (AREA)
  • 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.
CN201611135837.2A 2016-12-09 2016-12-09 It is a kind of free-floride water repellent fabric and fabric floride-free water-repellent finishing method Active CN106592204B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611135837.2A CN106592204B (en) 2016-12-09 2016-12-09 It is a kind of free-floride water repellent fabric and fabric floride-free water-repellent finishing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611135837.2A CN106592204B (en) 2016-12-09 2016-12-09 It is a kind of free-floride water repellent fabric and fabric floride-free water-repellent finishing method

Publications (2)

Publication Number Publication Date
CN106592204A CN106592204A (en) 2017-04-26
CN106592204B true CN106592204B (en) 2018-10-26

Family

ID=58598248

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611135837.2A Active CN106592204B (en) 2016-12-09 2016-12-09 It is a kind of free-floride water repellent fabric and fabric floride-free water-repellent finishing method

Country Status (1)

Country Link
CN (1) CN106592204B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108823966A (en) * 2018-04-17 2018-11-16 常宁市帝棉纺织制衣有限公司 A kind of nano self-cleaning fabric and preparation method thereof
CN109097999A (en) * 2018-07-09 2018-12-28 长乐佳纶纺织实业有限公司 A kind of aminophenyl silicone oil/graphene fabric and preparation method
CN108951278A (en) * 2018-07-28 2018-12-07 黄智慧 A kind of preparation method of automobile filter paper styrene-acrylic emulsion
CN109137492A (en) * 2018-08-02 2019-01-04 苏州市天翱特种织绣有限公司 A kind of free-floride fabric refuses the preparation method of dirty finishing agent
CN109853223A (en) * 2018-12-31 2019-06-07 盐城工学院 A kind of TiO2The preparation method of-rGo composite self-cleaning fabric
CN110774680B (en) * 2019-11-06 2022-05-20 云南咏竹科技有限公司 High-skin-affinity antibacterial fabric and preparation method thereof
CN111485418B (en) * 2020-03-18 2022-09-23 哈尔滨工业大学 Preparation method of plant fiber cloth with surface grafted with graphene oxide-silicon dioxide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021819A (en) * 2010-10-22 2011-04-20 东华大学 Fluorine-free superhydrophobic finishing agent containing modified nano silicon dioxide hydrosol and application thereof
CN104328653A (en) * 2014-10-11 2015-02-04 江南大学 Method for multifunctional sorting of textile by using graphene oxide derivative

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101457521B1 (en) * 2013-12-23 2014-11-03 한국과학기술연구원 Reduced graphene oxide coated filament and method for fabricating the same
CN105350282A (en) * 2015-12-12 2016-02-24 中原工学院 Preparation method for fluoride-free super-hydrophobic cotton fabric
CN105648757B (en) * 2015-12-30 2018-01-30 江阴市长泾花园毛纺织有限公司 A kind of water-repellent finishing method of bafta layer
CN106012543B (en) * 2016-07-05 2019-01-29 无锡嘉加科技有限公司 A kind of free-floride water repellent anti-soil agent and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021819A (en) * 2010-10-22 2011-04-20 东华大学 Fluorine-free superhydrophobic finishing agent containing modified nano silicon dioxide hydrosol and application thereof
CN104328653A (en) * 2014-10-11 2015-02-04 江南大学 Method for multifunctional sorting of textile by using graphene oxide derivative

Also Published As

Publication number Publication date
CN106592204A (en) 2017-04-26

Similar Documents

Publication Publication Date Title
CN106592204B (en) It is a kind of free-floride water repellent fabric and fabric floride-free water-repellent finishing method
CN107312166B (en) A kind of modified PET polyester and its preparation method and application
CN102021819B (en) Fluorine-free superhydrophobic finishing agent containing modified nano silicon dioxide hydrosol and application thereof
CN101961626B (en) Method for preparing ZrO2 aerogel
CN103046151B (en) Graphene blend regenerated cellulose fiber and preparation method thereof
CN101804986B (en) Method for preparing hollow silicon dioxide microsphere with controllable wall thickness by taking polystyrene microsphere as template
CN102765755A (en) Preparation method of blocky zirconium oxide aerogel
CN105110787A (en) Method for preparing photocatalytic foamed ceramics
CN110804878A (en) Low-temperature dyeing process for fiber textile fabric
CN102517887B (en) Method for preparing silicon protective in-situ deposition photocatalytic functional textile
CN106884313A (en) A kind of worsted fabric sol-gal process water-repellent finishing method
CN108385403B (en) A kind of antistatic antibiotic microfiber leather and preparation method thereof
CN102059086A (en) Experimental device for chemical reaction of bulk fibers
CN103566977B (en) A kind of dye-sensitized nano ferric oxide coated hollow glass micropearl method
CN108642654A (en) A kind of antimicrobial form textile fabric
CN103726320A (en) Preparation method of water repellent finishing agent
CN108755103B (en) Preparation method of photocatalytic self-cleaning anti-ultraviolet fabric
CN105088317B (en) A kind of preparation method of ceria film
CN108316027A (en) A kind of wet steaming technique of dyeing
CN104016672B (en) Rear-earth-doped ramie form SnO 2the preparation method of Air-Sensitive Porcelain Materials
CN109295548A (en) A kind of zirconium oxide hollow fibre and preparation method thereof
CN114351455B (en) Preparation method of crease-resistant silk fabric
CN105040073B (en) A kind of method that use two-step anodization prepares ceria film
CN108252105A (en) A kind of surface treatment method of glass fabric
CN113550136A (en) Method for cold stacking pure cotton spunlace non-woven fabric step by step

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A fluorine free and water repellent fabric and its fluorine free and water repellent finishing method

Effective date of registration: 20230925

Granted publication date: 20181026

Pledgee: Agricultural Bank of China Limited Wannian County Branch

Pledgor: Jiangxi Changshuo Outdoor Leisure Product Co.,Ltd.

Registration number: Y2023980058502

PE01 Entry into force of the registration of the contract for pledge of patent right