CN110205821A - A kind of green free-floride water-proof aagent and its application in fibre - Google Patents

A kind of green free-floride water-proof aagent and its application in fibre Download PDF

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CN110205821A
CN110205821A CN201910536616.3A CN201910536616A CN110205821A CN 110205821 A CN110205821 A CN 110205821A CN 201910536616 A CN201910536616 A CN 201910536616A CN 110205821 A CN110205821 A CN 110205821A
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floride
green
fibre
free water
proof aagent
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CN110205821B (en
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苏佳佳
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Guangzhou Baisichuang Technology Co ltd
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Guangzhou Baisichuang Technology Co ltd
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    • D—TEXTILES; PAPER
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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
    • D06M11/77—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
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
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    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a kind of floride-free water-proof aagent of green and its applications in fibre.The finishing agent gathers times siloxanes, the trapezoidal poly-organosilicon resin of ethyl phenyl sulfide methacryloxypropyl, cetyl trimethylammonium bromide, (3- mercapto propyl) trimethoxy silane, the trapezoidal poly-organosilicon resin/SiO of ethyl phenyl sulfide methacryloxypropyl by ethyl phenyl sulfide propyl mercapto propyl2Colloidal sol, photoinitiator, siloxanyl methacrylate, lauryl sodium sulfate, aliphatic acid polyethenoxy ether, ammonium persulfate, methyl methacrylate and hydroxyethyl methacrylate composition.The finishing agent is applied in fibre.Easy to industrialized production the present invention overcomes the deficiency of existing product, application method is simple, at low cost, has a good application prospect and economic benefit.

Description

A kind of green free-floride water-proof aagent and its application in fibre
Technical field
The invention belongs to TEXTILE CHEMICALS preparation and its application fields, and in particular to a kind of floride-free water-proof aagent of green and Its application in fibre.
Background technique
With the increasingly raising of living standard, requirement of the people to garment material various aspects is also higher and higher, personalized, high Shelvesization and moisture absorption, breathe freely, perspire, the functional textiles such as quick-drying, deodorization antibacterial, uvioresistant oneself become textile garment fabric Development trend.Waterproof refuses oil, easy decontamination Multifunctional finishing can significantly improve the surface property of fabric, make fabric be not easy by water, oil, The wetting of the spots such as coffee and contamination.In numerous water-proof aagents, fluorine-containing water repellent apply on the fabric after effect the most Obviously, but Most fabric fluorine-containing water repellent product contains PFOS.Current most widely used water-refusing oil-refusing finishing agent is fluorine-containing Organic polymer, the water repellency of such existing brilliance of water repellent has good oil repellency again, and durability is good, and not shadow Ring the original style of fiber, thus the favor by consumer.However water repellent finishing agent is applied extensively in textile processing technique General, common water repellent finishing agent is fluoro-acrylate copolymer lotion.But fluorinated compound is expensive, and produces fluorine-containing Auxiliary agent during finishing agent is perfluoro caprylic acid and its esters (PFOA) and perfluorooctane sulfonate (PFOS), they have potential Carcinogenicity can discharge fluorine compounds, harmful to human and environment in arrangement and after arranging.Since PFOA and PFOS are a kind of chemistry The high compound of stability has very high persistence in the environment, and can assemble in the environment, accumulates in vivo It is tired, it is difficult widely used perfluoro caprylic acid and its esters (PFOA) during decomposing production by metabolism and arranging, complete The Long carbon chains chemicals such as the pungent sulfonic acid of fluorine (PFOS) have bio-toxicity and environmental pollution.In consideration of it, finding and developing floride-free waterproof Product and waterproof technique are extremely urgent.Compared with fluorochemical, the advantages of organosilicon water repellent finishing agent, is numerous, such as environment friend It is good, low in cost, and there is good heat resistance, weatherability and uvioresistant performance etc., but organosilicon there is also mechanical strengths not In place of the deficiencies of foot, poor adhesive force.UV ultraviolet light solidifies finishing agent since fast with curing rate, environmental pollution is small, saves The energy to the applied widely of substrate and the advantages that be suitable for high-speed automated production and is paid more and more attention.But previous UV Solidifying the oligomer that finishing agent uses is mainly line polymer, there are viscosity it is big, oxygen inhibition is more serious the problems such as.To be answered With required viscosity and rheological property, need to be added a large amount of diluent to adjust, and the diluent used is mostly irritant Smell and volatile is easy to damage human health and ambient enviroment, limit its application.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of green floride-free anti- Water finishing agent.
Another object of the present invention is to provide a kind of application of the above-mentioned floride-free water-proof aagent of green in fibre.
The object of the invention is achieved through the following technical solutions:
A kind of floride-free water-proof aagent of green, the component comprising following mass percent:
10~20% component A, 10~20% component B and 60~80% component C；
Wherein, component A is (1~2): (4~6): (2~3): the ethyl phenyl sulfide propyl mercapto propyl of (0.5~1) by mass ratio Poly- times siloxanes, the trapezoidal poly-organosilicon resin of ethyl phenyl sulfide methacryloxypropyl, cetyl trimethylammonium bromide and (3- Mercapto propyl) trimethoxy silane composition；
Component B is (15~40) by mass ratio: the trapezoidal poly-organosilicon resin of 1 ethyl phenyl sulfide methacryloxypropyl/ SiO2Colloidal sol and photoinitiator composition；
Component C is (4~5): (0.03~0.06): (0.03~0.06): (0.015~0.03): (1~2) by mass ratio: Siloxanyl methacrylate, lauryl sodium sulfate, aliphatic acid polyethenoxy ether, ammonium persulfate, the methyl of (0.5~1) Methyl acrylate and hydroxyethyl methacrylate composition；
The sum of mass percent of said components A, B and C is 100%.
The trapezoidal poly-organosilicon resin/SiO of ethyl phenyl sulfide methacryloxypropyl2Ethyl phenyl sulfide methyl-prop in colloidal sol The trapezoidal poly-organosilicon resin of alkene monomethacryloxypropyl and SiO2The molar ratio of colloidal sol is 1:16~1:21.
The photoinitiator be preferably in DAROCUR 1173, IRGACURE 2100 and IRGACURE 2959 at least It is a kind of.
The siloxanyl methacrylate is preferably disiloxane methyl acrylate.
The aliphatic acid polyethenoxy ether is preferably dodecyl polyoxyethylene ether, cetyl polyoxyethylene ether and ten At least one of eight alkyl polyoxyethylene ethers.
A kind of above-mentioned floride-free water-proof aagent of green the preparation method comprises the following steps: by green floride-free water-proof aagent each component according to Ratio is uniformly mixed, and the floride-free water-proof aagent of green is made.
A kind of application of the above-mentioned floride-free water-proof aagent of green in fibre.
The fibre is to be made by least one of cellulose fibre, protein fibre and synthetic fibers fiber Woven fabric, knitted fabric or non-woven cloth.
A kind of application of the floride-free water-proof aagent of green in fibre, method particularly includes: it will be green floride-free anti- Water finishing agent and water are hybridly prepared into the finishing fluid that concentration is 5~30g/L, then pad fibre, ultraviolet light solidification.
Described to pad condition preferred are as follows: first infiltrates 30min, then second dipping and rolling (room temperature), pick-up 30-75wt%.
The second dipping and rolling was rolled after referring to fibre infiltration finishing fluid 30min through roll, is repeated and is padded once.
The ultraviolet light cured time is preferably 1~3min.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) the present invention overcomes the deficiencies of existing product, are able to achieve fibre water and oil repellant, easy to industrialized production, Application method is simple, at low cost, and waterproof performance is excellent, low-carbon energy-saving, has a good application prospect and economic benefit.
(2) present invention prepares finishing agent using the tree-like dissaving polymer with highly branched molecular topology, by Have the characteristics that intermolecular chain entanglement is few, dissolubility is good, viscosity is low, easy film forming and reactivity are high in it, overcomes linear low The disadvantage that finishing agent viscosity is big made from polymers, oxygen inhibition is more serious.
(3) present invention combines the respective advantage of organosilicon and acrylate, using environmentally friendly organosiloxane base and Long carbon chain alkyl provides waterproofing function, and a kind of photocuring water repellent finishing agent for being free of fluorine element of preparation is environmentally protective to prepare Water repellent finishing agent lays the foundation.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
DAROCUR1173 used in the embodiment of the present application is bought in Sigma-Aldrich company.
Disiloxane methyl acrylate synthesis used is referring to patent CN101497682A.
Steareth used (93), cetyl polyoxyethylene ether () and dodecane C10 Base polyoxyethylene ether (L4) purchase is in Sigma-Aldrich company.
It is to be arrived styrene modification by sulphur-alkene click-reaction that ethyl phenyl sulfide propyl mercapto propyl used, which gathers a times siloxanes, POSS-SH8It is upper to be made, method particularly includes:
Weigh POSS-SH8(0.01mol, 9.3g) is dissolved in 20mL dichloromethane solution as A liquid；Weigh styrene (4.16g, 0.04mol) and photoinitiator Irgacure-907 (0.02g is bought in Changzhou strength company) are dissolved in 20mL dichloro B liquid is used as in dichloromethane.A liquid is transferred in the single-necked flask with magnetic stirring apparatus first, stirring is opened and is used in combination The LED ultraviolet source of 365nm wavelength is irradiated；Then, B liquid is transferred to the constant pressure addition leakage being protected from light with aluminium foil In bucket, B liquid is added in A liquid with certain speed, is added dropwise to complete time control in or so half an hour.After B liquid is added dropwise to complete, mix It closes liquid and continues exposure stirring 2 hours under ultraviolet light.Rotary distillation obtains clear viscous liquids object after removing dichloromethane solvent Matter is washed repeatedly with methanol solution, finally it is placed in vacuum oven, and 24 hours are dried at 70 DEG C to get target product. (preparation method is detailed in: the preparation of the bionical patterning light solidifying coating of Gan Yanchang and its application study [D] Shanghai Communications University, 2015, wherein the preparation method of POSS-SH8 is detailed in: Lin, H；Wan,X；Jiang,X S；Wang,Q K；Yin,J,A nanoimprint lithography hybrid photoresist based on the thiol-ene system.Adv.Funct.Mater.:2011,21,2960-2967)。
The preparation method of the trapezoidal poly-organosilicon resin of ethyl phenyl sulfide methacryloxypropyl used in the embodiment of the present application is such as Under:
It is reacted first by click chemistry and styrene is clicked into synthesis ethyl phenyl sulfide third on mercaptopropyl trimethoxysilane Base trimethoxy silane (St-TMS): (3- mercaptopropyi) trimethoxy silane (MTPS, 9.26g, 0.047mol, purchase are weighed In lark prestige Reagent Company) it is dissolved in 20mL dichloromethane solution as A liquid；Weigh styrene (4.9g, 0.047mol) and Photoinitiator I-907 (20mg) is dissolved in 20mL dichloromethane solution as B liquid.A liquid is transferred to first and is stirred with magnetic force It mixes in the single-necked flask of device, opens and stir and be irradiated with the LED ultraviolet source of 365nm wavelength；Then, B liquid is shifted Into the constant pressure funnel being protected from light with aluminium foil, B liquid is added in A liquid with certain speed, is added dropwise to complete the time Control is in or so half an hour.After B liquid is added dropwise to complete, mixed liquor continues exposure stirring 2 hours, -0.1Mpa pressure under ultraviolet light Lower rotation is distilled off dichloromethane solvent and obtains product St-TMS.It (is detailed in: the bionical patterning light solidifying coating of Gan Yanchang Preparation and its application study [D] Shanghai Communications University, 2015).
The trapezoidal poly-organosilicon resin (LPSQ) of ethyl phenyl sulfide methacryloxypropyl under alkaline condition with St-TMS and MA-TMS (3- (methacryloxypropyl)-propyl trimethoxy silicane is bought in lark prestige Reagent Company) cohydrolysis obtains: weighing Deionized water (2.4g, 0.133mol) and K2CO3After (0.02g, 0.145mol) is uniformly mixed, tetrahydrofuran is added (4.0g, 0.056mol) is stirred 30 minutes.Then St-TMS (0.04mol) and MA-TMS (0.04mol) mixed solution is added, leads to Nitrogen protection is stirred to react 96 hours at room temperature, after standing a few hours, upper solution is gone, sticky mass is obtained.It is added The dissolution of 30mL methylene chloride, then extraction 5 times is washed with deionized.Methylene chloride phase is isolated, 10mL or so addition is concentrated to 100mL ice methanol solution, after being sufficiently stirred, mixed liquor is placed in -5 DEG C of environment and stands 3 hours, and upper layer methanol solution is gone to be glued Thick transparency material, the lower 40 DEG C of rotary distillations of -0.1MPa pressure remove small molecule and obtain clear viscous product.
SiO2The preparation method of colloidal sol refers to: Xiao Yiqun, Xie Zhiyong, Shen Jun, et al. sol-gel technology prepare SiO2 The structure control of film and stability study [J] light laser and the particle beams, 2006,18 (8): 1302-1306.With positive silicic acid second Ester (TEOS) is presoma, and ammonium hydroxide or HCl are catalyst, prepares SiO under alkalinity and acid condition respectively2Colloidal sol.Colloidal sol Process for preparation should carry out in the environment of clean cleaning, relative humidity are less than 60%.
The process for preparation of base catalysis colloidal sol is by TEOS, ammonium hydroxide (pH=12) and dehydrated alcohol according to the ratio between amount of substance After be mixed evenly at 1: 2: 40, it is placed on standing aging 4d under stable environment (20 DEG C, relative humidity 20%), colloidal sol presents light Blue latex shape.Alkaline sol after aging is flowed back 10h at 80 DEG C, the catalyst ammonia in colloidal sol is removed, to prevent colloidal sol Further hydrolytie polycondensation.
SiO2It is both placed in 4 DEG C of refrigerator-freezer and stores after the completion of colloidal sol preparation, to keep the relatively stable of colloidal sol.
Embodiment 1
A kind of floride-free water-proof aagent of green, by following mass percentage composition:
10% component A, 10% component B and 80% component C；
Wherein, component A is that the ethyl phenyl sulfide propyl mercapto propyl that mass ratio is 1:4:2:0.5 gathers times siloxanes, ethyl phenyl sulfide The trapezoidal poly-organosilicon resin of methacryloxypropyl, cetyl trimethylammonium bromide and (3- mercapto propyl) trimethoxy silane The mixture of composition；
Component B is the trapezoidal poly-organosilicon resin/SiO of ethyl phenyl sulfide methacryloxypropyl that mass ratio is 40:12It is molten The mixture of glue and photoinitiator composition；
Component C is the 1,1,3,3- tetramethyl disiloxane ylmethyl that mass ratio is 4:0.03:0.03:0.015:1:0.5 Acrylate, lauryl sodium sulfate, Steareth, ammonium persulfate, methyl methacrylate, methacrylic acid The mixture of hydroxyl ethyl ester composition；
The trapezoidal poly-organosilicon resin/SiO of ethyl phenyl sulfide methacryloxypropyl2Ethyl phenyl sulfide methacryl in colloidal sol The trapezoidal poly-organosilicon resin of oxygen propyl group and SiO2The molar ratio of colloidal sol is 1:16, and photoinitiator is DAROCUR 1173.
It is cotton that fabric to be arranged, which is mass ratio: washing (70:30) blended yarn weaved fabric.
The floride-free water-proof aagent of above-mentioned green is respectively formed and is proportionally uniformly mixed, the floride-free water-proof finish of green is made Agent；Green floride-free water-proof aagent and water are hybridly prepared into the finishing fluid that concentration is 10g/L, pad fibre, ultraviolet light Solidification.
Wherein, process flow are as follows: (infiltrate 30min, pick-up every time with finishing fluid infiltration fabric 30min → second dipping and rolling For 70wt%, room temperature) → ultraviolet light solidification 1min, obtain the fabric after finishing agent arranges.
Embodiment 2
A kind of floride-free water-proof aagent of green, by following mass percentage composition:
15% component A, 15% component B and 70% component C；
Wherein, component A is that the ethyl phenyl sulfide propyl mercapto propyl that mass ratio is 1.5:5:2.5:0.75 gathers times siloxanes, benzene second The trapezoidal poly-organosilicon resin of thioether methacryloxypropyl, cetyl trimethylammonium bromide and (3- mercapto propyl) trimethoxy The mixture of silane composition；
Component B is the trapezoidal poly-organosilicon resin/SiO of ethyl phenyl sulfide methacryloxypropyl that mass ratio is 30:12It is molten The mixture of glue and photoinitiator composition；
Component C is the 1,1,3,3- tetramethyl disiloxane that mass ratio is 4.5:0.045:0.045:0.015:1.5:0.75 Methyl acrylate, lauryl sodium sulfate, dodecyl polyoxyethylene ether, ammonium persulfate, methyl methacrylate, methyl The mixture of hydroxy-ethyl acrylate composition；
The trapezoidal poly-organosilicon resin/SiO of ethyl phenyl sulfide methacryloxypropyl2Ethyl phenyl sulfide methacryl in colloidal sol The trapezoidal poly-organosilicon resin of oxygen propyl group and SiO2The molar ratio of colloidal sol is 1:16, and photoinitiator is DAROCUR 1173.
It is wool that fabric to be arranged, which is mass ratio: washing (60:40) blended yarn weaved fabric.
The floride-free water-proof aagent of above-mentioned green is respectively formed and is proportionally uniformly mixed, the floride-free water-proof finish of green is made Agent；Green floride-free water-proof aagent and water are hybridly prepared into finishing fluid, finishing fluid concentration is 10%, pads fibre, purple Outer photocuring.
Wherein, process flow are as follows: (infiltrate 30min, pick-up every time with finishing fluid infiltration fabric 30min → second dipping and rolling For 70wt%, room temperature) → ultraviolet light solidification 2min, obtain the fabric after finishing agent arranges.
Embodiment 3
A kind of floride-free water-proof aagent of green, by following mass percentage composition:
20% component A, 20% component B and 60% component C；
Wherein, component A is that the ethyl phenyl sulfide propyl mercapto propyl that mass ratio is 2:6:3:1 gathers times siloxanes, ethyl phenyl sulfide first The trapezoidal poly-organosilicon resin of base acryloxypropyl, cetyl trimethylammonium bromide and (3- mercapto propyl) trimethoxy silane group At mixture；
Component B is the trapezoidal poly-organosilicon resin/SiO of ethyl phenyl sulfide methacryloxypropyl that mass ratio is 15:12It is molten The mixture of glue and photoinitiator composition；
Component C is the 1,1,3,3- tetramethyl disiloxane ylmethyl propylene that mass ratio is 5:0.06:0.06:0.03:2:1 Acid esters, lauryl sodium sulfate, cetyl polyoxyethylene ether, ammonium persulfate, methyl methacrylate, hydroxyethyl methacrylate second The mixture of ester composition；
The trapezoidal poly-organosilicon resin/SiO of ethyl phenyl sulfide methacryloxypropyl2Ethyl phenyl sulfide methacryl in colloidal sol The trapezoidal poly-organosilicon resin of oxygen propyl group and SiO2The molar ratio of colloidal sol is 1:16, and photoinitiator is DAROCUR 1173.
Fabric to be arranged is that mass ratio is fiber crops: cotton (30:70) blended yarn weaved fabric.
The floride-free water-proof aagent of above-mentioned green is respectively formed and is proportionally uniformly mixed, the floride-free water-proof finish of green is made Agent；Green floride-free water-proof aagent and water are hybridly prepared into the finishing fluid that concentration is 10%, pad fibre, UV light Change.
Wherein finishing technique process are as follows: (infiltrated 30min every time with finishing fluid infiltration fabric 30min → second dipping and rolling, rolled remaining Rate is 70wt%, room temperature) → ultraviolet light solidification 3min, obtain the fabric after finishing agent arranges.
The mechanical strength of sample of the present invention measures: according to the rule of American Society Testing and Materials standard ASTM D5034-95 It is fixed, use the broadwise tensile strength (ultimate strength) of tester for elongation measurement fabric.It is cut on each piece of fabric to be measured first Sample, size are 100 × 200mm, and long side is parallel to broadwise, and it is 21 ± 1 DEG C that all samples, which are placed in temperature, humidity is 65 ± Preparatory damping 24 hours in 2% standard environment, and tested in this standard environment；Sample is installed on tester, Long side is set to be parallel to the direction of pulling force, middle line is located at the center of two clamps, locks clamp, and starting tester uniform speed slow stretches Sample, until sample fracture records pulling force numerical value at this time.Retest sample takes the mean values of pulling force.
Broadwise tensile strength retention rate calculation formula is as follows:
BR=BS/BS0× 100%
The tensile strength (1b) of fabric after BS- is arranged in formula
BS0The tensile strength (1b) of non-finish fabric
The mechanical property of 1 sample of table
The present invention mainly passes through contact angle test to the water repellency of the fabric after finishing agent arrangement, spray performance is surveyed It tries to evaluate.
Contact angle test are as follows: textile swatch 1cm × 1cm after clip arranges, in DSA-30 type contact angle performance test equipment Upper test.
Water repellency test is by AATCC-22 standard (referring to GB4745-84 " the textile fabric surface moisture resistance measurement in China Method ") it is tested on YB813 type fabric degree of getting wet analyzer (Wenzhou Daiei textile standard instrument plant).It is commented with standard adhesional wetting card Point, water drenching experiment is carried out on water drenching instrument.
The water repellency of 2 fabric of table
Embodiment Contact angle (°) Spray scoring (dividing)
1 130.5 70
2 127.9 68
3 133.6 74
Contact angle size has reacted the amphipathic property on surface, and the bigger angle the more hydrophobic, due to being to do textile fabric surface The measurement of moisture resistance, so contact angle is bigger, the higher moisture resistance of scoring is better.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of floride-free water-proof aagent of green, which is characterized in that the component comprising following mass percent:
10~20% component A, 10~20% component B and 60~80% component C；
Wherein, component A is (1~2): (4~6): (2~3) by mass ratio: poly- times of the ethyl phenyl sulfide propyl mercapto propyl of (0.5~1) The trapezoidal poly-organosilicon resin of siloxanes, ethyl phenyl sulfide methacryloxypropyl, cetyl trimethylammonium bromide and (3- mercapto third Base) trimethoxy silane composition；
Component B is (15~40): the trapezoidal poly-organosilicon resin/SiO of 1 ethyl phenyl sulfide methacryloxypropyl by mass ratio2It is molten Glue and photoinitiator composition；
Component C is (4~5): (0.03~0.06): (0.03~0.06): (0.015~0.03): (1~2): (0.5 by mass ratio ~1) siloxanyl methacrylate, lauryl sodium sulfate, aliphatic acid polyethenoxy ether, ammonium persulfate, metering system Sour methyl esters and hydroxyethyl methacrylate composition；
The sum of mass percent of said components A, B and C is 100%.
2. the floride-free water-proof aagent of a kind of green according to claim 1, which is characterized in that the ethyl phenyl sulfide metering system The trapezoidal poly-organosilicon resin/SiO of monomethacryloxypropyl2In colloidal sol the trapezoidal poly-organosilicon resin of ethyl phenyl sulfide methacryloxypropyl with SiO2The molar ratio of colloidal sol is 1:16~1:21.
3. the floride-free water-proof aagent of a kind of green according to claim 1 or claim 2, which is characterized in that the siloxy group methyl Acrylate is disiloxane methyl acrylate.
4. the floride-free water-proof aagent of a kind of green according to claim 3, which is characterized in that the aliphatic acid polyethenoxy ether For at least one of dodecyl polyoxyethylene ether, cetyl polyoxyethylene ether and Steareth.
5. a kind of floride-free water-proof aagent of green according to claim 3, which is characterized in that the photoinitiator is At least one of DAROCUR 1173, IRGACURE 2100 and IRGACURE 2959.
6. a kind of application of any one of Claims 1 to 5 floride-free water-proof aagent of green in fibre.
7. application of the floride-free water-proof aagent of a kind of green in fibre according to claim 6, which is characterized in that institute Stating fibre is woven fabric, needle as made from least one of cellulose fibre, protein fibre and synthetic fibers fiber Fabric or non-woven cloth.
8. a kind of application of the floride-free water-proof aagent of green described according to claim 6 or 7 in fibre, feature exist In, method particularly includes: green floride-free water-proof aagent and water are hybridly prepared into the finishing fluid that concentration is 5~30g/L, then soaked Roll fibre, ultraviolet light solidification.
9. application of the floride-free water-proof aagent of a kind of green in fibre according to claim 8, which is characterized in that institute State the condition of padding are as follows: first infiltrate 30min, then second dipping and rolling, pick-up 30-75wt%.
10. application of the floride-free water-proof aagent of a kind of green in fibre according to claim 8, which is characterized in that The ultraviolet light curing time is 1~3min.
CN201910536616.3A 2019-06-20 2019-06-20 Green fluorine-free waterproof finishing agent and application thereof in fiber products Active CN110205821B (en)

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