A kind of uvioresistant finishing agent and preparation method thereof
Technical field
The invention belongs to uvioresistant finishing agent fields, more particularly to a kind of uvioresistant finishing agent and its preparation side
Method.
Technical background
For vertical irradiation into the sunlight of earth's surface, most of is visible light and infrared light, ultraviolet light after atmosphere filters
6% or so is only accounted for, however the absorption peak of the molecular structure of polysulfones, polyester terephthalate and polyurethane is located at ultraviolet region, gathers
The polymer such as styrene, polyglycerol fatty acid ester, polyacrylate, polyamide are also more sensitive to ultraviolet light, therefore above-mentioned substance is in purple
Under the irradiation of outer light, it is easy degradation.In addition, remaining catalyst and the micro peroxide generated during synthesis, processing, storage
The impurity such as compound, charge transfer complex can absorb ultraviolet light and lead to the polyvinyls such as polyolefin, polyvinyl chloride
Degradation.
Industrial common uvioresistant finishing agent is mostly ultraviolet absorbing agent and nanoparticle photomask agent.Ultraviolet light is inhaled
Receiving agent is a kind of organic compound that can selectively absorb ultraviolet light strongly and have high light fastness properties itself.It answers extensively at present
For benzophenone, benzotriazole compound.But the ultraviolet absorbing agent of small molecule is easy gasification, volatilization, is extracted by solvent
It takes and migrates to material surface and lose, to be unfavorable for the anti-ultraviolet property of material.Application No. is 200910153304.0
The ultraviolet light suction that broadband uvioresistant high light-fast finishing agent and preparation method and application are disclosed with benzotriazole, benzophenone
The uvioresistant finishing agent for receiving the preparations such as agent and defoaming agent, dispersing agent, water passes through the weaving of the methods of dyeing, final finishing processing
Product have certain anti-ultraviolet property, but its UPF value is relatively low, and ultraviolet ray transmissivity is high.
Nano-titanium dioxide in photomask agent has strong protective action, but its particle poor compatibility to ultraviolet light, is not easy
It is evenly dispersed in dispersion, mechanics and the decline of other performances are easily led to, uvioresistant effect is influenced.
Summary of the invention
Present invention aims to overcome that in the prior art using benzophenone, benzotriazole compound as anti-ultraviolet finishing
The defects of easy gasification of agent, volatilization, provides a kind of addition by acrylate, the nano-titanium dioxide of fluorochemical monomer graft modification
Uvioresistant finishing agent and preparation method thereof.
The present invention provides a kind of uvioresistant finishing agent, which contains ultraviolet absorbing agent, dispersing agent, defoaming
Agent, water, wherein the finishing agent also contains nano-titanium dioxide graft copolymer, the nano-titanium dioxide graft copolymer
For nano-titanium dioxide, acrylate monomer, fluorochemical monomer graft copolymer.
This law is bright to additionally provide the preparation method of above-mentioned uvioresistant finishing agent, this method comprises: by ultraviolet absorbing agent,
Dispersing agent, defoaming agent, water mixing, wherein be additionally added nano-titanium dioxide graft copolymer, the nano-silica in mixing
Change titanium graft copolymer is nano-titanium dioxide, acrylate monomer, fluorochemical monomer graft copolymer.
The nanometer titanium dioxide of acrylate and fluoropolymer monomer graft modification is added in prior art basis in the present invention
Titanium is played with ultraviolet-resistant absorbent and is acted synergistically, improves anti-ultraviolet performance, overcome organic ultraviolet-resistant absorbent
It is volatile, be extracted, gasify, and the disadvantages of performance is single.Acrylate and fluoropolymer monomer carry out nano-titanium dioxide
Graft modification generates the finely dispersed Nanocomposites microballoon in dispersed phase, improves the stably dispersing of nanoparticle
Property, avoid TiO2The deficiency of easy to reunite, difficult dispersion when the dispersion of aqueous dispersions high speed shear and ultrasonic disperse processing, to make to receive
The nano effect of rice titanium dioxide gives full play to.Contain fluorine monomer in nano-titanium dioxide graft copolymer, reduces grafting altogether
The surface tension of polymers, improves the compatibility of itself and ultraviolet-resistant absorbent dispersion liquid, and is not easy to form boundary defect, and can increase
The storage stability of strong product of the present invention.Uvioresistant finishing agent of the present invention can be used for the anti-ultraviolet finishing of textile.
Specific embodiment
Uvioresistant finishing agent disclosed by the invention contains ultraviolet absorbing agent, dispersing agent, defoaming agent, water, wherein this is whole
Reason agent also contains nano-titanium dioxide graft copolymer, the nano-titanium dioxide graft copolymer be nano-titanium dioxide,
Acrylate monomer, fluorochemical monomer graft copolymer.
Disclosed uvioresistant finishing agent according to the present invention, in terms of mass parts, the ultraviolet light of the uvioresistant finishing agent is inhaled
Receive agent 15-28 parts, 7-11 parts of dispersing agent, 2-3 parts of defoaming agent, 320-460 parts of water, nano-titanium dioxide graft copolymer 45-58
Part.
Wherein, the preparation method of the nano-titanium dioxide graft copolymer includes the following steps
A, a certain amount of nano-titania particle, silane coupling agent are weighed in dehydrated alcohol, it is ultrasonic after mixing evenly
Dispersion 10 minutes, heating water bath to 50-70 DEG C react 5 hours, 80 DEG C drying after grinding obtain modified nano-titanium dioxide grain
Son;
B, modified nano-titanium dioxide particle is added in a certain concentration polymerisable emulsifier aqueous solution, after mixing evenly
Ultrasonic disperse 10 minutes, initiator solution is added when heating water bath is to 70-80 DEG C, acrylate monomer is added dropwise and remaining draws
Agent aqueous solution is sent out, rear sustained response is added dropwise 5 hours, cooled to room temperature, filtering obtains uniform and stable nano-silica
Change titanium graft copolymer.
In the nano-titanium dioxide graft copolymer, in terms of mass parts, nano-titanium dioxide be 15-20 parts, third
Olefin(e) acid ester monomer is 54-68 parts, and fluorochemical monomer is 14-21 parts.
Silane coupling agent is not particularly limited, if contain C=C and hydrolyzable alcoxyl key in molecule, such as
Silane coupling agent can be γ-methacryloxypropyl trimethoxy silane (KH-570), vinyltriethoxysilane
(KH-151), vinyltrimethoxysilane (KH-171), vinyl three ('beta '-methoxy ethyoxyl) silane (KH-172).
Wherein, initiator is selected from one of sodium peroxydisulfate, ammonium persulfate, potassium peroxydisulfate, and dosage is 1-1.5 parts, uses
The water dissolution of Shi Yishi times of mass parts.In addition, it should be noted that, the water that the present invention uses is deionized water.
Wherein, polymerisable emulsifier is allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether ammonium sulfate (C21H77O3
(C2H4O)nSO3NH4, n=10), allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether (C21H77O3(C2H4O)nH, n=10).
The dosage of emulsifier is 12-19 parts, and two kinds of emulsifiers are prepared by 1: 1.
Wherein, the nano-titanium dioxide is rutile-type, and average grain diameter 30nm is commercially available.
Wherein, it is just pungent to be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid for the acrylate
One or more of ester, fluorochemical monomer is in hexafluorobutyl acrylate, dodecafluorhe-ptylacrylate, acrylic acid trifluoro ethyl ester
One or more.
The dispersing agent primarily serves the effect of emulsion dispersion ultraviolet absorbing agent, stable dispersion system, can be ability
One of the common dispersing agent in domain, such as Dispersant MF, dispersing agent NNO, Arlacel-60, Arlacel-80, Tween-60, Tween-80
Or it is a variety of.
The defoaming agent can be any defoaming agent commonly used in the art, such as DOW CORNING DC1410, DOW CORNING DC1520,
DOW CORNING AFE-7610.
Wherein, ultraviolet absorbing agent be Benzotriazole Ultraviolet Stabilizer and/or benzophenone ultraviolet absorbent,
Ultraviolet absorbing agent can be it is known in the art that for example, Benzotriazole Ultraviolet Stabilizer UV-P, UV-326, UV-327,
UV-328, UV-329, benzophenone ultraviolet absorbent UV-531, UV-9.
Preferably, Benzotriazole Ultraviolet Stabilizer is ultraviolet absorbent uv-326, in UV-327, UV-328
One or more, benzophenone ultraviolet absorbent are ultraviolet absorbent UV-531.Ultraviolet absorbent uv-326 is 2 '-
(2 '--3 '-tert-butyls -5 of hydroxyl '-aminomethyl phenyl) -5- chlorobenzotriazole, molecular formula C17H18N3OCl, CAS NO.:3864-99-
1;UV-327 is 2- (2 '-hydroxyls -3 ', 5 '-di-tert-butyl phenyl) -5- chlorobenzotriazole, molecular formula C20H24N3OCl, CAS
NO.:3864-99-1;UV-328 is 2- [2- hydroxyl -3,5- bis- (1,1- dimethyl propyl phenyl)] -2H- benzotriazole, molecule
Formula is C22H29N3O, CAS NO.:21615-48-6;UV-531 is [2- hydroxyl -4- (octyloxy) phenyl] phenyl ketone, and molecular formula is
C21H26O3, CAS NO.:1843-05-6.
The preparation method of uvioresistant finishing agent disclosed by the invention includes: by ultraviolet absorbing agent, dispersing agent, defoaming
Agent, water mixing, wherein nano-titanium dioxide graft copolymer is additionally added in mixing, the nano-titanium dioxide grafting is altogether
Polymers is nano-titanium dioxide, acrylate monomer, fluorochemical monomer graft copolymer;In terms of mass parts, the anti-ultraviolet finishing
320-460 parts of 2-3 parts of 7-11 parts of 15-28 parts of ultraviolet absorbing agent, dispersing agent, defoaming agent, the water of agent, nano-titanium dioxide grafting
45-58 parts of copolymer.
Wherein, specific steps when ultraviolet absorbing agent, dispersing agent, defoaming agent, water mixing are as follows:
1) ultraviolet absorbing agent, dispersing agent, defoaming agent, water are placed in ball milling instrument, abrading-ball is added;
2) at room temperature ball milling 3-4 hours;
3) it filters, obtains the dispersion liquid of ultraviolet absorbing agent.
It, can be by graft copolymer when nano-titanium dioxide graft copolymer is mixed with ultraviolet radiation absorption agent dispersing liquid obtained
It is added directly into dispersion liquid, dispersion liquid can also be added in graft copolymer, then be stirred evenly.
Below by embodiment, the present invention will be described in more detail.
Embodiment 1
(1) preparation of nano-titanium dioxide graft copolymer
A, 15 parts of nano-titania particles, 2 parts of silane coupling agents are weighed in 150mL dehydrated alcohol, after mixing evenly
Ultrasonic disperse 10 minutes, heating water bath to 50 DEG C react 5 hours, 80 DEG C drying after grinding obtain modified nano-titanium dioxide grain
Son;The silane coupling agent is γ-methacryloxypropyl trimethoxy silane (KH-570).
B, modified nano-titanium dioxide particle is added in the solution of 12 parts of polymerisable emulsifiers and 300mL water, stirring
Ultrasonic disperse 10 minutes after uniformly is added the aqueous solution of 0.5 part of initiator potassium persulfate, is added dropwise 54 parts when heating water bath is to 70 DEG C
The aqueous solution of acrylate monomer, 14 parts of fluorochemical monomers and 0.5 part of initiator potassium persulfate, it is small to be added dropwise rear sustained response 5
When, cooled to room temperature, filtering obtains uniform and stable nano-titanium dioxide graft copolymer;The acrylate monomer
For 6 parts of methyl acrylate, 8 parts of ethyl acrylate, 24 parts of n-butyl acrylate, 16 parts of n-octyl, fluorochemical monomer third
Olefin(e) acid hexafluoro butyl ester.
(2) preparation of the dispersion liquid of ultraviolet absorbing agent
1) by 15 parts of ultraviolet absorbing agents (5 parts of UV-326,5 parts of UV-327,5 parts of UV-328), 7 parts of dispersing agent (dispersions
2 parts of agent MF, 2 parts of dispersing agent NNO, 1 part of Arlacel-60,2 parts of Tween-60), 2 parts of defoaming agents (DOW CORNING DC1410), 320 parts
Water is placed in ball milling instrument, and abrading-ball is added;
2) ball milling 3 hours at room temperature;
3) it filters, obtains the dispersion liquid of ultraviolet absorbing agent.
(3) preparation of uvioresistant finishing agent
Nano-titanium dioxide graft copolymer made from 45 parts of steps (1) is added to the ultraviolet absorbing agent of step (2)
In dispersion liquid, stir evenly to get uvioresistant finishing agent.
Embodiment 2
(1) preparation of nano-titanium dioxide graft copolymer
A, 17 parts of nano-titania particles, 3 parts of silane coupling agents are weighed in 200mL dehydrated alcohol, after mixing evenly
Ultrasonic disperse 10 minutes, heating water bath to 60 DEG C react 5 hours, 80 DEG C drying after grinding obtain modified nano-titanium dioxide grain
Son;The silane coupling agent is vinyltriethoxysilane (KH-151).
B, modified nano-titanium dioxide particle is added in the solution of 15 parts of polymerisable emulsifiers and 300mL water, stirring
Ultrasonic disperse 10 minutes after uniformly is added the aqueous solution of 0.5 part of initiator ammonium persulfate, is added dropwise 61 parts when heating water bath is to 75 DEG C
The aqueous solution of acrylate monomer, 18 parts of fluorochemical monomers and 0.7 part of initiator ammonium persulfate, it is small to be added dropwise rear sustained response 5
When, cooled to room temperature, filtering obtains uniform and stable nano-titanium dioxide graft copolymer;The acrylate monomer
For 13 parts of ethyl acrylate, 48 parts of n-butyl acrylate, fluorochemical monomer is 7 parts of hexafluorobutyl acrylate, ten difluoro heptan of acrylic acid
7 parts of ester, 4 parts of acrylic acid trifluoro ethyl ester.
(2) preparation of the dispersion liquid of ultraviolet absorbing agent
1) by 22 parts of ultraviolet absorbing agents (4 parts of UV-326,6 parts of UV-327,7 parts of UV-328,5 parts of UV-531), 9 parts
Dispersing agent (2 parts of Dispersant MF, 2 parts of dispersing agent NNO, 3 parts of Arlacel-80,2 parts of Tween-80), 3 parts of defoaming agent (DOW CORNINGs
DC1520), 390 parts of water are placed in ball milling instrument, and abrading-ball is added;
2) ball milling 4 hours at room temperature;
3) it filters, obtains the dispersion liquid of ultraviolet absorbing agent.
(3) preparation of uvioresistant finishing agent
Nano-titanium dioxide graft copolymer made from 52 parts of steps (1) is added to the ultraviolet absorbing agent of step (2)
In dispersion liquid, stir evenly to get uvioresistant finishing agent.
Embodiment 3
(1) preparation of nano-titanium dioxide graft copolymer
A, 20 parts of nano-titania particles, 4 parts of silane coupling agents are weighed in 250mL dehydrated alcohol, after mixing evenly
Ultrasonic disperse 10 minutes, heating water bath to 70 DEG C react 5 hours, 80 DEG C drying after grinding obtain modified nano-titanium dioxide grain
Son;The silane coupling agent is vinyl three ('beta '-methoxy ethyoxyl) silane (KH-172).
B, modified nano-titanium dioxide particle is added in the solution of 19 parts of polymerisable emulsifiers and 300mL water, stirring
Ultrasonic disperse 10 minutes after uniformly is added the aqueous solution of 0.5 part of initiator sodium peroxydisulfate, is added dropwise 68 parts when heating water bath is to 80 DEG C
The aqueous solution of acrylate monomer, 21 parts of fluorochemical monomers and 1 part of initiator sodium peroxydisulfate, is added dropwise rear sustained response 5 hours,
Cooled to room temperature, filtering, obtains uniform and stable nano-titanium dioxide graft copolymer;The acrylate monomer is
N-butyl acrylate, fluorochemical monomer are 4 parts of hexafluorobutyl acrylate, 5 parts of dodecafluorhe-ptylacrylate, acrylic acid trifluoro ethyl ester 12
Part.
(2) preparation of the dispersion liquid of ultraviolet absorbing agent
1) by 28 parts of ultraviolet absorbing agents (28 parts of UV-531), 11 parts of dispersing agents (2 parts of Dispersant MFs, dispersing agent NNO 2
Part, 3 parts of Arlacel-60,4 parts of Tween-80), 3 parts of defoaming agents (DOW CORNING AFE-7610), 460 parts of water be placed in ball milling instrument, add
Enter abrading-ball;
2) ball milling 4 hours at room temperature;
3) it filters, obtains the dispersion liquid of ultraviolet absorbing agent.
(3) preparation of uvioresistant finishing agent
The ultraviolet radiation absorption agent dispersing liquid of step (2) is added to the grafting of nano-titanium dioxide made from 58 parts of steps (1)
In copolymer, stir evenly to get uvioresistant finishing agent.
Comparative example
Referring to application No. is 200910153304.0 broadband uvioresistant high light-fast finishing agent and preparation method and applications
Embodiment 1, prepare uvioresistant finishing agent.
15g Benzotriazole Ultraviolet Stabilizer UV-326,10g benzophenone ultraviolet is added into ball milling instrument to absorb
Then agent UV-531,1.5g dispersing agent M-9,1.5g dispersing agent SP-762 and 150g abrading-ball adds 10g water, room temperature thereto again
Lower ball milling 10h.After ball milling, gained dispersion liquid is filtered to and is added water constant volume, it is 25g/L that total amount containing ultraviolet absorbing agent, which is made,
Broadband uvioresistant high light-fast finishing agent.
The application of embodiment 1-3 and comparative example:
The anti-purple of 20g acrylic ester adhesive (solid content 53%), 50g embodiment 1-3 and comparative example is added into 1 liter of water
Outside line finishing agent, with acrylic thickeners adjusting viscosity to 5000 centipoises or so, by the method for surface covering, in 32*
Apply 80g/m on the gambroon of 32/130*802Uvioresistant finishing agent, after 100 DEG C, 5 minutes preliminary dryings, then at
175 DEG C bake 1 minute.
The anti-ultraviolet property of the cotton arranged through anti-outside line finishing agent presses GB/T18830-2009 " textile antiultraviolet
The measurement of performance " method test, test equipment Labsphere, washing methods is referring to AATCC 13, and test result is as follows:
The uvioresistant performance of each example uvioresistant finishing agent of table 1
As can be seen from Table 1, the UPF value through embodiment 1-3 uvioresistant finishing agent treated cotton is greater than 55, T (UVA)
AV has reached excellent uvioresistant grade then less than 5%, and performance is good compared with comparative example.