CN106752996A - Ultraviolet and ultrared PVB films and preparation method thereof can simultaneously be intercepted - Google Patents
Ultraviolet and ultrared PVB films and preparation method thereof can simultaneously be intercepted Download PDFInfo
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- CN106752996A CN106752996A CN201611199520.5A CN201611199520A CN106752996A CN 106752996 A CN106752996 A CN 106752996A CN 201611199520 A CN201611199520 A CN 201611199520A CN 106752996 A CN106752996 A CN 106752996A
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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- C08K13/02—Organic and inorganic ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
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- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K5/00—Use of organic ingredients
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/10—Properties of the layers or laminate having particular acoustical properties
- B32B2307/102—Insulating
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- B32—LAYERED PRODUCTS
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/304—Insulating
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
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Abstract
Ultraviolet and ultrared PVB films and preparation method thereof can be simultaneously intercepted the present invention relates to one kind, ultraviolet and ultrared PVB films can be simultaneously intercepted to be combined and constituted by upper strata, middle level, lower film successively, middle level film thickness is 110 150 microns, and the upper and lower film thickness is 150 450 microns；The middle layer membrane materials are prepared by the modified PVB resin powder that melting means is 5 8g/10min, and the upper and lower thin-film material is prepared by the modified PVB resin powder that melting means is 3 4g/10min；After the preparation method of modified PVB resin powder is the raw material condensation reaction that will be chosen, modified PVB resin powder is prepared by neutralisation treatment, dehydration and drying again, the three layers of PVB films for preparing are applied to doubling glass and can effectively intercept the ultraviolet that wavelength is the infrared ray of 780 2500nm, wavelength is 200 380nm.
Description
Technical field
The present invention relates to a kind of infrared barrier PVB films, belong to folder infrared barrier glue glass applications field.
Background technology
In recent years, with the fast development of China's real estate, glass curtain wall is widely used in heavy construction, heat-insulated
Glass is designed using LOW-E, double glazing mostly, but the potential safety hazard brought therewith is also more and more.Meanwhile, it is domestic at present to pacify
Full glass industry commonly uses PVB intermediate coats, as expanding economy proposes power conservation requirement higher to thermal-insulative safety glass.
The wavelength of solar radiation is mainly in 200-2500nm, and the wavelength of its middle-ultraviolet lamp, can between 200-380nm
The wavelength of light is seen between 380-780nm, and (wherein 780nm-1500nm is near red to ultrared wavelength between 780-2500nm
Outside line, 1500nm-2500nm is middle infrared (Mid-IR)).Ultraviolet is smaller in total sunshine ratio, and about 5%, but it is each
Plant the main cause of material accelerated ageing.Ultrared energy accounting is higher, and about 50%, infrared light is to make indoor temperature liter
Principal element high.
In order to obtain the PVB doubling glass with effect of heat insulation, a kind of method is that low-e is plated on doubling glass is heat-insulated
Layer or hollow heat insulation layer；A kind of method is the fenestrated membrane that adhesive tape has effect of heat insulation on doubling glass；A kind of method is in PVB productions
During adulterate organic IR absorbing dye so as to prepare colour film；Still an alternative is that during PVB films are made
A small amount of inorganic nano heat-insulating slurry is added to prepare PVB nano heat-insulating glued membranes.But first three methods change doubling glass
Structure, production technology, and transmitance, than relatively low, service life is shorter, and a kind of only last method is better.Therefore,
Need effect of heat insulation more preferably simultaneously transparency also will height, but in current thermal isolation film, the transparency of good heat-insulation effect and clear
Degree is poor, and transparency and definition effect of heat insulation high are again poor.Therefore a kind of good heat-insulation effect is needed, while can keep good again
Transparency and definition thermal isolation film.
Chinese patent CN203530211U, CN103044828A, CN1555989A and CN102863917A are disclosed and passed through
ATO or ITO nanometers infrared effect of heat insulation of functional particles improvement PVB films of addition, infrared in having the disadvantage to intercept (1500~
2500nm) with far infrared (＞ 2500nm), near infrared ray (790~1500nm) barriering effect thermo-responsive to human body is very poor.
Chinese patent CN104262874A is disclosed a kind of dynamic and is intercepted infrared ray and anti-purple using inorganic nano materials such as caesium tungsten bronzes
The preparation method of the PVB film of outside line.Chinese patent CN104877582A discloses a kind of heat-insulated glued membranes of high-performance PVB, its choosing
It is tungsten oxide nanometer slurry, has prepared performance better than the heat-insulated glued membranes of PVB using the preparation such as nano ATO, ITO, AZO.
Chinese patent CN104059548A proposes simultaneously intercept ultraviolet and ultrared PVB films and preparation method thereof, from GTO
Nano dispersion fluid is well mixed as near infrared ray absorption with PVB resin powder, plasticizer, antioxidant and ultra-violet absorber
After to put into and obtain infrared barrier PVB films in double screw extruder.It is thin that Chinese patent CN202344958 discloses a kind of XIR
Film heat reflection Sandwich energy-saving film, although reached reducing energy consumption, the purpose of energy-conservation, but its preparation technology it is complicated, compound plus
Work operation is numerous and diverse time-consuming, in process, easily produces bubble, and thermal isolation film easily produces contraction distortion phenomenon, and causes
Defective goods rate is higher, causes substantial amounts of waste, considerably increases production cost.
In view of patent document uses nano-metal-oxide as the infrared absorbing agents of PVB films, nano-particle both at home and abroad
Absorb infrared light and play effect of heat insulation, but purple is subject to because nano-particle is difficult to dispersion and nano-particle in PVB resin
Outer light irradiation easily changes colour, and causes the insulation product of the modified PVB films of metal oxide nanoparticles can not the marketization, the present invention
Nano-particle scattering problem and discoloration problem are mainly solved, a kind of infrared barrier PVB films of three-decker are provided for market.
The content of the invention
In view of patent document uses nano-metal-oxide as the infrared absorbing agents of PVB films, nano-particle both at home and abroad
Absorb infrared light and play effect of heat insulation, but purple is subject to because nano-particle is difficult to dispersion and nano-particle in PVB resin
Outer light irradiation easily changes colour, and for discoloration problem, we have studied Discoloration mechanism, devises three layers of complex thin film structure, middle
Layer PVB contains metal oxide nanoparticles, plays absorption and intercepts infrared, superficial layer PVB obstruct action of ultraviolet radiation, effectively
The nano-metal-oxide in intermediate layer is avoided to be changed colour by ultraviolet irradiation.This scheme can effectively solve discoloration problem, obtain aberration
The small, mist degree of change is low, good weatherability infrared barrier PVB films.
In order to solve the above-mentioned problems in the prior art, the present invention is provided can simultaneously intercept ultraviolet and ultrared
PVB films and preparation method thereof.Infrared barrier PVB films of the present invention are successively by upper strata, middle level, lower film complex group
Into middle level film thickness is 110-150 microns, and the upper and lower film thickness is 150-450 microns；The original of wherein middle layer film
Material PVB resin powder is that melting means high contains nano-metal-oxide, plays INFRARED ABSORPTION iris action, and two outside layers have to glass
Good cohesive force, while intercepting ultraviolet, the nano-metal-oxide for being prevented effectively from middle level is changed colour by ultraviolet irradiation.
Above-mentioned middle layer membrane materials, for the modified PVB resin powder of 5-8g/10min is prepared, are flowed by melting means with height
Dynamic property, curtain coating is easily formed 110-150 microns of uniform film.
Above-mentioned the upper and lower thin-film material, for the modified PVB resin powder of 3-4g/10min is prepared, is flowed by melting means
Dynamic property is poor, and the film of formation is easily controllable at 300-500 microns.
Above-mentioned upper, middle and lower-ranking film resin formula includes modified PVB resin powder that mass percent is 72% and matter
Amount percentage is 28% plasticizer 3G8.
The component and mass percent of above-mentioned modified PVB resin powder be：
Polyvinyl alcohol：9-10wt%
N-butanol：6-7wt%
Antioxidant：0.01-0.03wt%
Ultraviolet absorber：0.01-0.02wt%
Nano-oxide：0.01-0.02%wt
Surface tension modifier：0-0.01wt%
Hydrochloric acid：2-3wt%
Balance of water.
Above-mentioned antioxidant is selected from the mixture of phenols and phosphorous acid esters, wherein described phenols is selected from four (3,5- bis- uncles
Butyl -4- hydroxyls) benzenpropanoic acid pentaerythritol ester (being commonly called as 1010), 2- di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenols), β-(3,
5- di-tert-butyl-hydroxy phenyls) one kind in the positive octadecanol ester of propionic acid；Described phosphorous acid esters are selected from three (2,4- bis-
The tert-butyl group) phenyl-phosphite (being commonly called as 168), double diphosphites of stearyl alcohol season penta, double (3,5- di-tert-butyl-phenyl) seasons
One kind in penta tetrol diphosphites.
Above-mentioned UV absorbers are Benzotriazole Ultraviolet Stabilizer, selected from 2- (the 2 ˊ-ˊ of hydroxyl-5-methyl)-benzene
And triazole, 2- (the 2 ˊ-ˊ of hydroxyl-3-ˊ of the tert-butyl group-5-methyl) chloro- BTAs of-5-, 2- (2 ˊ-5 ˊ of the ˊ of hydroxyl-3-di-t-butyl)-
The chloro- BTAs of 5-, 2'- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) -5- chlorobenzotriazoles (being commonly called as UV-326), 2-
It is a kind of in (the 2 ˊ-ˊ of hydroxyl-5-t-octyl)-BTA.
Above-mentioned surface tension modifier is inorganic salts, selected from potassium acetate, potassium formate, magnesium acetate, calcium acetate, sodium acetate
In one kind.
Above-mentioned nano-oxide is the one kind in nano-ITO, nano ATO, nanometer GTO, nanometer tungsten bronze；More preferably
Nanometer tungsten bronze.
When the middle layer film of infrared barrier PVB films is prepared, raw material PVA viscosity is controlled to 24-28mPas
(testing standard GB/T 12010.2-2010), average degree of polymerization 1500-1800 (testing standard GB/T 12010.5-2010), alcohol
Solution degree 98-99% (testing standard GB/T 12010.5-2010), the commercially available trade mark in market has Changchun chemical industry (Jiangsu) limited public affairs
Take charge of the trade mark BF-14, BF-17, BF-14W.
When the upper and lower film of infrared barrier PVB films is prepared, raw material PVA viscosity is 28-30mPa
S (test mark GB/T12010.2-2010), average degree of polymerization 1700-2500 (testing standard GB/T 12010.5-2010), alcoholysis
Degree 98-99% (testing standard GB/T 12010.5-2010), the commercially available trade mark in market has Changchun chemical industry (Jiangsu) Co., Ltd
The trade mark BP-20, BP-24, BP-26.
The mass concentration of above-mentioned hydrochloric acid is 31% (testing standard GB 320-2006).
The resistivity of above-mentioned pure water >=18M Ω .CM (testing standard GB6682-92).
Present invention additionally comprises the preparation method of above-mentioned modified PVB resin powder, i.e., synthesized by from raw material PVB resin powder
Antioxidant, ultraviolet absorber, surface tension modifier, nano-oxide are added in journey.
Specific step is：
(1) condensation reaction
First, solution of the concentration less than 10% is made into 90-95 DEG C of water and appropriate polyvinyl alcohol, by solution cooling
To after 40-45 DEG C, hutanal is added, and by antioxidant, ultraviolet absorber, the nano-oxide of proportioning, surface tension adjustment
Agent.Stirring 1-3h；After reaction mixture is cooled to 20-25 DEG C, the appropriate hydrochloric acid of addition, insulation reaction at least 1-5 hours, then will
Reaction mixture is delivered to condensation reaction kettle, and 40 DEG C, then insulation reaction 1-2 hours were gradually heating at 1 hour, uses again afterwards
55 DEG C, then insulation reaction 1-2 hours are gradually heating within 1 hour, are then cooled to room temperature；
(2) neutralisation treatment
Reaction solution after the cooling is delivered into washing kettle to wash 5-6 times, 51-65 DEG C is warming up to afterwards, added appropriate
Soda bath adjusts pH value to 8-10, then is incubated 2-3 hours, fully neutralizes deacidification；
(3) it is dehydrated and dries
It is less than to moisture content after centrifuge dewatering after washing 6-8 times again to the reaction solution neutralized after deacidification
15%, enter after cyclone dryer is dried with air-flow and the modified PVB resin powder is obtained.
Compared with prior art, the beneficial effects of the present invention are：
(1) modified antioxidant, ultraviolet absorber, nano-oxide and surface tension have been used in resin-oatmeal building-up process
Conditioning agent is modified, and in the range of the specific composition and proportioning of above-mentioned auxiliary agent, the synergy between each composition is obtained
Fully play, technique effect is optimal.On the one hand, heat resistance is good, shows 2 hours values of chromatism of resistance to 180 DEG C of constant temperature and is less than 1, passes
The PVB resin powder temperature tolerance for producing of uniting is poor, easy xanthochromia, and resistance to 180 DEG C of constant temperature, the 2 hours values of chromatism of performance are between 1-2.5.The opposing party
Face, shows good heat-proof quality, and it is, more than 20%, especially to use to show as the modified PVB resin powder infrared barrier rate of nano-ITO
The modified PVB resin powder of nanometer tungsten bronze is more than 90% to infrared rejection rate, and conventional PVB resin powder is to infrared rejection rate
Less than 10%.Have again exactly has moderate adhesion strength to glass, and it is 5-6 grades of level to show as to the percussion value of glass, and
Conventional PVB resin powder is 7-9 grades to the caking property percussion value of glass.
(2) preparation method of the invention cleverly adds antioxidant, ultraviolet suction in raw material PVB resin powder building-up process
Receive agent, surface tension modifier, function nano particle so that these auxiliary agents may be uniformly dispersed in resin-oatmeal, is modified
PVB resin powder, the modified PVB resin powder of acquisition can directly extrude curtain coating production PVB films together with plasticizer so that PVB
PVB resin powder and antioxidant, ultraviolet absorber, surface tension modifier, nano-particle is eliminated in film production technology to mix
Material premix link, thoroughly solves nano-particle and auxiliary agent disperses problem of non-uniform in resin-oatmeal, improves PVB film extrusions
The production efficiency of curtain coating, eliminates spice premix link it is possible to prevente effectively from powder pollutes.
(3) the three layers of infrared barrier PVB films prepared using different modified resin powder of the invention can be effective
The noise in the range of human ear sensitivity 1000-4000Hz is intercepted, infrared barrier effect 3- can be lifted compared with general thickness PVB
5dB。
Brief description of the drawings
The SEM figures of infrared barrier PVB films material object prepared by Fig. 1 embodiments 7.
The infrared barrier PVB films of the preparation of Fig. 2 embodiments 7 and the infrared barrier Contrast on effect of common PVB laminated glass.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that specific embodiment described herein is only used to explain the present invention, without structure
Into limitation of the present invention.
The specific preparation method of modified resin powder is as follows
(1) condensation reaction：
First, solution of the concentration less than 10% is made into using 95 DEG C of water and appropriate polyvinyl alcohol in a kettle., will
The solution cool to 45 DEG C add appropriate auxiliary agents (antioxidant, ultraviolet absorber, nano-oxide, surface tension modifier) and
Hutanal is stirred 1h；Secondly, the reaction mixture is cooled to 20 DEG C, adds appropriate hydrochloric, insulation is anti-
Should at least 1 hour, then reaction mixture is delivered to two kettles of condensation, be gradually heating to 40 DEG C at 1 hour, then insulation reaction 1 is small
When, afterwards again with being gradually heating within 1 hour 55 DEG C, then insulation reaction 1 hour, then cool to room temperature；
(2) neutralisation treatment：
Reaction solution after the cooling is delivered into washing kettle to wash 6 times, 45 DEG C are warming up to afterwards, add appropriate caustic soda molten
Liquid adjusts pH value to 9, then is incubated 3 hours, fully neutralizes deacidification；
(3) it is dehydrated and dries：
To it is described neutralize deacidification after reaction solution wash 6 times again after after centrifuge dewatering to moisture content less than 10% with
Air-flow enters the i.e. prepared modified polyvinyl butyral resin finished product after cyclone dryer is dried.
Embodiment 1-6 is prepared according to above-mentioned specific preparation method, and specific raw material and proportioning are referring to table 1.Comparative example
In without any auxiliary agent, be also prepared according to above-mentioned specific preparation method.
The formula of the PVB resin powder of the embodiment of table 1 and comparative example
For the explanation of table 1：
(1) embodiment 1-3 is the PVA raw material for using, and PVA viscosity is controlled to 24-28mPas (testing standard GB/
T12010.2-2010), average degree of polymerization 1500-1800 (testing standard GB/T 12010.5-2010), alcoholysis degree 98-99%
(testing standard GB/T 12010.5-2010), market purchase is BF- for the trade mark of Changchun chemical industry (Jiangsu) Co., Ltd production
14, it is high to melt finger that infrared barrier resin PVB is synthesized, and melts finger at 5-8g/10min (140 DEG C, 21.6kg counterweights), and feature is
Processing good leveling property, curtain coating is easily formed 100-200 microns of uniform film.For preparing intermediate layer film.
(2) embodiment 4-6 is the PVA raw material for using, and PVA viscosity is 28-30mPas (test mark GB/T12010.2-
2010), average degree of polymerization 1700-2500 (testing standard GB/T 12010.5-2010), alcoholysis degree 98-99% (testing standards
GB/T 12010.5-2010), market purchase is BP-20 for the trade mark of Changchun chemical industry (Jiangsu) Co., Ltd production, and reaction is obtained
PVB features be melt finger it is relatively low, viscosity is high, and mechanical mechanics property is good, it is ensured that the security of doubling glass.For preparing bottom thin
Film.
Following performance test is carried out to the above-mentioned modified PVB resin powder for preparing.
(1) finger method of testing is melted：
1st, instrument：XNR-400GM type melt flow rate (MFR) analyzers, Changzhou De Tu precision instruments Co., Ltd.
2nd, method：By plasticizer：PVB powder material=1:3 ratio weighs corresponding 3G8 plasticizer and PVB powder material, past
It is accurate in the PVB resin powder of 3.75g that 1.25g plasticizer are added dropwise, it is uniformly mixing to obtain testing sample with glass bar.Wait XNR-
400GM type melt flow rate (MFR) analyzer barrels are warming up to 140 DEG C of setting value, and stabilization 10min extracts piston rod, plus treat test sample
Product.Piston rod compacting is reinserted, after 21.6kg counterweights are added after 4~6 minutes temperature stabilizations, when material bar drops to lower Marking ring
Start test when mutually neat with barrel, mono- sample of testing time 5min is weighed from the weight for melting the batten for referring to the outflow of tester membrana oralis
It is m1, m2, m3, m4, m5.
3 calculate：Melt finger=(m1+m2+m3+m4+m5) * 2/5 (unit：g/10min)
(2) chromatism test method：
1st, 2 pieces of ultra-clear glasses (thickness of wiped clean are taken：2mm is long：10cm 10cm wide).
2nd, the PVB resin powder of 3-5g is taken, is uniformly layered in the middle of 2 blocks of glass, be then placed within 180 DEG C of drying box constant temperature 10
Minute obtains test sample.Sample is cooled to room temperature and measures L1, a1, b1 using Agilent CARRY5000 color difference meters.
3rd, sample is put into constant temperature 2 hours in 180 DEG C of drying boxes, sample be cooled to room temperature using color difference meter measure L2, a2,
b2。
4th, value of chromatism is calculated：Aberration refers to represent that two kinds of colors give people the difference on color perception with the method for numerical value.
CIE1976 (or Lab) system, turned into now countries in the world formally adopt, as international colour examining standard.Modified PVB
180 DEG C of resin-oatmeal in drying box constant temperature before and after 2 hours sample all press L, a, b demarcate color, then 180 DEG C of constant temperature are before and after 2 hours
Total color difference △ Eab and every individual event aberration between the two can be calculated with following equation：
Luminosity equation：△ L=L1-L2 formulas (1)
Colour difference：△ a=a1-a2；△ b=b1-b2 formulas (2)
Total color difference：Formula (3)
(3) infrared barrier rate method of testing：Tested according to the sample preparations of GB GB/T 2680.
(4) percussion value method of testing：Tested according to professional standard JC/T2166-2013 sample preparations.
Specific test result is as follows：
The characteristic of the PVB resin powder of table 2
Be can be seen that from above-mentioned test result：Resin-oatmeal of the invention is by antioxidant, ultraviolet absorber, follow-up PVB glue
Can be without this analog assistant in piece process, it is to avoid breading operation, reduce powder pollution, the PVB resin that is modified powder resistance to ring
Border excellent performance, shows as modified PVB resin powder 180 DEG C of temperature constant temperature 2 hours chroma difference less than 1, and comparative example is not used
Antioxidant and modified 180 DEG C of the conventional PVB resin powder constant temperature 2 hours chroma difference of ultraviolet absorber are more than 1；Infrared heat-proof quality
Excellent, embodiment 1 and 3 is modified using nano-ITO, and infrared barrier rate is more than 20%；Embodiment 2 is modified using nanometer tungsten bronze,
Infrared barrier rate is more than 90%, and embodiment 4 and comparative example do not use nano-oxide to be modified, and infrared barrier rate is less than 10% water
It is flat；Caking property of the PVB films to glass is effectively controlled, by JC/T2166-2013 standards, embodiment of the present invention 1-6 is used
The modified PVB resin powder of surface tension modifier taps value stabilization in 5-6 grades of level to the adhesion strength index of glass, and contrasts
It is 7-9 grades to the adhesion strength index percussion value of glass that example 1-2 does not use the conventional PVB resin powder powder of surface tension modifier.
Embodiment 7
The modified PVB resin powder 72kg of Example 3, the common 28kg of plasticizer 3G8, are existed by 52 type double screw extruders
Plastified at a temperature of 160 DEG C, plasticizing resin imports three layers of middle B modules of mould；The modified PVB resin powder of Example 5
The common 28kg of 72kg, plasticizer 3G8, is plastified by 95 type double screw extruders at a temperature of 160 DEG C, and three layers of mould are imported after plasticizing
The upper and lower of tool.The PVB films with infrared barrier performance are obtained by three layers of mould film extrusion.
Product is carried out into sem analysis, and its infrared barrier effect is tested, it is as a result as follows：
From accompanying drawing 1 as can be seen that the intima-media thickness of the PVB films is 131 microns, upper strata is 375 microns, and lower floor is
437 microns.
From accompanying drawing 2 as can be seen that infrared barrier film has significantly relative to conventional film in wavelength 780-2500nm
Barriering effect, testing standard is GB/T2680, and glass structure is 2mm glass+0.76PVB film+2mm glass, wherein infrared resistance
It is 98% every the infrared barrier rate of the doubling glass of PVB films, sheltering coefficient is 0.63, it is seen that transmittance is 77%, it is seen that
Luminous reflectance is 8%；The infrared barrier rate of the doubling glass of conventional PVB films is 7%, and sheltering coefficient is 0.88, it is seen that light is saturating
Penetrate than being 92%, it is seen that luminous reflectance is 8%, learnt from infrared barrier rate and sheltering coefficient, infrared barrier PVB glue of the invention
Piece has excellent infrared interrupting performance.
Although by referring to the preferred embodiments of the present invention, invention has been described, this area it is common
It will be appreciated by the skilled person that various changes can be made to it in the form and details, without departing from appended right
The spirit and scope of the present invention that claim is limited.
Claims (7)
1. ultraviolet and ultrared PVB films can be intercepted simultaneously, it is characterised in that multiple by upper strata, middle level, lower film successively
It is combined into, middle level film thickness is 110-150 microns, the upper and lower film thickness is 150-450 microns；The middle layer film
By melting means for the modified PVB resin powder of 5-8g/10min is prepared, the upper and lower thin-film material is 3-4g/ by melting means to material
The modified PVB resin powder of 10min is prepared.
2. it is according to claim 1 simultaneously to intercept ultraviolet and ultrared PVB films, it is characterised in that described
Upper, middle and lower-ranking film resin formula is 28% including modified PVB resin powder that mass percent is 72% and mass percent
Plasticizer 3G8.
3. it is according to claim 1 simultaneously to intercept ultraviolet and ultrared PVB films, it is characterised in that described
The component and mass percent of modified PVB resin powder be：
Polyvinyl alcohol：9-10wt%
N-butanol：6-7wt%
Antioxidant：0.01-0.03wt%
Ultraviolet absorber：0.01-0.02wt%
Nano-oxide：0.01-0.02%wt
Surface tension modifier：0-0.01wt%
Hydrochloric acid：2-3wt%
Balance of water.
4. it is according to claim 3 simultaneously to intercept ultraviolet and ultrared PVB films, it is characterised in that described anti-
Oxygen agent is selected from the mixture of phenols and phosphorous acid esters, wherein described phenols is selected from four (3,5- di-t-butyl -4- hydroxyls) benzene
Propionate, 2- di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenols), β-(3,5- di-tert-butyl-hydroxy phenyls) third
One kind in sour positive octadecanol ester；Described phosphorous acid esters are selected from three (2,4- di-t-butyls) phenyl-phosphites, double 18
Alkylol season penta diphosphites, the one kind in double (3,5- di-tert-butyl-phenyl) pentaerythritol diphosphites；Described purple
Outer light absorber is Benzotriazole Ultraviolet Stabilizer, selected from 2- (the 2 ˊ-ˊ of hydroxyl-5-methyl)-BTA, 2- (2 ˊ-hydroxyl
The ˊ of base-3-ˊ of the tert-butyl group-5-methyl) the chloro- BTAs of-5-, 2- (2 ˊ-5 ˊ of the ˊ of hydroxyl-3-di-t-butyl) chloro- BTAs of-5-,
2'- (the 2'- hydroxyl-3'- tert-butyl group-5'- aminomethyl phenyls)-5- chlorobenzotriazoles, 2- (the 2 ˊ-ˊ of hydroxyl-5-t-octyl)-benzo three
It is a kind of in azoles；The surface tension modifier is inorganic salts, selected from potassium acetate, potassium formate, magnesium acetate, calcium acetate, sodium acetate
In one kind；The nano-oxide is the one kind in nano-ITO, nano ATO, nanometer GTO, nanometer tungsten bronze；More preferably
Nanometer tungsten bronze；The mass concentration of the hydrochloric acid is 31%；The resistivity of the pure water >=18M Ω .CM.
5. it is according to claim 3 simultaneously to intercept ultraviolet and ultrared PVB films, it is characterised in that when used for
When preparing the middle layer film that can simultaneously intercept ultraviolet and ultrared PVB films, raw material PVA viscosity is controlled to 24-
28mPas, average degree of polymerization 1500-1800, alcoholysis degree 98-99%；Ultraviolet and infrared ray can be simultaneously intercepted when used for preparing
PVB films the upper and lower film when, raw material PVA viscosity be 28-30mPas, average degree of polymerization 1700-2500, alcohol
Solution degree 98-99%.
6. it is according to claim 3 simultaneously to intercept ultraviolet and ultrared PVB films, it is characterised in that described to change
Property PVB resin powder preparation method be, by from raw material PVB resin powder building-up process add antioxidant, ultraviolet absorber,
Surface tension modifier, nano-oxide.
7. it is according to claim 6 simultaneously to intercept ultraviolet and ultrared PVB films, it is characterised in that described to change
The preparation method of property PVB resin powder is：
(1) condensation reaction
First, solution of the concentration less than 10% is made into 90-95 DEG C of water and appropriate polyvinyl alcohol, the solution is cooled to
After 40-45 DEG C, add hutanal, and by proportioning antioxidant, ultraviolet absorber, nano-oxide, surface tension modifier,
Stirring 1-3h；After reaction mixture is cooled to 20-25 DEG C, the appropriate hydrochloric acid of addition, insulation reaction at least 1-5 hours, then will be anti-
Answer mixed liquor to be delivered to condensation reaction kettle, 40 DEG C, then insulation reaction 1-2 hours were gradually heating at 1 hour, afterwards again with 1
Hour is gradually heating to 55 DEG C, then insulation reaction 1-2 hours, then cools to room temperature；
(2) neutralisation treatment
Reaction solution after the cooling is delivered into washing kettle to wash 5-6 times, 51-65 DEG C is warming up to afterwards, add appropriate caustic soda
Solution adjusts pH value to 8-10, then is incubated 2-3 hours, fully neutralizes deacidification；
(3) it is dehydrated and dries
15% is less than to moisture content after centrifuge dewatering after washing 6-8 times again to the reaction solution neutralized after deacidification, with
Air-flow enters the i.e. prepared modified PVB resin powder after cyclone dryer is dried.
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