CN109627997A - A kind of low haze polyolefin adhesive film and preparation method thereof - Google Patents

A kind of low haze polyolefin adhesive film and preparation method thereof Download PDF

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Publication number
CN109627997A
CN109627997A CN201811566624.4A CN201811566624A CN109627997A CN 109627997 A CN109627997 A CN 109627997A CN 201811566624 A CN201811566624 A CN 201811566624A CN 109627997 A CN109627997 A CN 109627997A
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parts
adhesive film
nano
low haze
polyolefin adhesive
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罗吉江
符书臻
崔如玉
花超
朱瑜芳
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New Materials Co Ltdsuzhou Duchamps
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New Materials Co Ltdsuzhou Duchamps
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
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  • Joining Of Glass To Other Materials (AREA)

Abstract

The invention discloses a kind of low haze polyolefin adhesive films, including following component: grafted polyethylene resin, master batch, polyolefin resin, auxiliary agent, wherein the master batch includes following component: polyolefin resin, nano-metal-oxide, nano silica, oleic acid, dispersing agent, silane coupling agent, wherein the partial size of nano-metal-oxide is less than 80 nm；The partial size of nano silica is less than 30 nm.The present invention by being added to nano-metal-oxide and nano silica simultaneously in master batch, and nano silica partial size is much smaller than nano-metal-oxide, close cladding can be formed on its surface, the surface for reducing metal oxide can, dispersibility is improved, and good dispersibility facilitates the reduction of its mist degree and improves heat-proof quality.

Description

A kind of low haze polyolefin adhesive film and preparation method thereof
Technical field
The invention belongs to glass film and its preparation field, in particular to a kind of low haze polyolefin adhesive film and its preparation side Method.
Background technique
Laminated glass be by two panels or divided glass, between pressed from both sides one or more layers organic polymer intermediate coat, by spy After different high temperature precompressed (or vacuumizing) and high-temperature high-pressure craft processing, it is integrated glass and intermediate coat permanent adhesive compound Glass product.Even if this glass fragmentation in use, fragment can be also bonded on film, so that broken glass surface is still protected It holds clean and tidy smooth.As a kind of current optimal safety glass, laminated glass be widely used in the vehicles, building with And the fields such as public place.
Wherein, polymer intermediate coat (also known as laminated glass intermediate coat) is the most important of decision laminated glass security performance Component, light transmission, with glassy bond performance, mechanical property, flexibility, in terms of all have strict requirements. Currently, laminated glass intermediate coat mainly includes polyvinyl butyral (PVB) glue film, ethylene-vinyl acetate copolymer (EVA) glue Film and ionic intermediate coat (SGP glue film) three classes.Wherein PVB glue film has high light transmittance, caking property and weatherability, has simultaneously Excellent mechanical property and impact resistance is most widely used laminated glass intermediate coat, occupies 95% or more the market share. The high-grade PVB resin powder country currently used for preparing PVB glue film can not produce, and almost rely on import, therefore PVB glue film price entirely It is expensive.EVA adhesive film translucency is high, cheap, but mechanical property is poor, and contains acetic acid group in molecule, and weatherability is bad, It is only used for production ambetti and low-grade building safety glass.SGP glue film has good translucency, caking property and weather-proof Property, while there is high intensity and modulus of shearing, it is ideal building safety middle membrane of glass, but such glue film is global at present only A company, Du Pont can produce, and the price is very expensive, be only applied to the glass curtain wall of high performance requirements at present.
Therefore, it develops a kind of moderate and has excellent performance (good mechanical performance, lower temperature resistance and good weatherability, ground fog Degree) laminated glass intermediate coat, at the first-class problem of China's laminated glass industry.
On the other hand, the polyethylene as one of five big general-purpose plastics, yield and consumption figure occupy various synthetic resin it It is first.Polyethylene transparency is good, more soft, but its high temperature resistance is poor, and mechanical property and chemical-resistance are also very limited. For example, Chinese invention patent application CN201410502588.0 discloses a kind of POE laminated glass intermediate coat, POE resin is connect Branch silane coupling agent, crosslinking is generated between silane coupling agent, so that glue film is formed network, is improved the adhesive property of glue film, machine Tool intensity and mechanical property；It can be adapted for the variety classes interlayer glass such as windshield, building safety glass, ambetti Glass application.However, actual experiment finds that the thickness of this laminated glass intermediate coat is larger (generally all in 0.75mm or so), thoroughly Light rate is poor, and mist degree is higher；And tensile strength is poor, low temperature impact strength is poor.
Therefore, the performance of glue film how is further increased on the basis of existing technology, especially how to be reduced mist degree, is improved Tensile strength and low temperature impact strength, and still maintain lower cost, it is clear that there is positive realistic meaning.
Summary of the invention
Goal of the invention of the invention is to provide a kind of low haze polyolefin adhesive film and preparation method thereof.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: a kind of low haze polyolefin adhesive film, with quality Part meter, including following component:
Wherein:
The grafted polyethylene resin is made by the following method: 0.2-0.5 parts of initiators are dissolved in 0.05-2.0 parts In crosslinking agent, 100 parts of polyvinyl resins are stirring evenly and then adding into, melting extrusion granulation is carried out after mixing evenly, can be obtained and connect Branch polyvinyl resin；
The polyolefin resin is selected from one or more of polyethylene, polypropylene, ethylene-alpha-olefin copolymer；
The auxiliary agent includes antioxidant and light stabilizer；
The master batch, in terms of mass parts, including following component:
Wherein, the nano-metal-oxide is selected from WO3、ZnO、TiO2And Al2O3One or more of, the nanometer The partial size of metal oxide is less than 80nm；The partial size of the nano silica is less than 30nm；The polyolefin resin is selected from poly- One or more of ethylene, polypropylene, ethylene-alpha-olefin copolymer.
Above, the low haze polyolefin adhesive film with a thickness of 0.3-0.6mm, preferably 0.4-0.55mm, more preferably For 0.50mm.
Above, the grafted polyethylene resin is made by the following method: 0.2-0.5 parts of initiators are dissolved in In 0.05-2.0 parts of crosslinking agents, 100 parts of polyvinyl resins are stirring evenly and then adding into, stirs in machine in height and is stirred with 600 revs/min of speed It is put into after mixing 30 minutes and carries out melting extrusion granulation in double screw extruder, obtain grafted polyethylene resin.
Above, the grafted polyethylene resin can be 71 parts, 72 parts, 75 parts, 80 parts, 85 parts, 86 parts, 87 parts, 88 Part, 89 parts.
The master batch can be 3 parts, 4 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts.
The polyolefin resin can be 11 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 26 parts, 27 parts, 28 Part, 29 parts.
The master batch, in terms of mass parts, including following component:
Wherein, the nano-metal-oxide can be 25 parts, 30 parts, 35 parts, 40 parts, 50 parts, 60 parts, 70 parts, 75 parts, 76 Part, 77 parts, 78 parts, 79 parts.The nano silica can be 35 parts, 40 parts, 50 parts, 60 parts, 70 parts, 75 parts, 80 parts, 85 Part, 88 parts, 89 parts.
The partial size of the nano-metal-oxide is less than 80nm；Preferably, the partial size of nano-metal-oxide is less than 70nm； It is furthermore preferred that the partial size of nano-metal-oxide is less than 60nm.
The partial size of the nano silica is less than 30nm；Preferably, the partial size of nano silica is less than 20nm；It is more excellent Choosing, the partial size of nano silica is less than 15nm.
In above-mentioned technical proposal, the crosslinking agent is vinyltrimethoxysilane or vinyltriethoxysilane.Institute Stating initiator is organic peroxide.
In above-mentioned technical proposal, the dispersing agent is selected from polyacrylamide, sodium silicate nanahydrate, Sodium Polyacrylate, tristearin One or more of sour sodium, calcium stearate, sodium tripolyphosphate, calgon and sodium pyrophosphate.
Preferably, the dispersing agent is the polyacrylamide and sodium silicate nanahydrate that mass ratio is 1:2, and order of addition Are as follows: sodium silicate nanahydrate is added after first adding polyacrylamide.
In above-mentioned technical proposal, the silane coupling agent is selected from γ-glycidoxypropyltrimewasxysilane, ethylene Base trimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl triacetyl oxygen Base silane, γ-one or more of r-chloropropyl trimethoxyl silane and γ-mercaptopropyl trimethoxysilane.
In above-mentioned technical proposal, the antioxidant is selected from four [β-(3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid] ten Eight alkyl alcohol esters, double octadecyl pentaerythritol diphosphites, three (2,4- di-tert-butyl-phenyl) phosphite esters, β-(4- hydroxyl One or more of base -3,5- di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester.
In above-mentioned technical proposal, the light stabilizer be selected from it is poly- [6- [(1,1,3,3- tetramethyl butyl) amino]] -1,3, Oneself two support-[(2,2,6,6- tetramethyl -4- of bis- [(2,2,6,6,-tetramethyl-4-piperidyl) the imino group] -1,6- of 5- triazine -2,4- Piperidyl) imino group] with the compound of poly-succinic (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine ethanol) ester, it is bis- (2,2, 6,6- tetramethyl -4- piperidyl) sebacate, succinic acid and (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine alcohols) polymer And one or more of 2,2,6,6- tetramethyl -4- piperidines stearate.
In above-mentioned technical proposal, master batch is first prepared, then prepares low haze polyolefin adhesive film according to the proportion；
The master batch the preparation method is as follows:
(1) nano-metal-oxide is added in dispersing agent, after being uniformly dispersed, is concentrated and dried, is ground up, sieved, screens partial size Powder less than 80nm, is then uniformly mixed with oleic acid, obtains the nanometer metal oxide powder of oleic acid processing；
(2) nano silica is added in dispersing agent and is surface-treated, after being uniformly dispersed, is concentrated and dried；It is ground Sieve, screening partial size are the nano silica powder less than 20nm；
(3) above-mentioned oleic acid is handled into obtain nanometer metal oxide powder, nano silica powder, silane coupling agent mixing Uniformly, polyolefin resin is then added, after being uniformly mixed, extruder is added and carries out reactive extrursion, is cooled down, is made after extrusion Grain, can be obtained master batch.
In the step (3), the extruder uses screw extruder, and temperature range is 120-160 DEG C, screw speed For 160-240rpm.
The present invention is claimed a kind of using laminated glass made from above-mentioned low haze polyolefin adhesive film simultaneously.
A kind of preparation method of low haze polyolefin adhesive film, includes the following steps:
(1) preparation of grafted polyethylene resin:
0.2-0.5 parts of initiators are dissolved in 0.05-2.0 parts of crosslinking agents, 100 parts of polyethylene trees are stirring evenly and then adding into Rouge carries out melting extrusion granulation after mixing evenly, grafted polyethylene resin can be obtained；
(2) preparation of master batch
(a) nano-metal-oxide is added in dispersing agent, after being uniformly dispersed, is concentrated and dried, is ground up, sieved, screens partial size Powder less than 80nm, is then uniformly mixed with oleic acid, obtains the nanometer metal oxide powder of oleic acid processing；
(b) nano silica is added in dispersing agent and is surface-treated, after being uniformly dispersed, is concentrated and dried；It is ground Sieve, screening partial size are the nano silica powder less than 20nm；
(c) nanometer metal oxide powder, the nano silica powder, silane coupling agent mixing handled above-mentioned oleic acid Uniformly, polyolefin resin is then added, after being uniformly mixed, extruder is added and carries out reactive extrursion, is cooled down, is made after extrusion Grain, can be obtained master batch；
(3) preparation of low haze polyolefin adhesive film:
Grafted polyethylene resin, polyolefin resin, master batch, auxiliary agent are uniformly mixed according to the ratio, single screw rod is then added and squeezes Reactive extrursion is carried out in machine out, finally by extrusion, curtain coating, cooling, is cut, winding process, it is poly- that the low haze can be obtained Alkene glue film.
In the step (3), the temperature range for controlling screw extruder is 160-185 DEG C, screw speed 200- 300rpm。
Mechanism of the invention is as follows: first preparing master batch, and is added to nano-metal-oxide and dioxy simultaneously in master batch SiClx, due to nano-metal-oxide surface be cut off chemical bond be ionic bond or highly polar key, easily with the very strong water of polarity Molecule combines, and most metal oxide powder surfaces are accompanying by polar group (as-OH), it is easy to because of polarity absorption or The moisture absorption and generate agglomeration, be not easy to disperse；And nano silica partial size is much smaller than nano-metal-oxide, it can be in its table Face forms close cladding, reduces the surface energy of metal oxide, improves dispersibility, and good dispersibility facilitates its mist degree Reduce and improve heat-proof quality；In addition, nano silica stable physical property, partial size are small, and large specific surface area, surface hydroxyl Base content is high, and contains a large amount of Si=O unsaturated bond, can react with silane coupling agent etc., form three-dimensional net structure, Improve adhesive strength and tensile strength.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1. the present invention develops a kind of new low haze polyolefin adhesive film, by being added to nano metal simultaneously in master batch Oxide and nano silica, and nano silica partial size is much smaller than nano-metal-oxide, can be formed on its surface Close cladding, reduce metal oxide surface can, improve dispersibility, and good dispersibility facilitate its mist degree reduction, And improve heat-proof quality；Experiment also indicates that: with the prior art (POE of Chinese invention patent application CN201410502588.0 Laminated glass intermediate coat) it compares, low haze polyolefin adhesive film of the invention has lower mist degree and excellent light transmittance, and draws It stretches intensity and low temperature impact strength also greatly promotes, achieve significant effect；
2. then master batch is mixed system with grafted polyethylene resin and polyolefin resin again by first preparing master batch by the present invention Standby low haze polyolefin adhesive film, has not only given full play to the excellent in performance of grafted polyethylene resin, has reduced costs, and master batch The whole low haze polyolefin adhesive film that is modified as provide superior performance, especially there is lower mist degree and excellent Tensile strength and low temperature impact strength, thus can be completely applied to the vehicles, high-end building and public place etc. Field；
3. the preparation method of low haze polyolefin adhesive film of the invention is simple, and cost is relatively low, is suitable for popularization and application.
Specific embodiment
Embodiment 1
A kind of low haze polyolefin adhesive film, film thickness 0.50mm；Preparation method is as follows:
(1) preparation of grafted polyethylene resin:
It is 3:1's that 0.25 part of cumyl peroxide (DCP) (Nanjing You Pu Chemical Co., Ltd.), which is dissolved in 1 part of ratio, (the excellent general chemical industry in Nanjing is limited with vinyltriethoxysilane for vinyltrimethoxysilane (Nanjing You Pu Chemical Co., Ltd.) Company) in mixture, being stirring evenly and then adding into 100 parts of linear low molecular weight polyethylene, (Yangtze petro-chemical corporation, density are 0.921g/cm3, the melt flow rate (MFR) of 190 DEG C/2.16kg is 2g/10min), it stirs in machine in height and is stirred with 500 revs/min of speed It is put into after mixing 30 minutes and carries out melting extrusion granulation in double screw extruder, obtain grafted polyethylene resin；
(2) preparation of master batch:
Polyacrylamide and sodium silicate nanahydrate are successively added in deionized water and configure enough aqueous dispersants, The mass concentration of middle polyacrylamide is 10%, and the mass concentration of sodium silicate nanahydrate is 20%；
Then 50 parts of nano-oxide WO3It is added in 100 parts of aqueous dispersants after high speed grinding, ultrasonic disperse is equal It after even, is concentrated and dried, and crushed and be sieved with micron ultra shifter, the powder that screening partial size is 50-80nm, by powder and 6 parts Oleic acid is uniformly mixed, and obtains the WO of oleic acid processing3Nanometer powder；
30 parts of nano silicas (Carter new material Co., Ltd is protected in Nanjing) are added in 20 parts of aqueous dispersants, are surpassed After sound is uniformly dispersed, it is concentrated and dried, is crushed and be sieved with micron ultra shifter, the nano oxidized silicon powder that screening partial size is 5-20nm Body；
Then the WO above-mentioned oleic acid handled3Powder, nano silica powder, 5 parts of vinyltrimethoxysilanes are added Height stirs machine, after mixing evenly, 100 parts of low molecular weight polyethylenes is added, and stirs machine with height and is uniformly mixed, and material addition twin-screw is squeezed Reactive extrursion is carried out in machine out, screw extruder temperature is 150 DEG C, screw speed 200rpm, squeezes out cooling granulation and obtains institute Need master batch；
(3) preparation of low haze polyolefin adhesive film:
By 60 parts of grafted polyethylene resins, 5 parts of master batches, 10 parts of linear low molecular weight polyethylene, 30 parts of random copolymerizations poly- third The double octadecyl pentaerythritol diphosphites of alkene, 1.0 parts of antioxidant, 1.0 parts of light stabilizer succinic acid with (hydroxyl -2,2 4-, 6,6- tetramethyl -1- piperidine alcohols) polymer height be added stir in machine and be uniformly mixed, then material carried out in screw extruder instead It should squeeze out, control screw extruder temperature is 180 DEG C, screw speed 250rpm, finally by extrusion, curtain coating, cooling, sanction It cuts, winding process, low haze polyolefin adhesive film S1 can be obtained.
Laminated glass is prepared, it is specific as follows: above-mentioned low haze polyolefin adhesive film S1 to be placed among two blocks of glass, after precompressed At 120 DEG C, pressurization discharge interlayer bubble in the autoclave under the conditions of 13.5Mpa, two sheet glass of bonding obtain laminated glass.
Embodiment 2
A kind of low haze polyolefin adhesive film, film thickness 0.50mm；Preparation method is as follows:
(1) preparation of grafted polyethylene resin: process is same as Example 1；
(2) preparation of master batch: process is same as Example 1；
(3) preparation of low haze polyolefin adhesive film:
By 90 parts of grafted polyethylene resins, 5 parts of master batches, 10 parts of linear low molecular weight polyethylene, 1.0 parts of antioxidant double 18 Alkyl pentaerythritol diphosphites, 1.0 parts of light stabilizer succinic acid and (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine alcohols) Polymer height be added stir in machine and be uniformly mixed, then material is subjected to reactive extrursion in screw extruder, controls Screw Extrusion Machine temperature is 180 DEG C, screw speed 250rpm, finally by extrusion, curtain coating, cooling, cuts, winding process, can be obtained Low haze polyolefin adhesive film S2.
Laminated glass is prepared, it is specific as follows: above-mentioned low haze polyolefin adhesive film S2 to be placed among two blocks of glass, after precompressed At 120 DEG C, pressurization discharge interlayer bubble in the autoclave under the conditions of 13.5Mpa, two sheet glass of bonding obtain laminated glass.
Embodiment 3
A kind of low haze polyolefin adhesive film, film thickness 0.50mm；Preparation method is as follows:
(1) preparation of grafted polyethylene resin: process is same as Example 1；
(2) preparation of master batch:
Polyacrylamide and sodium silicate nanahydrate are successively added in deionized water and configure enough aqueous dispersants, The mass concentration of middle polyacrylamide is 10%, and the mass concentration of sodium silicate nanahydrate is 20%；
Then 50 parts of nano-oxide Al2O3It is added in 100 parts of aqueous dispersants after high speed grinding, ultrasonic disperse It after uniformly, is concentrated and dried, and crushed and be sieved with micron ultra shifter, the powder that screening partial size is 50-80nm, by powder and 6 Part oleic acid is uniformly mixed, and obtains the Al of oleic acid processing2O3Nanometer powder；
30 parts of nano silicas (Carter new material Co., Ltd is protected in Nanjing) are added in 20 parts of aqueous dispersants, are surpassed After sound is uniformly dispersed, it is concentrated and dried, is crushed and be sieved with micron ultra shifter, the nano oxidized silicon powder that screening partial size is 5-20nm Body,
Then the Al above-mentioned oleic acid handled2O3Nanometer powder, nano silica powder, 5 parts of vinyltrimethoxysilanes Height is added and stirs machine, after mixing evenly, 100 parts of block copolymerization polypropylenes (Shanghai match section, density 0.90g/cm is added3, 190 DEG C/melt flow rate (MFR) of 2.16kg is 2.5g/10min), machine is stirred with height and is uniformly mixed, and double screw extruder is added in material Middle carry out reactive extrursion, screw extruder temperature are 150 DEG C, screw speed 200rpm, squeeze out cooling granulation and obtain required mother Grain；
(3) preparation of low haze polyolefin adhesive film:
By 70 parts of grafted polyethylene resins, 10 parts of master batches, 20 parts of block copolymerization polypropylenes, the double octadecanes of 0.8 part of antioxidant Base pentaerythritol diphosphites, 1.2 parts of light stabilizer succinic acid and (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine alcohols) Polymer addition height, which stirs in machine, to be uniformly mixed, then material is carried out reactive extrursion in screw extruder, controls screw extruder Temperature is 180 DEG C, screw speed 250rpm, finally by extrusion, curtain coating, cooling, cuts, winding process, can be obtained low Mist degree polyolefin adhesive film S3.
Laminated glass is prepared, it is specific as follows: above-mentioned low haze polyolefin adhesive film S3 to be placed among two blocks of glass, after precompressed At 120 DEG C, pressurization discharge interlayer bubble in the autoclave under the conditions of 13.5Mpa, two sheet glass of bonding obtain laminated glass.
Embodiment 4
It is identical as material used in Example 1 and preparation method, only difference is that: it is controlled when film extrusion thin Film thickness is 0.30mm；The subsequent laminated glass process for preparing is the same as embodiment 1.
Embodiment 5
It is identical as material used in Example 1 and preparation method, only difference is that: it is controlled when film extrusion thin Film thickness is 0.45mm.The subsequent laminated glass process for preparing is the same as embodiment 1.
Embodiment 6
It is identical as material used in Example 1 and preparation method, only difference is that: control screw extruder 150 DEG C of temperature.The subsequent laminated glass process for preparing is the same as embodiment 1.
Embodiment 7
It is identical as material used in Example 1 and preparation method, only difference is that: control screw extruder 170 DEG C of temperature.The subsequent laminated glass process for preparing is the same as embodiment 1.
Comparative example 1
A kind of polyolefin adhesive film, film thickness 0.50mm；Preparation method is as follows:
(1) preparation of master batch
Polyacrylamide and sodium silicate nanahydrate are successively added in deionized water and configure enough aqueous dispersants, The mass concentration of middle polyacrylamide is 10%, and the mass concentration of sodium silicate nanahydrate is 20%；
Then 50 parts of nano-oxide WO3It is added in 100 parts of aqueous dispersants after high speed grinding, ultrasonic disperse is equal It after even, is concentrated and dried, and crushed and be sieved with micron ultra shifter, the powder that screening partial size is 50-80nm, by powder and 6 parts Oleic acid is uniformly mixed, and obtains the WO of oleic acid processing3Nanometer powder；
30 parts of nano silicas (Carter new material Co., Ltd is protected in Nanjing) are added in 20 parts of aqueous dispersants, are surpassed After sound is uniformly dispersed, it is concentrated and dried, is crushed and be sieved with micron ultra shifter, the nano oxidized silicon powder that screening partial size is 5-20nm Body；
By above-mentioned nano silica powder, the WO of above-mentioned oleic acid processing3Powder, 5 parts of vinyltrimethoxysilanes are added Height stirs machine, after mixing evenly, 100 parts of low molecular weight polyethylenes is added, and stirs machine with height and is uniformly mixed, and material addition twin-screw is squeezed Reactive extrursion is carried out in machine out, screw extruder temperature is 150 DEG C, screw speed 200rpm, squeezes out cooling granulation and obtains institute Need master batch；
(3) preparation of laminated glass intermediate coat:
By 90 parts of linear low molecular weight polyethylene, 10 parts of master batches, double two phosphorous of octadecyl pentaerythrite of 1.0 parts of antioxidant The polymer of acid esters, 1.0 parts of light stabilizer succinic acid and (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine alcohols) is added height and stirs machine In be uniformly mixed, then material is subjected to reactive extrursion in screw extruder, control screw extruder temperature is 180 DEG C, screw rod Revolving speed is 250rpm, finally by extrusion, curtain coating, cooling, is cut, winding process, and laminated glass intermediate coat A1 can be obtained.
Prepare laminated glass, it is specific as follows: above-mentioned laminated glass intermediate coat A1 is placed among two blocks of glass, after precompressed 120 DEG C, pressurization discharge interlayer bubble in the autoclave under the conditions of 13.5Mpa, two sheet glass of bonding obtain laminated glass.
Comparative example 2
A kind of laminated glass intermediate coat, film thickness 0.50mm；Preparation method is as follows:
(1) preparation of grafted polyethylene resin: process is identical as comparative example 1；
(2) preparation of laminated glass intermediate coat:
By 70 parts of grafted polyolefin resins, 10 parts of nano-oxide WO3, 20 parts of linear low molecular weight polyethylene, 1.0 parts it is anti- The double octadecyl pentaerythritol diphosphites of oxygen agent, 1.0 parts of light stabilizer succinic acid and (4- hydroxyl -2,2,6,6- tetramethyl - 1- piperidine alcohols) polymer height be added stir in machine and be uniformly mixed, then material is subjected to reactive extrursion in screw extruder, controlled Screw extruder temperature is 180 DEG C, screw speed 250rpm, finally by extrusion, curtain coating, cooling, is cut, winding process, Laminated glass intermediate coat A2 can be obtained.
Prepare laminated glass, it is specific as follows: above-mentioned laminated glass intermediate coat A2 is placed among two blocks of glass, after precompressed 120 DEG C, pressurization discharge interlayer bubble in the autoclave under the conditions of 13.5Mpa, two sheet glass of bonding obtain laminated glass.
Comparative example 3
A kind of laminated glass intermediate coat, with reference to Chinese invention patent application CN201410502588.0 disclosed embodiment 1 Content prepared, film with a thickness of 0.78mm.
Above-described embodiment and comparative example are tested for the property, the specific method is as follows:
(1) light transmittance test is according to examination as defined in GB2680-1994 " test methods such as building glass transmission of visible light " Test operating method progress；
(2) mist degree test is according to test as defined in GB5137.2-2002 " automotive safety glass optical property test method " Operating method carries out；
(3) peel strength, test is according to examination as defined in GB/T2792 " 180 ° of peeling strength test methods of pressure-sensitive tape " Test operating method progress；
(4) tensile strength test according to GB/T1040.3-2006 " measurement of plastic tensile performance " third portion: film and Experimental working technique as defined in the experimental condition of thin slice carries out；
(5) elongation at break is according to ASTM D638 standard testing；
(6) shrinking percentage test is according to experimental working technique as defined in GB/T 13541 " electrically using plastic film test method " It carries out；
(7) low temperature impact strength test is carried out according to GB/T2423.1-2008 " electric and electronic product environmental test "；
(8) hydrothermal aging test is carried out according to GB/T7141-2008 " plastics thermal aging test method " prescriptive procedure, test Condition is respectively as follows: 80 DEG C of temperature, relative humidity 80%, time 100h；- 40 DEG C of temperature, time 100h.
Test result is referring to following table:
As seen from the above table, the excellent combination property of embodiment 1-7 not only has low haze and high transparency, but also stretches Intensity and low temperature impact strength are also very high, and adhesion strength is also very high, illustrate that it can be advantageously applied to laminated glass Among；Compared to comparative example 1 (not adding grafted polyethylene resin), embodiment is in mist degree, high transparency, tensile strength, low temperature Impact strength and heat ageing etc. all have the promotion increased；Compared to comparative example 2 (not adding master batch), embodiment exists There is great improvement in terms of mist degree and light transmittance；Compared to comparative example 3, the present invention not only greatly reduces thicknesses of layers, Er Qie Mist degree, high transparency, tensile strength, low temperature impact strength etc. all have the promotion increased.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest scope of cause.

Claims (10)

1. a kind of low haze polyolefin adhesive film, it is characterised in that: in terms of mass parts, including following component:
Wherein:
The grafted polyethylene resin is made by the following method: 0.2-0.5 parts of initiators are dissolved in 0.05-2.0 parts of crosslinkings In agent, 100 parts of polyvinyl resins are stirring evenly and then adding into, carry out melting extrusion granulation after mixing evenly, it is poly- that grafting can be obtained Vinyl；
The polyolefin resin is selected from one or more of polyethylene, polypropylene, ethylene-alpha-olefin copolymer；
The auxiliary agent includes antioxidant and light stabilizer；
The master batch, in terms of mass parts, including following component:
Wherein, the nano-metal-oxide is selected from WO3、ZnO、TiO2And Al2O3One or more of, the nano metal oxygen The partial size of compound is less than 80nm；The partial size of the nano silica is less than 30nm；The polyolefin resin is selected from polyethylene, gathers One or more of propylene, ethylene-alpha-olefin copolymer.
2. low haze polyolefin adhesive film according to claim 1, it is characterised in that: the crosslinking agent is vinyl trimethoxy Base silane or vinyltriethoxysilane.
3. low haze polyolefin adhesive film according to claim 1, it is characterised in that: the dispersing agent is selected from polyacrylamide Amine, sodium silicate nanahydrate, Sodium Polyacrylate, odium stearate, calcium stearate, sodium tripolyphosphate, calgon and sodium pyrophosphate One or more of.
4. low haze polyolefin adhesive film according to claim 3, it is characterised in that: the dispersing agent is that mass ratio is 1:2 Polyacrylamide and sodium silicate nanahydrate, and order of addition are as follows: add sodium silicate nanahydrate after first adding polyacrylamide.
5. low haze polyolefin adhesive film according to claim 1, it is characterised in that: the silane coupling agent is selected from γ-contracting Water glycerol oxygroup propyl trimethoxy silicane, vinyltrimethoxysilane, vinyltriethoxysilane, three (β-of vinyl Methoxy ethoxy) silane, vinyltriacetoxy silane, γ-r-chloropropyl trimethoxyl silane and γ-mercapto propyl trimethoxy One or more of base silane.
6. low haze polyolefin adhesive film according to claim 1, it is characterised in that: the antioxidant be selected from four [β-(3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid] octadecyl alcohol ester, double octadecyl pentaerythritol diphosphites, three (2, 4- di-tert-butyl-phenyl) phosphite ester, one of β-(4- hydroxyl -3,5- di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester or It is several.
7. low haze polyolefin adhesive film according to claim 1, it is characterised in that: the light stabilizer is selected from poly- { [6- [(1,1,3,3- tetramethyl butyl) amino]] bis- [(2,2,6,6,-tetramethyl-4-piperidyl) imido of -1,3,5- triazine -2,4- Base] -1,6- oneself two support-[(2,2,6,6- tetramethyl -4- piperidyl) imino groups] with poly-succinic (4- hydroxyl -2,2,6,6- four Methyl-1-piperidine ethanol) compound of ester, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, succinic acid and (4- hydroxyl Base -2,2,6,6- tetramethyl -1- piperidine alcohols) polymer and one of 2,2,6,6- tetramethyl -4- piperidines stearate Or it is several.
8. low haze polyolefin adhesive film according to claim 1, it is characterised in that: first prepare master batch, then according to the proportion Prepare low haze polyolefin adhesive film；
The master batch the preparation method is as follows:
(1) nano-metal-oxide is added in dispersing agent, after being uniformly dispersed, is concentrated and dried, is ground up, sieved, screening partial size is less than The powder of 80nm, is then uniformly mixed with oleic acid, obtains the nanometer metal oxide powder of oleic acid processing；
(2) nano silica is added in dispersing agent and is surface-treated, after being uniformly dispersed, is concentrated and dried；It is ground up, sieved, sieves Selecting partial size is the nano silica powder less than 20nm；
(3) nanometer metal oxide powder, nano silica powder, the silane coupling agent handled above-mentioned oleic acid mixes equal It is even, polyolefin resin is then added, after being uniformly mixed, extruder is added and carries out reactive extrursion, is cooled down, is made after extrusion Grain, can be obtained master batch.
9. using laminated glass made from any one low haze polyolefin adhesive film in claim 1 to 8.
10. a kind of preparation method of low haze polyolefin adhesive film, which comprises the steps of:
(1) preparation of grafted polyethylene resin:
0.2-0.5 parts of initiators are dissolved in 0.05-2.0 parts of crosslinking agents, 100 parts of polyvinyl resins are stirring evenly and then adding into, Melting extrusion granulation is carried out after mixing evenly, and grafted polyethylene resin can be obtained；
(2) preparation of master batch
(a) nano-metal-oxide is added in dispersing agent, after being uniformly dispersed, is concentrated and dried, is ground up, sieved, screening partial size is less than The powder of 80nm, is then uniformly mixed with oleic acid, obtains the nanometer metal oxide powder of oleic acid processing；
(b) nano silica is added in dispersing agent and is surface-treated, after being uniformly dispersed, is concentrated and dried；It is ground up, sieved, sieves Selecting partial size is the nano silica powder less than 20nm；
(c) by above-mentioned oleic acid handle nanometer metal oxide powder, nano silica powder, silane coupling agent mix it is equal It is even, polyolefin resin is then added, after being uniformly mixed, extruder is added and carries out reactive extrursion, is cooled down, is made after extrusion Grain, can be obtained master batch；
(3) preparation of low haze polyolefin adhesive film:
Grafted polyethylene resin, polyolefin resin, master batch, auxiliary agent are uniformly mixed by the proportion according to claim 1, are then added single Reactive extrursion is carried out in screw extruder, finally by extrusion, curtain coating, cooling, is cut, winding process, can be obtained described low Mist degree polyolefin adhesive film.
CN201811566624.4A 2018-12-19 2018-12-19 A kind of low haze polyolefin adhesive film and preparation method thereof Pending CN109627997A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110885496A (en) * 2019-12-17 2020-03-17 苏州度辰新材料有限公司 Antistatic heat-conducting polyolefin composition and preparation method thereof
CN115895093A (en) * 2023-02-16 2023-04-04 天津华德科技有限公司 Antistatic breathable film and preparation method thereof

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JPH03166283A (en) * 1989-11-24 1991-07-18 Nippon Unicar Co Ltd Adhesive resin and composite material
CN101678398A (en) * 2007-03-26 2010-03-24 Toto株式会社 Photocatalyst-coated object and photocatalytic coating fluid therefor
CN103059753A (en) * 2012-12-25 2013-04-24 江苏鹿山光伏科技有限公司 Polyolefin packaging adhesive film, preparation method thereof and application thereof
CN106753056A (en) * 2016-12-29 2017-05-31 苏州度辰新材料有限公司 White polyolefin packaging adhesive film for solar cell module and preparation method thereof

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JPH03166283A (en) * 1989-11-24 1991-07-18 Nippon Unicar Co Ltd Adhesive resin and composite material
CN101678398A (en) * 2007-03-26 2010-03-24 Toto株式会社 Photocatalyst-coated object and photocatalytic coating fluid therefor
CN103059753A (en) * 2012-12-25 2013-04-24 江苏鹿山光伏科技有限公司 Polyolefin packaging adhesive film, preparation method thereof and application thereof
CN106753056A (en) * 2016-12-29 2017-05-31 苏州度辰新材料有限公司 White polyolefin packaging adhesive film for solar cell module and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110885496A (en) * 2019-12-17 2020-03-17 苏州度辰新材料有限公司 Antistatic heat-conducting polyolefin composition and preparation method thereof
CN115895093A (en) * 2023-02-16 2023-04-04 天津华德科技有限公司 Antistatic breathable film and preparation method thereof

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Application publication date: 20190416