CN108544826A - Montmorillonite-based high-barrier nano composite film and preparation method thereof - Google Patents

Montmorillonite-based high-barrier nano composite film and preparation method thereof Download PDF

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Publication number
CN108544826A
CN108544826A CN201810426301.9A CN201810426301A CN108544826A CN 108544826 A CN108544826 A CN 108544826A CN 201810426301 A CN201810426301 A CN 201810426301A CN 108544826 A CN108544826 A CN 108544826A
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montmorillonite
film
adhesive
barrier
nano
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吴明在
白志满
焦尚青
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Anhui University
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Anhui University
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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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1276—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives water-based adhesive
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B32B2038/168—Removing solvent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a montmorillonite-based high-barrier nano composite film and a preparation method thereof, wherein a barrier bonding layer formed by montmorillonite nano modified adhesive is arranged between an inner polymer film and an outer polymer film, wherein the montmorillonite nano modified adhesive is prepared by taking montmorillonite as a reinforcement and uniformly dispersing the montmorillonite in the adhesive by a solution blending method. The montmorillonite-based nano composite film prepared by the method has excellent barrier and mechanical properties and good transparency, and solves the problem of poor barrier property of the existing flexible transparent film; the process of the invention is convenient for industrial production, the raw materials are simple and easy to obtain, and the process is suitable for packaging foods and medicines with higher requirements on barrier property.

Description

A kind of montmorillonite base high-barrier nano laminated film and preparation method thereof
Technical field
The invention belongs to montmorillonite-based nano field of material technology, and in particular to a kind of montmorillonite base high-barrier nano THIN COMPOSITE Film.
Background technology
Polymer thin-film material with its excellent comprehensive performance, as substitutes such as glass, ceramics and metals in food and It is more and more widely used in pharmaceutical packing.However, there is the shortcomings that ventilative and moisture-inhibiting in polymer thin-film material, easily Cause food spoilage, drug pharmacological property to weaken, influences the long-term preservation of food and drug.Therefore, polymer thin-film material is improved Barrier property is always the focus and emphasis of domestic and international packaging industry research.Plastic film packaging industry mainly uses multilayer at present Composite film material solves the problems, such as thin-film barrier poor performance, wherein it is high barrier material (such as aluminium foil, ethylene-second to have one layer Enol copolymer)；Or last layer barrier material (such as aluminium, aluminium oxide, silica) is plated on film substrate；In addition, using resistance Every property coating method, polyvinylidene chloride is coated in film surface, improves thin-film barrier performance.However, above-mentioned high-isolation film Packaging material exists such as：Film translucency is poor, production equipment and the shortcomings of technology relies on import, production cost is high.
The main component of montmorillonite is silicates, and lamellar spacing is only 0.96~2.1nm.When in the polymeric material When reaching nano-dispersion, montmorillonite-based nano lamella may act as impermeable blocker unit in the polymer, and gas is in order to expand It dissipates through polymer, then needs to bypass montmorillonite-based nano lamella, permeation pathway is forced to extend, limitation gas molecule infiltration.Therefore, Using " blocking effect " and " multipath effect " of nano imvite lamella in a polymer matrix, polymerization can be effectively improved The barrier property of object film.According to Chang (Polym Sci Part B:Polym Phys,2003,41(1):94-103) and Thellen(Polymer,2005,46(25):Research 11716-11727) et al., it is 1~6wt%'s to prepare montmorillonite content Poly-lactic acid/montmorillonite composite membrane, the purer polylactic acid of transmission rates of the oxygen in composite membrane reduce by 15%~30%.
The method of high-isolation film material is prepared mainly using montmorillonite-based nano powder as modification currently with montmorillonite Filler is realized and is covered first by means of the methods of solution blending, melt blending, master batch melt blending, reactive extrursion, in-situ polymerization The dispersion of de- soil in a polymer matrix, then prepares THIN COMPOSITE by forming methods such as curtain coating, calendering, blowing, biaxial tensiones Film.Such as：Patent CN107033557A discloses a kind of barrier property PBAT laminated films and the preparation method and application thereof, this method PBAT basis materials, laminar nano inorganic matter, levelling agent and antifoaming agent are proportionally added into organic solvent, it is made uniformly to divide It dissipates in a solvent, then solution casting method is used to prepare film forming.When OMMT is the 0.5wt% of PBAT contents, with blank sample pair Than penetrability has dropped 36.11%.Patent CN102464873A discloses a kind of biaxially stretched polylactic acid/montmorillonite Composite film And its preparation method and application, each component including polylactic acid, montmorillonite is uniformly mixed by certain content, through melt blending and After curtain coating, poly-lactic acid/montmorillonite composite membrane is made in biaxial tension, and the composite membrane of preparation has excellent barrier property.Patent CN103205049A discloses a kind of high-barrier antibacterial PE films and preparation method thereof, and nano-compound modified masterbatch is added to LDPE In matrix, high-barrier antibacterial film is obtained by extrusion-blown modling, wherein modified master by load nano-ZnO organo montmorillonite, LDPE and maleic anhydride grafted polyethylene blending extrusion obtain；Compared with pure PE films, the oxygen transit dose of high-barrier antibacterial PE films 31% is reduced, water vapo r transmission amount declines 40%, and antibiotic rate reaches 99.7%.Patent also has as associated class：Patent CN105623209A is disclosed " method that melt phase polycondensation prepares high water vapor barrier polyester film "；Patent CN101768302A It discloses " preparation method of high barrier property polyethylene/nylon 6 in-situ nanocomposite "；Patent CN106750267A is disclosed " a kind of nanometer of 6/66 resin of copolymer nylon and preparation method thereof and its application in film packaging " etc..Above-mentioned patent disclosure Method essentially relates to two steps：The first step is by the methods of solution blending, melt blending or in-situ polymerization by montmorillonite It is distributed in polymer, solution blending needs additionally to use a large amount of organic solvent during this, and there are difficult solvent recovery, rings The problems such as border is polluted and the production cost increases, melt blending processing technology is simple, but the dispersion performance of montmorillonite is poor, in situ Polymerization needs to study existing polymerization technique, and film packaging manufacturing enterprise needs by upstream polymerisation object production enterprise The cooperation of industry is unfavorable for extensive industrialization；Second step is to be received polymer-montmorillonoid by different film forming technique Nano composite material is shaped to thin-film material, this process needs to explore existing moulding process.Therefore, the above method prepares work Skill is complicated, cumbersome, cost is higher, does not meet the production requirement of current state's inner polymer film packaging industry high-isolation film, and It needs to be transformed existing equipment, technique, is unfavorable for large-scale commercial introduction and application.
Invention content
For the technological deficiency of existing high barrier food and Key works Drug packing film, the present invention proposes a kind of montmorillonite base High-barrier nano laminated film and preparation method thereof, technical problem to be solved are：Using montmorillonite as reinforcing agent, tool is prepared There is the transparency high separation nano compound film of high barrier, easy processing, low cost, high comprehensive performance.
The present invention solves above-mentioned technical problem, adopts the following technical scheme that：
The present invention discloses a kind of montmorillonite base high-barrier nano laminated film first, and feature is, the nanometer is multiple It is that barrier adhesive layer is provided between internal layer polymer film and outer polymer film to close film；The barrier adhesive layer is Montmorillonite-based nano modified adhesive；The montmorillonite-based nano modified adhesive is to pass through solution blending using montmorillonite as reinforcement Method, it is evenly dispersed and obtained in adhesive.
Wherein：
The internal layer polymer film is polyethylene film, polypropylene film, polyvinylidene chloride film, ethylene-vinegar Sour ethylene copolymer films or ethylene-vinyl alcohol copolymer film；The outer polymer film is polypropylene film, polyamides Amine film, pet film, polycarbonate film, polyethylene naphthalate film or polyvinyl chloride Film.
The adhesive is water-borne acrylic type adhesive, water-based polyurethane adhesive, polyester solvent type polyurethane Class adhesive, polyether solvent type polyurethane class adhesive or polyolefin solvent type polyurethane class adhesive.
In the montmorillonite-based nano modified adhesive, the quality of montmorillonite account for adhesive solid content 0.02~ 5.0wt%.The montmorillonite is the organo montmorillonite that organo montmorillonite or silane coupling agent are handled.The silane coupling agent For γ-aminopropyl triethoxysilane, γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicanes or γ-methacryloxypropyl Base propyl trimethoxy silicane.
The preparation method of the organo montmorillonite of silane coupling agent processing is to carry out according to the following steps：1-10mL silane is taken first Coupling agent instills in 70-700mL absolute ethyl alcohols, and pH is titrated between 4~6 with 1mol/L oxalic acid solutions, hydrolyzes 1 hour, obtains Coupling agent after must hydrolyzing；Then it takes organo montmorillonite 5-50g to be dissolved in 100-1000mL absolute ethyl alcohols, and is coupled after the hydrolysis Agent is placed in three-necked flask together, 60-80 DEG C of stirring in water bath, condensing reflux 1-3h, product washes of absolute alcohol, at 80 DEG C Dry, ground 200 mesh sieve is to get the organo montmorillonite handled to silane coupling agent.
The present invention further discloses the preparation methods of above-mentioned montmorillonite base high-barrier nano laminated film, including following step Suddenly：
(1) montmorillonite is added in solvent, at ambient temperature 40~90min of ultrasonic disperse, obtains montmorillonite suspension Liquid；
(2) montmorillonite suspension liquid is added in adhesive, under the conditions of 20~45 DEG C mechanical agitation 60~ 120min obtains montmorillonite-based nano modified adhesive；
(3) dry type composite algorithm is utilized, by way of roll-in, montmorillonite-based nano modified adhesive is coated in outer layers of polymer The inner surface of object film after montmorillonite-based nano modified adhesive is dried and to form film, then covers internal layer polymer film, to Inside and outside two layers of polymers film is set to be bonded together；
(4) film after will be compound 48~120h of maturation process in 30~60 DEG C of curing chamber, that is, obtain montmorillonite base High-barrier nano laminated film.
Preferably, in step (1), the solvent is distilled water or ethyl acetate.
Preferably, in step (3), the combination process of dry type composite algorithm is：Butt spread is 1.5~3.0g/m2, cable Roller is 140~200 mesh, and drying tunnel temperature subregion is set as 40~70 DEG C, 50~80 DEG C, 60~90 DEG C, and compound roller temperature is 50~80 DEG C, recombination velocity is 50~200m/min, and composite pressure is 0.2~0.6MPa.
Compared with prior art, beneficial effects of the present invention are embodied in：
1, the present invention prepares nano compound film by reinforcing agent of montmorillonite, effectively increases the barrier property of laminated film Can, and the translucency of gained laminated film is good, excellent in mechanical performance, solves the problems, such as that transparent membrane barrier property is bad, It can be applied to the higher food of barrier and Key works Drug packing.
2, the preparation method is that montmorillonite is distributed to the aqueous and solvent type between inside and outside two layers of polymers film In adhesive, organic solvent, and montmorillonite good dispersion property additionally need not be largely used.
3, the forming method of laminated film of the present invention is the dry type composite algorithm based on food product packing film industry routine, is utilized Existing equipment, it is technology maturation, simple for process, of low cost, it is more suitable for large-scale industrial production, and barriering effect is more It is good.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below by embodiment to this hair The performance of bright preparation method and products obtained therefrom is described in detail.The following contents is only to be lifted made by the design to the present invention Example and explanation, affiliated those skilled in the art make various modifications or additions to the described embodiments or It substitutes by a similar method, it as long as it does not deviate from the concept of invention or beyond the scope defined by this claim, should all It belongs to the scope of protection of the present invention.
In following embodiments：Solvent for use type polyurethane adhesive model LH-7755, purchase close adhesive from Jiangsu power Co., Ltd；Aqueous polyurethane adhesive model JH-826 used is bought from Jiangsu Berry spy's new material Co., Ltd；It is used Organo montmorillonite model DK1N is bought from Zhejiang Fenghong New Material Co., Ltd.；Organic illiteracy of silane coupling agent processing De- soil self-control.
Embodiment 1
Weigh solvent borne polyurethane adhesive host agent (solid content：75wt%) 3.85kg, curing agent (solid content 75wt%) 0.77kg, ethyl acetate 5.38kg are compareed host agent, curing agent and ethyl acetate mechanical agitation 120min at room temperature Solvent borne polyurethane adhesive.
Selection is outer, internal layer polymer film is respectively bidirectional stretching polypropylene film (BOPP) and cast polypropylene film (CPP), uniformly mixed control solvent type polyurethane adhesive is poured into adhesive slot, the bubble in be bonded dose disappears substantially After removing, control BOPP/CPP laminated films are obtained using dry type composite algorithm.The combination process parameter of wherein dry compound machine is：It is dry Base spread is 1.5g/m2, 160 mesh of cable roll, three sections of oven temperatures are respectively 56 DEG C, 58 DEG C, 63 DEG C, and compound roller temperature is 50 DEG C, recombination velocity 100m/min, composite pressure 0.3MPa.
Control BOPP/CPP laminated films are placed on 40 DEG C of curing chambers, maturation process 48h finally obtains control BOPP/ CPP laminated film products.
After tested, the performance of control BOPP/CPP laminated films obtained by the present embodiment is as follows：OTR oxygen transmission rate is 873.52cm3/(m2× for 24 hours × 0.1MPa), moisture-vapor transmission is 2.67g/ (m2×24h)；Pull-off force (vertical/horizontal) is 45.18/89.18N, it is 135.87/28.94% that elongation at break is (vertical/horizontal), and anti-pendulum force is 1.015N；Peeling force is 1.23N/15mm。
Embodiment 2
Weigh solvent borne polyurethane adhesive host agent (solid content：75wt%) 3.85kg, curing agent (solid content 75wt%) 0.77kg, ethyl acetate 5.38kg, organo montmorillonite 17.3g.
Organo montmorillonite is added in ethyl acetate, at ambient temperature ultrasonic disperse 40min, obtains organo montmorillonite Suspension；Then the suspension of organo montmorillonite is added in host agent, at room temperature after mechanical agitation 60min, is added solid Agent continues mechanical agitation 60min, obtains organic montmorillonite nano and is modified solvent borne polyurethane adhesive.
Selection is outer, internal layer polymer film is respectively bidirectional stretching polypropylene film (BOPP) and cast polypropylene film (CPP), uniformly mixed organic montmorillonite nano is modified solvent borne polyurethane adhesive to pour into adhesive slot, to be bonded dose In bubble substantially eliminate after, obtain montmorillonite base high-barrier BOPP/CPP nano compound films using dry type composite algorithm.Wherein The combination process parameter of dry compound machine is：Butt spread is 1.5g/m2, 160 mesh of cable roll, three sections of oven temperatures are respectively 56 DEG C, 58 DEG C, 63 DEG C, compound roller temperature is 50 DEG C, recombination velocity 100m/min, composite pressure 0.3MPa.
Laminated film is placed in 40 DEG C of curing chambers, maturation process 48h, finally obtains montmorillonite base high-barrier BOPP/ CPP nano compound film products.
After tested, the performance of montmorillonite base high-barrier BOPP/CPP nano compound films obtained by the present embodiment is as follows：Oxygen Transmitance is 473.01cm3/(m2× for 24 hours × 0.1MPa), moisture-vapor transmission is 1.74g/ (m2×24h)；Pull-off force (vertical/ It is horizontal) it is 47.41/95.16N, (vertical/horizontal) elongation at break is 139.58/28.96%, and anti-pendulum force is 1.05N；Peeling force is 1.32N/15mm。
Embodiment 3
The present embodiment prepares laminated film product by 2 identical method of embodiment, differs only in：Organo montmorillonite adds Dosage is 34.6g.
After tested, the performance of montmorillonite base high-barrier BOPP/CPP nano compound films obtained by the present embodiment is as follows：Oxygen Transmitance is 509.49cm3/(m2× for 24 hours × 0.1MPa), moisture-vapor transmission is 1.67g/ (m2×24h)；Pull-off force (vertical/ It is horizontal) it is 49.80/98.61N, (vertical/horizontal) elongation at break is 154.61/31.39%, and anti-pendulum force is 1.01N；Peeling force is 1.39N/15mm。
Embodiment 4
The present embodiment prepares laminated film product by 2 identical method of embodiment, differs only in：Organo montmorillonite is replaced It is changed to the organo montmorillonite 17.3g of γ-aminopropyl triethoxysilane processing, preparation method is as follows：5mL γ-are taken first Aminopropyl triethoxysilane instills in 350mL absolute ethyl alcohols, and it is 5 to be titrated to pH value with 1mol/L oxalic acid solutions, and hydrolysis 1 is small When, coupling agent after being hydrolyzed；Then organo montmorillonite 25g is taken to be dissolved in 500mL absolute ethyl alcohols, together with coupling agent after hydrolysis It is placed in three-necked flask, 75 DEG C of stirring in water bath, condensing reflux 2h, it is product washes of absolute alcohol, dry, ground at 80 DEG C 200 mesh sieve is to get the organo montmorillonite handled to γ-aminopropyl triethoxysilane.
After tested, the performance of montmorillonite base high-barrier BOPP/CPP nano compound films obtained by the present embodiment is as follows：Oxygen Transmitance is 455.70cm3/(m2× for 24 hours × 0.1MPa), moisture-vapor transmission is 1.70g/ (m2×24h)；Pull-off force (vertical/ It is horizontal) it is 48.16/96.34N, (vertical/horizontal) elongation at break is 141.77/31.75%, and anti-pendulum force is 1.02N；Peeling force is 1.38N/15mm。
Embodiment 5
Weigh aqueous polyurethane adhesive host agent (solid content 30%) 10kg, curing agent 0.4kg, distilled water 200g.
By host agent, curing agent and distilled water mechanical agitation 120min at room temperature, control aqueous polyurethane adhesive is obtained.
Selection is outer, internal layer polymer film is respectively pet film (PET) and polyethylene film (PE), uniformly mixed control aqueous polyurethane adhesive is poured into adhesive slot, the bubble in be bonded dose substantially eliminates Afterwards, control PET/PE laminated films are obtained using dry type composite algorithm.The combination process parameter of wherein dry compound machine is：On butt Glue amount is 2.2g/m2, 140 mesh of cable roll, three sections of oven temperatures are respectively 70 DEG C, 80 DEG C, 90 DEG C, and compound roller temperature is 70 DEG C, multiple Sum velocity is 100m/min, composite pressure 0.5MPa.
Laminated film is placed in 30 DEG C of curing chambers, maturation process 120h, finally obtains control PET/PE laminated films Product.
After tested, the performance of control PET/PE laminated films obtained by the present embodiment is as follows：OTR oxygen transmission rate is 102.22cm3/(m2× for 24 hours × 0.1MPa), moisture-vapor transmission is 4.14g/ (m2×24h)；Pull-off force (vertical/horizontal) is 49.28/50.76N, it is 79.48/67.82% that elongation at break is (vertical/horizontal), and anti-pendulum force is 1.01N；Peeling force is 3.29N/ 15mm。
Embodiment 6
Weigh aqueous polyurethane adhesive host agent (solid content 30%) 10kg, curing agent 0.4kg, organo montmorillonite 17.0g, Distilled water 200g.
Organo montmorillonite is added in distilled water, at ambient temperature ultrasonic disperse 40min, obtains organo montmorillonite Suspension；Then the suspension of organo montmorillonite is added in aqueous polyurethane adhesive host agent, at room temperature mechanical agitation After 60min, curing agent is added, continues mechanical agitation 60min, obtains organic montmorillonite nano modified aqueous polyurethane adhesive.
Selection is outer, internal layer polymer film is respectively pet film (PET) and polyethylene film (PE), uniformly mixed organic montmorillonite nano modified aqueous polyurethane adhesive is poured into adhesive slot, in be bonded dose Bubble substantially eliminate after, obtain montmorillonite base high-barrier PET/PE laminated films using dry type composite algorithm.Wherein dry type is compound The combination process parameter of machine is：Butt spread is 2.2g/m2, 140 mesh of cable roll, three sections of oven temperatures are respectively 70 DEG C, 80 DEG C, 90 DEG C, compound roller temperature be 70 DEG C, recombination velocity 100m/min, composite pressure 0.5MPa.
Laminated film is placed in 30 DEG C of curing chambers, maturation process 120h, finally obtains montmorillonite base high-barrier PET/ PE laminated film products.
After tested, the performance of montmorillonite base high-barrier PET/PE nano compound films obtained by the present embodiment is as follows：Oxygen is saturating It is 73.80cm to cross rate3/(m2× for 24 hours × 0.1MPa), moisture-vapor transmission is 2.62g/ (m2×24h)；Pull-off force (vertical/horizontal) is 55.87/56.38N, it is 90.77/89.84% that elongation at break is (vertical/horizontal), and anti-pendulum force is 1.00N；Peeling force is 4.60N/ 15mm。
Embodiment 7
The present embodiment prepares laminated film product by 6 identical method of embodiment, differs only in：Organo montmorillonite adds Dosage is 34.0g.
After tested, the performance of montmorillonite base high-barrier PET/PE nano compound films obtained by the present embodiment is as follows：Oxygen is saturating It is 79.13cm to cross rate3/(m2× for 24 hours × 0.1MPa), moisture-vapor transmission is 3.24g/ (m2×24h)；Pull-off force (vertical/horizontal) is 56.18/54.12N, it is 83.55/85.33% that elongation at break is (vertical/horizontal), and anti-pendulum force is 1.09N；Peeling force is 4.27N/ 15mm。
Embodiment 8
The present embodiment prepares laminated film product by 6 identical method of embodiment, differs only in：Organo montmorillonite is replaced It is changed to the organo montmorillonite 17.0g of γ-aminopropyl triethoxysilane processing, preparation method is the same as embodiment 4.
After tested, the performance of montmorillonite base high-barrier PET/PE nano compound films obtained by the present embodiment is as follows：Oxygen is saturating It is 72.31cm to cross rate3/(m2× for 24 hours × 0.1MPa), moisture-vapor transmission is 2.50g/ (m2×24h)；Pull-off force (vertical/horizontal) is 58.32/55.29N, it is 85.01/87.67% that elongation at break is (vertical/horizontal), and anti-pendulum force is 1.07N；Peeling force is 4.83N/ 15mm.It these are only exemplary embodiment of the present invention, be not intended to limit the invention, all spirit and original in the present invention All any modification, equivalent and improvement made by within then etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of montmorillonite base high-barrier nano laminated film, it is characterised in that：The nano compound film is in interior layers of polymer Barrier adhesive layer is provided between object film and outer polymer film；The barrier adhesive layer is that montmorillonite-based nano is modified bonding Agent；The montmorillonite-based nano modified adhesive, by solution blended process, is uniformly divided in adhesive using montmorillonite as reinforcement It dissipates and is made.
2. a kind of montmorillonite base high-barrier nano laminated film according to claim 1, it is characterised in that：The internal layer Thin polymer film be polyethylene film, polypropylene film, polyvinylidene chloride film, ethylene-vinyl acetate copolymer film or Ethylene-vinyl alcohol copolymer film；The outer polymer film is polypropylene film, polyamide film, poly- terephthaldehyde Sour glycol ester film, polycarbonate film, polyethylene naphthalate film or polyvinyl chloride film.
3. a kind of montmorillonite base high-barrier nano laminated film according to claim 1, it is characterised in that：The bonding Agent is water-borne acrylic type adhesive, water-based polyurethane adhesive, polyester solvent type polyurethane class adhesive, polyether solvent type Polyurethane binding or polyolefin solvent type polyurethane class adhesive.
4. a kind of montmorillonite base high-barrier nano laminated film according to claim 1, it is characterised in that：It is taken off in described cover In native nano modification adhesive, the quality of montmorillonite accounts for 0.02~5.0wt% of adhesive solid content.
5. a kind of montmorillonite base high-barrier nano laminated film according to claim 1, it is characterised in that：The illiteracy is de- Soil is the organo montmorillonite that organo montmorillonite or silane coupling agent are handled.
6. a kind of montmorillonite base high-barrier nano laminated film according to claim 5, it is characterised in that：The silane The preparation method of the organo montmorillonite of coupling agent treatment is to carry out according to the following steps：
It takes 1-10mL silane coupling agents to instill in 70-700mL absolute ethyl alcohols first, pH is titrated to 4 with 1mol/L oxalic acid solutions Between~6, hydrolyze 1 hour, coupling agent after being hydrolyzed；Then organo montmorillonite 5-50g is taken to be dissolved in the anhydrous second of 100-1000mL It in alcohol, and is placed in three-necked flask together with coupling agent after the hydrolysis, 60-80 DEG C of stirring in water bath, condensing reflux 1-3h, product With dry at washes of absolute alcohol, 80 DEG C, ground 200 mesh sieve to get the organo montmorillonite handled to silane coupling agent.
7. a kind of montmorillonite base high-barrier nano laminated film according to claim 5 or 6, it is characterised in that：Described Silane coupling agent is γ-aminopropyl triethoxysilane, γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicanes or γ-first Base acryloyloxypropyltrimethoxysilane.
8. a kind of preparation method of any one of claim 1~7 montmorillonite base high-barrier nano laminated film, special Sign is, includes the following steps：
(1) montmorillonite is added in solvent, at ambient temperature 40~90min of ultrasonic disperse, obtains montmorillonite suspension liquid；
(2) montmorillonite suspension liquid is added in adhesive, 60~120min of mechanical agitation under the conditions of 20~45 DEG C is obtained To montmorillonite-based nano modified adhesive；
(3) dry type composite algorithm is utilized, by way of roll-in, it is thin that montmorillonite-based nano modified adhesive is coated in outer layer copolymer The inner surface of film after montmorillonite-based nano modified adhesive is dried and to form film, then covers internal layer polymer film, to make Inside and outside two layers of polymers film is bonded together；
(4) film after will be compound 48~120h of maturation process in 30~60 DEG C of curing chamber, that is, obtain montmorillonite base high resistant Every nano compound film.
9. preparation method according to claim 8, it is characterised in that：In step (1), the solvent is distilled water or second Acetoacetic ester.
10. preparation method according to claim 8, it is characterised in that：In step (3), the combination process of dry type composite algorithm For：Butt spread is 1.5~3.0g/m2, cable roll be 140~200 mesh, drying tunnel temperature subregion be set as 40~70 DEG C, 50 ~80 DEG C, 60~90 DEG C, compound roller temperature be 50~80 DEG C, recombination velocity be 50~200m/min, composite pressure be 0.2~ 0.6MPa。
CN201810426301.9A 2018-05-07 2018-05-07 Montmorillonite-based high-barrier nano composite film and preparation method thereof Pending CN108544826A (en)

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CN109575410A (en) * 2018-11-22 2019-04-05 杭州普信塑料包装有限公司 A kind of high barrier packing bottle for pesticide and preparation method thereof
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CN111020503A (en) * 2019-12-10 2020-04-17 湖北大学 Application of montmorillonite in magnetron sputtering target material, montmorillonite film obtained by using montmorillonite and application of montmorillonite film
CN111020503B (en) * 2019-12-10 2021-07-30 湖北大学 Application of montmorillonite in magnetron sputtering target material, montmorillonite film obtained by using montmorillonite and application of montmorillonite film
CN112406240A (en) * 2020-10-19 2021-02-26 深圳市鼎通新材料科技有限公司 Degradable environment-friendly film material, preparation method and application thereof
CN112210102A (en) * 2020-10-27 2021-01-12 银金达(上海)新材料有限公司 High-barrier PETG (polyethylene terephthalate glycol) aluminized composite film and preparation method thereof
CN112920722A (en) * 2021-03-31 2021-06-08 苏州赛伍应用技术股份有限公司 Water-blocking packaging adhesive film and preparation method thereof
CN113524843A (en) * 2021-08-03 2021-10-22 海南赛诺实业有限公司 High-barrier composite film and preparation method thereof
CN114179474A (en) * 2021-12-14 2022-03-15 厦门长塑实业有限公司 Antibacterial high-barrier biaxially-oriented polyamide film and preparation method and application thereof
CN117124685A (en) * 2023-10-26 2023-11-28 汕头市鑫瑞奇诺包装材料有限公司 Polyethylene single-material composite film, preparation method and application thereof in high-barrier food packaging
CN117124685B (en) * 2023-10-26 2024-01-02 汕头市鑫瑞奇诺包装材料有限公司 Polyethylene single-material composite film, preparation method and application thereof in high-barrier food packaging

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Application publication date: 20180918