Elastomeric laminate film and method of making same

Abstract

The application relates to the field of laminated films, and particularly discloses an elastomer laminated film and a preparation method thereof, the laminated film comprising a film layer I and a film layer II; the film layer I and the film layer II are formed by alternately stacking at least two of polyurethane elastomer, polyolefin elastomer and polyester resin; the polyurethane elastomer comprises the following raw materials in parts by weight: polyether polyol 10-25 parts, isocyanate 15-30 parts, catalyst 1-2.5 parts and acrylic ester copolymer 3-7 parts; the polyolefin elastomer comprises the following raw materials in parts by weight: olefin monomer 20-35 parts, emulsion 4-9 parts, initiator 1-4 parts, stabilizer 0.5-1 part and filler 1-3 parts. The prepared laminated film has excellent elastic modulus and tear strength, the elastic modulus is more than 30%, the tear strength is as high as more than 700 N, the laminated film can effectively block ultraviolet rays and has high visible light transmittance, can be applied to a bending interface with large curvature, and has a wide application range.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of laminated films, more particularly, it relates to an elastomeric laminated film and a preparation method thereof. BACKGROUND

[0002] Thermoplastic resins, especially biaxially stretched polyester films, have excellent mechanical properties, electrical properties, dimensional stability, optical transparency and chemical resistance, and are widely used in many fields such as automotive window films, optical display fields, architectural glass films, packaging films, etc. In recent years, the trend of functionalization, thinning and low cost has developed rapidly, and higher requirements have been put forward for the performance of various polyester films.

[0003] At present, the laminated films designed on the market are all made by mixing two or three thermoplastic resins, and the different refractive indexes between different resins are used to reflect or absorb light in a specific wavelength range, but such laminated films have small elasticity and low tear strength, and cannot be used in curved interfaces with large curvature. SUMMARY

[0004] The present application provides an elastomeric laminated film and a preparation method thereof, the prepared laminated film has excellent elastic modulus and tear strength, can effectively block ultraviolet rays and has high visible light transmittance, can be applied to curved interfaces with large curvature, and has wide application range.

[0005] In a first aspect, the present application provides an elastomeric laminated film using the following technical scheme:

[0006] An elastomeric laminated film, the laminated film comprises film layer I and film layer II with a mass ratio of 1:(1-2); the film layer I and the film layer II are formed by alternately stacking at least two of polyurethane elastomer, polyolefin elastomer and polyester resin;

[0007] The polyurethane elastomer comprises the following raw materials by weight: polyether polyol 10-25 parts, isocyanate 15-30 parts, catalyst 1-2.5 parts, and acrylic ester copolymer 3-7 parts;

[0008] The polyolefin elastomer comprises the following raw materials by weight: olefin monomer 20-35 parts, emulsion 4-9 parts, initiator 1-4 parts, stabilizer 0.5-1 parts, and filler 1-3 parts.

[0009] At least two of polyurethane elastomer, polyolefin elastomer and polyester resin are selected for alternately stacking, which has good bonding force and compatibility, and the obtained film layer I and film layer II contain the same structural units and are stacked with each other, so that the precision of the laminated film is higher, the bonding force between adjacent film layer interfaces is also higher, so that the product is not prone to interlayer peeling (delamination) problem during use, and the tear strength is good.

[0010] The laminated film obtained by using the film layer I and the film layer II is a multilayer optical elastomer with effective UV blocking and high visible light transmittance, which has good elastic modulus and excellent tear strength, and can be used in curved interfaces with large curvature. In the field of automobile manufacturing, the laminated film has good adhesion with the vehicle window functional film, and can effectively block UV rays, reduce the transmission of sunlight, reduce the temperature inside the vehicle, and thus provide a comfortable and safe driving environment, and reduce the damage caused by UV rays to the people and objects inside the vehicle. It can also be used for large building glass films, and the product has excellent adhesion with the glass, can effectively block UV rays, prolong the service life of indoor objects, reduce glare, and improve comfort.

[0011] The polyurethane elastomer is prepared by condensation reaction of polyether polyol and isocyanate under the action of a catalyst to form a prepolymer with blocked isocyanate groups. The prepolymer has isocyanate groups and polyether segments, which can further react with the acrylic ester copolymer to form longer polymer chains, which is beneficial to the compatibility between the obtained polyurethane elastomer and other components. The acrylic ester copolymer not only has good elasticity, but also can adjust the flowability and viscosity of the material, so that the obtained polyurethane elastomer material has good elasticity and excellent mechanical properties, and the laminated film has excellent elastic modulus and improved tear strength, so that the laminated film can be applied to curved interfaces with large curvature and has wide application range.

[0012] The polyolefin elastomer is prepared by polymerization of olefin monomers. The olefin monomers gradually polymerize to form high molecular polymers during the polymerization reaction. The emulsion and stabilizer can reduce the interfacial tension and make the olefin monomers more easily form a colloidal emulsion, control the size and distribution of polymer particles during the polymerization process, and obtain a polyolefin elastomer with excellent elasticity and softness. The filler not only can increase the density and uniformity of the material and improve the tear strength of the material, but also can reduce the penetration of UV rays by absorbing and scattering UV rays to effectively block UV rays.

[0013] Preferably, the olefin monomer includes one of vinyl acetate and vinyl chloride.

[0014] Further, the olefin monomer is preferably vinyl acetate.

[0015] By using the above technical solution, selecting appropriate olefin monomers is beneficial to forming a polyolefin elastomer with excellent elastic modulus and flexibility.

[0016] Preferably, the stabilizer includes one of octanol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether, and octanol sulfate.

[0017] By adopting the above technical scheme, the octanol polyoxyethylene ether, the cetylphenol polyoxyethylene ether and the octanol sulfate are used as the surfactants, which can effectively reduce the interfacial tension, help to stably disperse the olefin monomers, more easily form the emulsion colloid, and be conducive to the size and distribution of the polymer particles, thereby regulating the product performance of the polyolefin elastomer and assisting in improving the compatibility between the polyolefin elastomer and other components.

[0018] Preferably, the emulsion comprises one of vinyl chloride-vinyl acetate copolymer, styrene butadiene rubber emulsion and acrylic emulsion.

[0019] By adopting the above technical scheme, the presence of the emulsion can make the different polymers have good adhesion, and the high molecular substances in the emulsion can further participate in the polymerization reaction of the olefin monomers, enhance the mechanical properties of the material and the compatibility between different materials, and the emulsion can also adjust the viscosity and fluidity of the system to a certain extent and improve the processing performance of the material.

[0020] Preferably, the filler comprises at least one of titanium dioxide, ethyl cellulose and nano-silicon dioxide.

[0021] Further, the filler is preferably titanium dioxide and ethyl cellulose in a mass ratio of 2:(0.5-1).

[0022] By adopting the above technical scheme, the titanium dioxide, the ethyl cellulose and the nano-silicon dioxide can all be used as the filler to be filled into the film product to enhance the mechanical properties of the film, the titanium dioxide has better ultraviolet blocking performance and can assist the laminated film to have excellent ultraviolet blocking performance and high visible light transmittance, and the ethyl cellulose is conducive to improving the compatibility between the polyolefin elastomer and other components.

[0023] Preferably, the polyester resin comprises one of polymethyl methacrylate, polyvinyl acetate and polycarbonate modified by a silane coupling agent.

[0024] Further, the silane coupling agent is KH550 or KH560.

[0025] The modification of the polymethyl methacrylate or the polyvinyl acetate by the silane coupling agent can effectively improve the surface properties and the compatibility between different materials.

[0026] Preferably, the polyurethane elastomer has a melt index of 10-20 g / 10 min at 200-210℃, and the polyolefin elastomer has a melt index of 15-25 g / 10 min at 200-210℃.

[0027] By adopting the above technical scheme, the melt indexes of the polyurethane elastomer and the polyolefin elastomer are further optimized to ensure the processing performance of the material.

[0028] Preferably, the film layer I is composed of 60-75wt% polyurethane elastomer and 25-40wt% polyester resin.

[0029] Preferably, the film layer II is composed of 30-40wt% polyurethane elastomer and 70-60wt% polyolefin elastomer.

[0030] Further, the difference between the refractive indexes of the film layer I and the film layer II is greater than 0.09.

[0031] By using the above technical solution, the composition of the film layer I and the film layer II is optimized, so that the laminated film not only has excellent elastic modulus and tear strength, but also can effectively block ultraviolet rays and has high visible light transmittance.

[0032] In a second aspect, the application provides a preparation method of an elastomer laminated film, which uses the following technical solution:

[0033] A preparation method of an elastomer laminated film, comprising the following steps:

[0034] Preparation of polyurethane elastomer: mixing polyether polyol with 40-65% total weight of isocyanate, adding a catalyst to generate a polyurethane prepolymer by reaction at elevated temperature; dissolving an acrylic ester copolymer and the remaining isocyanate in an organic solvent, and adding the polyurethane prepolymer to continue the reaction, to obtain a polyurethane elastomer;

[0035] Preparation of polyolefin elastomer: uniformly mixing olefin monomers with a stabilizer to obtain a mixture, uniformly dispersing an emulsion and a filler in an aqueous solvent, and adding the mixture to the aqueous solvent under the action of an initiator, to generate a polyolefin elastomer by reaction at elevated temperature;

[0036] Alternately laminating the film layer I and the film layer II, extruding into a film, and performing bidirectional stretching to obtain an elastomer laminated film.

[0037] Further, the multiple of bidirectional stretching is between 5-15 times, preferably 5-8 times; so that the polymer molecules are oriented during the stretching process, and corresponding mechanical and mechanical properties are obtained.

[0038] Further, in the step of preparing the polyurethane elastomer, the polyether polyol includes one of polyethylene glycol PEG-600, polypropylene glycol, and polytetrahydrofuran. The catalyst is an organic tin compound, and the organic solvent is dimethyl sulfoxide or dimethyl formamide. The reaction temperature is 50-70℃, and the reaction time is 30-55min.

[0039] Further, in the step of preparing the polyolefin elastomer, the initiator is one of benzoyl peroxide and dimercaptodiisopropyl alcohol; the aqueous solvent is propylene glycol or ethylene glycol. The reaction temperature is 60-80℃, and the reaction time is 1-2h.

[0040] By adopting the technical scheme, in the process of preparing the polyurethane elastomer, the polyether polyol is first reacted with part of the isocyanate to generate a polyurethane prepolymer, then reacted with the isocyanate to form a longer polymer chain and a three-dimensional network structure, in the reaction process, the isocyanate in the isocyanate can react with the amino group in the polyurethane prepolymer to form a urea bond structure, forming a network structure with high cross-linking, and the existence of the urea bond enhances the elastic modulus of the polyurethane elastomer, realizing the dual regulation of the strength and elasticity of the polyurethane elastomer.

[0041] In the step of preparing the polyolefin elastomer, the emulsion and the filler are uniformly dispersed in the aqueous phase solvent and then reacted with the olefin monomer, which helps the polymerization reaction to proceed and accelerates the reaction rate, and at the same time, it is beneficial to the excellent dispersibility of the olefin monomer, maintains the uniformity of the reaction, reduces the unevenness in the polymerization process, and controls the comprehensive performance of the polyolefin elastomer.

[0042] In summary, the present application has the following beneficial effects:

[0043] 1. At least two of the polyurethane elastomer, the polyolefin elastomer and the polyester resin are selected for alternating superposition, which has good bonding force and compatibility, and the obtained film layer I and film layer II contain the same structural units and are mutually laminated, so that the precision of the laminated film is higher, the bonding force between adjacent film layer interfaces is also higher, so that the product is not prone to interlayer peeling (delamination) problem during use, and the tear strength is good.

[0044] 2. The laminated film obtained by the film layer I and the film layer II is a multilayer optical elastomer with high visible light transmittance and effective ultraviolet blocking, which has good elastic modulus and excellent tear strength, and can be used for curved interfaces with large curvature. In the field of automobile manufacturing, the use of window functional film, the laminated film has good adhesion with the window, and can effectively block ultraviolet rays, reduce the transmission of sunlight, and reduce the temperature in the car, thereby providing a comfortable and safe driving environment, and reducing the damage of ultraviolet rays to the people and objects in the car. It can also be used for large building glass film, and the product has excellent adhesion with glass, can effectively block ultraviolet rays, prolong the service life of indoor objects, reduce dazzling strong light, and improve comfort. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 The process flow diagram of the preparation method of the elastic laminated film of the present application. DETAILED DESCRIPTION

[0046] The embodiments of the present application will be described in detail below with examples, but those skilled in the art will understand that the following examples are only for illustration of the present application, and should not be regarded as limiting the scope of the present application, the specific conditions not noted in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer, the reagents or instruments not noted the manufacturer are all the conventional products that can be purchased in the market. Among them: polymethyl methacrylate CAS number: 9011-14-7; vinyl chloride-acetic acid ethylene copolymer CAS number: 9003-22-9; polyvinyl acetate CAS number: 9003-20-7; polytetrahydrofuran CAS number: 24979-97-3; acrylic emulsion CAS number: 25085-34-1, octanol polyoxyethylene ether CAS number: 26468-86-0; acrylic ester copolymer CAS number: 25035-69-2, alkyl glycoside CAS number: 141464-42-8.

[0047] Example

[0048] Example 1

[0049] An elastomer laminated film, the laminated film is film layer I and film layer II with a mass ratio of 1:1; film layer I is composed of 60wt% of polyurethane elastomer and 40wt% of polyester resin; film layer II is composed of 30wt% of polyurethane elastomer and 70wt% of polyolefin elastomer; wherein the polyester resin is prepared by the following steps: after hydrolysis of 0.1kg silane coupling agent KH550, uniformly spray on the surface of 10kg polymethyl methacrylate;

[0050] The polyurethane elastomer includes the following raw materials: 10kg of polyether polyol, 15kg of isocyanate, 1kg of catalyst, 7kg of acrylic ester copolymer; wherein the polyether polyol is polyethylene glycol PEG-600, the catalyst is diethyl tin ester, and the isocyanate is toluene diisocyanate; the melt index of the polyurethane elastomer under the condition of 205℃ and 5000g load is 20g / 10min;

[0051] The polyolefin elastomer includes the following raw materials: 35kg of olefin monomer, 9kg of emulsion, 4kg of initiator, 0.5kg of stabilizer, and 1kg of filler; wherein the olefin monomer is acetic acid-vinyl, the emulsion is acrylic emulsion, the stabilizer is octanol sulfate, and the filler is nano silicon dioxide; the melt index of the polyolefin elastomer under the condition of 205℃ and 5000g load is 15g / 10min;

[0052] A preparation method of an elastomer laminated film, comprising the following steps:

[0053] Preparation of polyurethane elastomer: polyether polyol is mixed with 65% total weight of isocyanate, catalyst is added, and the temperature is raised to 50°C for 55 minutes to form a polyurethane prepolymer; the acrylic ester copolymer and the remaining isocyanate are dissolved in dimethyl sulfoxide solution, and the polyurethane prepolymer is added to continue the reaction to obtain the polyurethane elastomer;

[0054] Preparation of polyolefin elastomer: olefin monomers are mixed with stabilizer to obtain a mixture, the emulsion and filler are uniformly dispersed in propylene glycol, and then added to the mixture, and under the action of initiator benzoyl peroxide, the temperature is raised to 60°C for 2 hours to obtain the polyolefin elastomer;

[0055] Preparation of film layer I: the polyurethane elastomer and polyester resin are heated to a molten state by a twin-screw extruder according to the formula amount, and then sent to a distributor after passing through a melt pump and a filter screen, and stacked alternately in the order of polyurethane elastomer and polyester resin to form film layer I; preparation of film layer II: the polyolefin elastomer and polyester resin are heated to a molten state by a twin-screw extruder according to the formula amount, and then sent to a distributor after passing through a melt pump and a filter screen, and stacked alternately in the order of polyolefin elastomer and polyester resin to form film layer II; the film layer I and the film layer II are heated to a molten state by a twin-screw extruder, and then sent to a distributor after passing through a melt pump and a filter screen, and stacked alternately in the order of film layer I and film layer II, extruded into a film, and stretched in two directions, with a stretching ratio of 6 times, to obtain the elastomer laminated film.

[0056] Example 2

[0057] An elastomer laminated film, the laminated film comprising film layer I and film layer II in a mass ratio of 1:2; the film layer I is composed of 75 wt% of polyurethane elastomer and 25 wt% of polyester resin; the film layer II is composed of 30 wt% of polyurethane elastomer and 70 wt% of polyolefin elastomer;

[0058] The polyester resin is prepared by the following steps: 0.1 kg of silane coupling agent KH560 is hydrolyzed and uniformly sprayed on the surface of 10 kg of polyvinyl acetate;

[0059] The polyurethane elastomer comprises the following raw materials: 25 kg of polyether polyol, 30 kg of isocyanate, 2.5 kg of catalyst, and 3 kg of acrylic ester copolymer; the polyether polyol is polytetrahydrofuran, the catalyst is diethyl tin ester, and the isocyanate is diphenyl methane diisocyanate; the melt index of the polyurethane elastomer under the condition of 205°C and a load of 5000 g is 10 g / 10 min;

[0060] The polyolefin elastomer comprises the following raw materials: 20 kg of olefin monomer, 4 kg of emulsion, 1 kg of initiator, 1 kg of stabilizer, and 3 kg of filler; wherein the olefin monomer is vinyl chloride, the emulsion is a butadiene-styrene rubber emulsion, the stabilizer is octanol polyoxyethylene ether, and the filler is ethyl cellulose and nano-silicon dioxide at a mass ratio of 1:2; the melt index of the polyolefin elastomer under the condition of 5000 g load at 205℃ is 25 g / 10 min;

[0061] A method for preparing an elastomer laminated film, comprising the following steps:

[0062] Preparation of a polyurethane elastomer: mixing polyether polyol with 40% of total weight of isocyanate, adding catalyst, heating to 70℃ and reacting for 30 min to form a polyurethane prepolymer; dissolving the remaining isocyanate and acrylate copolymer in a dimethylformamide solution, and adding the polyurethane prepolymer to continue the reaction to obtain a polyurethane elastomer;

[0063] Preparation of a polyolefin elastomer: uniformly mixing olefin monomer and stabilizer to obtain a mixture, uniformly dispersing emulsion and filler in ethylene glycol, and then adding them to the mixture, under the action of initiator dimercaptodiisopropyl alcohol, heating to 80℃ and reacting for 1 h to obtain a polyolefin elastomer;

[0064] Preparation of film layer I: heating polyurethane elastomer and polyester resin to a molten state according to the formula amount through a double screw extruder, sending them to a distributor after passing through a melt pump and a filter screen, and alternately stacking them in the order of polyurethane elastomer and polyester resin to form film layer I; preparation of film layer II: heating polyolefin elastomer and polyester resin to a molten state according to the formula amount through a double screw extruder, sending them to a distributor after passing through a melt pump and a filter screen, and alternately stacking them in the order of polyolefin elastomer and polyester resin to form film layer II; heating film layer I and film layer II to a molten state through a double screw extruder, sending them to a distributor after passing through a melt pump and a filter screen, and alternately stacking them in the order of film layer I and film layer II, extruding them into a film, and performing bidirectional stretching with a stretching ratio of 10 times to obtain an elastomer laminated film.

[0065] Example 3

[0066] The difference from example 1 is that the laminated film comprises film layer I and film layer II at a mass ratio of 1:1.5; film layer I is composed of 50 wt% of polyurethane elastomer, 20 wt% of polyolefin elastomer, and 30 wt% of polyester resin; film layer II is composed of 50 wt% of polyester resin and 50 wt% of polyolefin elastomer; and the rest is the same as example 1.

[0067] Example 4

[0068] The difference from Example 1 is that the laminated film comprises film layer I and film layer II in a mass ratio of 1:1; film layer I is composed of 65wt% polyurethane elastomer and 35wt% polyester resin; film layer II is composed of 35wt% polyurethane elastomer and 65wt% polyolefin elastomer; and the rest is the same as Example 1.

[0069] Example 5

[0070] The difference from Example 4 is that the polyester resin is prepared by the following steps: after hydrolysis of 0.1kg silane coupling agent KH550, it is uniformly sprayed on the surface of 10kg polycarbonate, and the rest is the same as Example 4.

[0071] Example 6

[0072] The difference from Example 5 is that the polyurethane elastomer comprises the following raw materials: 20kg polyether polyol, 30kg isocyanate, 1.8kg catalyst, and 5.5kg acrylic ester copolymer; wherein the polyether polyol is polypropylene glycol; the melt index of the polyurethane elastomer under the condition of 205℃ and 5000g load is 16.456g / 10min;

[0073] Preparation of polyurethane elastomer: mix the polyether polyol with 55% of the total weight of isocyanate, add the catalyst, heat to 60℃ and react for 50min to form a polyurethane prepolymer; dissolve the acrylic ester copolymer and the remaining isocyanate in a dimethyl sulfoxide solution, and add to the polyurethane prepolymer to continue the reaction to obtain the polyurethane elastomer;

[0074] The rest is the same as Example 5.

[0075] Example 7

[0076] The difference from Example 6 is that the polyolefin elastomer comprises the following raw materials: 30kg olefin monomer, 6.5kg emulsion, 3.1kg initiator, 1kg stabilizer, and 2kg filler; wherein the olefin monomer is vinyl acetate, the emulsion is chloroethylene-vinyl acetate copolymer, the stabilizer is cetylphenol polyoxyethylene ether, and the filler is titanium dioxide and ethyl cellulose in a mass ratio of 2:0.8; the melt index of the polyolefin elastomer under the condition of 205℃ and 5000g load is 21.834g / 10min;

[0077] Preparation of polyolefin elastomer: mix the olefin monomer with the stabilizer to obtain a mixture, uniformly disperse the emulsion and the filler in propylene glycol, and then add to the mixture; under the action of the initiator benzoyl peroxide, heat to 70℃ and react for 1.8h to obtain the polyolefin elastomer; and the rest is the same as Example 6.

[0078] Example 8

[0079] The difference from Example 7 is that the emulsion is butyronitrile emulsion of SH-820 type, the filler is calcium carbonate, and the rest is the same as Example 7.

[0080] Comparative Example

[0081] Comparative Example 1

[0082] The difference from Example 7 is that the film layer I is polyester resin, and the rest is the same as Example 7.

[0083] Comparative Example 2

[0084] The difference from Example 7 is that the film layer II is polyolefin elastomer, and the rest is the same as Example 7.

[0085] Comparative Example 3

[0086] The difference from Example 7 is that the mass ratio of the film layer I and the film layer II is 3:1, and the rest is the same as Example 7.

[0087] Comparative Example 4

[0088] The difference from Example 7 is that in the step of preparing the polyurethane elastomer, the polyether polyol, the isocyanate and the catalyst are heated to 60°C to react completely to form the polyurethane elastomer, and the rest of the components are the same as Example 7.

[0089] Comparative Example 5

[0090] The difference from Example 7 is that the polyolefin elastomer is prepared by mixing the olefin monomer and the stabilizer uniformly to obtain a mixture, and under the action of the initiator benzoyl peroxide, the mixture is heated to 70°C to react for 1.8h to obtain the polyolefin elastomer; and the rest of the components are the same as Example 7.

[0091] Performance Test

[0092] The laminated films prepared in Examples 1-8 and Comparative Examples 1-4 are subjected to tear strength test according to ISO 6383-2-2005 “Determination of tear resistance of plastics films and sheets”, visible light transmittance test according to GB / T1040.3-2006 “Determination of tensile properties of plastics-Part 3: test conditions for films and sheets”, and ultraviolet barrier rate test according to ASTM E903, and the results are recorded in Table 1.

[0093] Table 1

[0094]

[0095]

[0096] It can be seen from the combination of Examples 1-8 and Table 1 that the obtained laminated film is a multilayer optical elastomer with effective ultraviolet blocking and high visible light transmittance, good elastic modulus, an elastic modulus of more than 330 MPa, excellent tear strength, a tear strength of more than 70 N / mm, good adhesion to the curved interface, wide application range, and the like.

[0097] It can be seen from the combination of Example 7 and Comparative Examples 1-2 and Table 1 that in Comparative Example 1, the film layer I is a polyester resin, and although there are the same polymer structural units when the film layer I is stacked with the film layer II, the interfacial adhesion between adjacent film layers still has a certain influence, the tear strength of the laminated film decreases, the elastic modulus significantly decreases, and the ultraviolet blocking performance also significantly decreases. In Comparative Example 2, the film layer I is replaced with a polyolefin elastomer, and the tear strength of the laminated film significantly decreases, and the elastic modulus of the material is also affected to a certain extent. This is because at least two of the polyurethane elastomer, the polyolefin elastomer, and the polyester resin are alternately stacked, the film layer I and the film layer II contain the same structural units and are stacked with each other, the precision of the laminated film is higher, the compatibility is better, the elasticity is more excellent, the interfacial adhesion between adjacent film layers is higher, and the product is not prone to interlayer peeling (delamination) during use, and the tear strength is good.

[0098] It can be seen from the combination of Example 7 and Comparative Example 3 and Table 1 that in Comparative Example 3, the amount of the film layer I and the film layer II is unbalanced, which changes the overall composition structure of the obtained laminated film, and significantly reduces the comprehensive performance of the laminated film.

[0099] It can be seen from the combination of Example 7 and Comparative Example 4 and Table 1 that in Comparative Example 4, no acrylate copolymer is added, and the polymerization is completed at one time, and the obtained polyurethane elastomer has poor mechanical properties and elasticity. This is because the polyether polyol and the isocyanate are used as raw materials, and under the action of a catalyst, a prepolymer with a blocked isocyanate group is first formed. The prepolymer has isocyanate groups and polyether segments, and can further react with the acrylate copolymer to form a longer polymer chain. The acrylate copolymer not only has good elasticity, but also can adjust the flowability and viscosity of the material, so that the obtained polyurethane elastomer material has good elasticity and excellent mechanical properties, and endows the laminated film with excellent elastic modulus and improved tear strength.

[0100] It can be seen from the combination of Example 7 and Comparative Example 5 and Table 1 that the comprehensive performance of the laminated film obtained by not using the emulsion and the filler to react in Comparative Example 5 is significantly reduced. This is because the polyolefin monomer is gradually polymerized to form a high molecular polymer during the polymerization reaction using the olefin monomer as the raw material. The emulsion and the stabilizer can reduce the interfacial tension, improve the compatibility with other components, make the olefin monomer more easily form a colloidal emulsion, control the size and distribution of the polymer particles during the polymerization reaction, and obtain a polyolefin elastomer with excellent elasticity and softness. The filler can not only increase the density and uniformity of the material and improve the tear strength of the material, but also reduce the penetration of ultraviolet rays by absorbing and scattering ultraviolet rays, effectively block the ultraviolet rays, and endow the laminated film with good elastic modulus and tear strength, so that it has excellent ultraviolet blocking performance.

[0101] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. An elastomeric laminate film characterized by, The laminated film comprises film layer I and film layer II with a mass ratio of 1:(1-2); the film layer I and the film layer II are alternately laminated by at least two of polyurethane elastomer, polyolefin elastomer and polyester resin; The polyurethane elastomer comprises the following raw materials by weight: polyether polyol 10-25 parts, isocyanate 15-30 parts, catalyst 1-2.5 parts, and acrylic ester copolymer 3-7 parts; The polyolefin elastomer comprises the following raw materials by weight: olefin monomer 20-35 parts, emulsion 4-9 parts, initiator 1-4 parts, stabilizer 0.5-1 part, and filler 1-3 parts; The difference between the refractive indexes of the film layer I and the film layer II is greater than 0.09; The film layer I is composed of 60-75 wt% of polyurethane elastomer and 25-40 wt% of polyester resin; The film layer II is composed of 30-40 wt% of polyurethane elastomer and 70-60 wt% of polyolefin elastomer; The preparation method of the elastomer laminated film comprises the following steps: Preparation of polyurethane elastomer: polyether polyol is mixed with 40-65% of total weight of isocyanate, a catalyst is added, and a polyurethane prepolymer is generated by reaction under heating; acrylic ester copolymer and the remaining isocyanate are dissolved in an organic solvent, and the polyurethane prepolymer is added for further reaction to obtain the polyurethane elastomer; Preparation of polyolefin elastomer: olefin monomer is uniformly mixed with a stabilizer to obtain a mixture, the emulsion and the filler are uniformly dispersed in an aqueous solvent, and then added to the mixture, and the polyolefin elastomer is obtained by reaction under heating with the action of the initiator; The film layer I and the film layer II are alternately laminated, extruded into a film, and bidirectionally stretched to obtain the elastomer laminated film.

2. The elastomeric laminate film of claim 1, wherein: The olefin monomer comprises one of vinyl acetate and vinyl chloride.

3. The elastomeric laminate film of claim 2, wherein: The stabilizer comprises one of octanol polyoxyethylene ether, cetylphenol polyoxyethylene ether and octanol sulfate.

4. The elastomeric laminate film of claim 3, wherein: The emulsion comprises one of vinyl chloride-vinyl acetate copolymer, butadiene rubber emulsion and acrylic emulsion.

5. The elastomeric laminate film of claim 4, wherein: The filler comprises at least one of titanium dioxide, ethyl cellulose and nano-silicon dioxide.

6. The elastomeric laminate film of claim 1, wherein: The polyester resin comprises one of polymethyl methacrylate, polyvinyl acetate and polycarbonate modified by a silane coupling agent.

7. The elastomeric laminate film of claim 1, wherein: The melt index of the polyurethane elastomer at 200-210℃ is 10-20 g / 10min, and the melt index of the polyolefin elastomer at 200-210℃ is 15-25 g / 10min.

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