Modified polymethyl methacrylate, composition forming the same, and high-barrier water vapor reflective film made therefrom

Abstract

The present invention provides a composition for forming modified polymethyl methacrylate, a composition for forming the same, and a high-barrier water vapor reflective film made thereof. The above-mentioned composition for forming modified polymethyl methacrylate includes polymethyl methacrylate resin, polyketone resin and intercalated modified mica powder. The inventors found that by blending the intercalated modified mica powder with polymethyl methacrylate resin and polyketone resin, on the one hand, the modified polymethyl methacrylate (modified PMMA) formed thereby has good weather resistance, density, wear resistance, tensile strength, etc., and is conducive to reducing the probability of its breakage and pulverization; on the other hand, by mixing in a polyketone resin with better water vapor barrier performance, the modified PMMA also has excellent water vapor barrier performance and extends its service life. On this basis, compared with the existing PMMA, the modified PMMA formed by using the above-mentioned composition has excellent water vapor barrier properties, weather resistance, wear resistance and tensile strength.

Description

Technical Field

[0001] The present invention relates to the fields of polymer materials and film materials, and in particular to modified polymethyl methacrylate, a composition thereof and a high-barrier water vapor reflective film made thereof. Background Art

[0002] Reflective sheeting is a specialized thin film material made using the principle of retroreflection. It is widely used in safety and protection applications, including road and traffic markings, reflective vehicle signs, specialized work clothing, fire signs, railway signs, and mining area signs. Its safety warning effects play a significant role in protecting human life and property. For example, reflective sheeting applied to traffic signs reflects light from vehicle headlights back to the driver, making the warning information visible.

[0003] The text and graphic information on reflective sheeting can be printed using inkjet technology. This technology uses specialized printing equipment to directly print the graphic information onto the reflective sheeting used for signage. This method offers high production efficiency and reliable quality, but the lifespan of reflective sheeting containing graphic information is significantly affected by the protective film. To ensure the graphic information on these reflective sheeting products lasts longer, people have begun applying waterproof coatings or protective layers to the reflective sheeting to protect it from the effects of long-term exposure to harsh environments such as sunlight and rain.

[0004] Currently, polyester materials such as PET (polyethylene terephthalate) and PMMA (polymethyl methacrylate) are commonly used as reflective sheeting. However, these materials have poor water vapor barrier properties. When exposed to rain for a long time, water droplets attached to the surface of the reflective sheeting will erode into the interior of the reflective sheeting, causing the reflective sheeting to lose brightness and significantly shortening the product lifespan. Furthermore, reflective sheeting protective film manufacturers use pure PMMA plastic pultrusion, which also has poor water vapor barrier properties. This results in a short shelf life of the pattern information set on the film and its inability to withstand rain erosion.

[0005] On this basis, it is particularly important to reduce the water vapor transmission rate of the protective film on the reflective sheeting and improve the water vapor barrier performance of the protective film in order to extend the service life of the reflective sheeting. Summary of the Invention

[0006] The main purpose of the present invention is to provide a modified polymethyl methacrylate, a composition thereof, and a high-barrier water vapor reflective film made therefrom, so as to solve the problems of poor water vapor barrier performance, unstable light reflection performance, and poor weather resistance of reflective film products made of polymethyl methacrylate in the prior art.

[0007] In order to achieve the above object, the present invention provides a composition for forming modified polymethyl methacrylate. The composition for forming modified polymethyl methacrylate comprises polymethyl methacrylate resin, polyketone resin and intercalated modified mica powder.

[0008] Furthermore, the composition for forming modified polymethyl methacrylate comprises, by weight, 60 to 80 parts of polymethyl methacrylate resin, 5 to 20 parts of polyketone resin and 1 to 5 parts of intercalated modified mica powder; preferably, as shown in the structure of formula (I), the intercalated modified mica powder is selected from C 10～18 Mica powder modified with alkylammonium bromide, wherein R1 is selected from C 10～18 R2, R3 and R4 are independently selected from C 1～3 Alkyl;

[0009]

[0010] More preferably, the alkylammonium bromide is one or more selected from the group consisting of dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide and octadecyltrimethylammonium bromide.

[0011] Furthermore, the weight average molecular weight of the polymethyl methacrylate resin is 200,000 to 300,000; and the weight average molecular weight of the polyketone resin is 400,000 to 600,000.

[0012] Furthermore, the composition for forming modified polymethyl methacrylate further comprises talc modified with a coupling agent; preferably, the composition for forming modified polymethyl methacrylate further comprises 1 to 5 parts by weight of talc modified with a coupling agent; preferably, the coupling agent used in the preparation of the talc modified with a coupling agent is selected from one or more of the group consisting of silane coupling agents, titanate coupling agents and aluminate coupling agents.

[0013] Furthermore, the composition for forming the modified polymethyl methacrylate further comprises a compatibilizer; preferably, the composition for forming the modified polymethyl methacrylate further comprises 1 to 10 parts of a compatibilizer by weight.

[0014] Furthermore, the compatibilizer is selected from polymethyl methacrylate grafted with maleic anhydride and / or ethylene octene copolymer grafted with maleic anhydride.

[0015] Furthermore, the composition for forming modified polymethyl methacrylate further comprises, by weight: 0.1 to 1 parts of antioxidant and 1 to 6 parts of plasticizer.

[0016] Furthermore, the intercalated modified mica powder has a flaky structure, and the average flaky thickness of the intercalated modified mica powder is 1 to 10 nm, and the diameter is 0.1 to 1 μm.

[0017] In order to achieve the above object, another aspect of the present invention further provides a modified polymethyl methacrylate, which is prepared from the above-mentioned composition for forming polymethyl methacrylate by sequentially undergoing melt extrusion, biaxial stretching and heat setting.

[0018] Another aspect of the present invention provides a high-barrier water vapor reflective film, comprising a substrate layer and a pattern layer disposed on the surface of the substrate layer, wherein the substrate layer comprises a film layer formed of the modified polymethyl methacrylate.

[0019] Applying the technical solution of the present invention, the inventors discovered that blending intercalated modified mica powder with polymethyl methacrylate resin and polyketone resin can, on the one hand, result in a modified polymethyl methacrylate (PMMA) with improved weather resistance, compactness, abrasion resistance, and tensile strength, while also reducing the likelihood of breakage and pulverization. Furthermore, by incorporating a polyketone resin with enhanced vapor barrier properties, the modified PMMA also possesses excellent vapor barrier properties and extends its service life. Consequently, compared to existing PMMA, the modified PMMA formed using this composition exhibits superior vapor barrier properties, weather resistance, abrasion resistance, and tensile strength. DETAILED DESCRIPTION

[0020] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0021] As described in the background art, existing polymethyl methacrylate reflective sheeting products suffer from poor water vapor barrier properties, unstable light reflection properties, and poor weather resistance. To address these technical issues, the present application, in a first aspect, provides a composition for forming modified polymethyl methacrylate. The composition comprises a polymethyl methacrylate resin, a polyketone resin, and intercalated modified mica powder.

[0022] Polymethyl methacrylate (PMMA) resin, as a long-chain polymer compound, possesses advantages such as colorlessness, transparency, high mechanical strength, and chemical resistance. However, its molecular structure contains ester bonds, making it susceptible to water vapor corrosion in high-humidity environments. In intercalation-modified mica powder, organic molecules are inserted between its layers through ion exchange reactions, expanding the interlayer spacing and improving the interlayer microenvironment. This changes the inner and outer surfaces of the layered mica powder from hydrophilic to hydrophobic, enhancing the affinity between the silicate structure and the polymer chains within the mica powder, and reducing the surface energy of the mica powder. This allows for intercalation modification of the mica powder, which further improves its dispersibility during the blending process.

[0023] The inventors discovered that blending intercalated modified mica powder with polymethyl methacrylate resin and polyketone resin can, on the one hand, produce a modified polymethyl methacrylate (PMMA) with improved weather resistance, compactness, abrasion resistance, and tensile strength, while also reducing the likelihood of breakage and pulverization. Furthermore, the addition of a polyketone resin with enhanced vapor barrier properties also imparts excellent vapor barrier properties to the modified PMMA, extending its service life. Consequently, compared to existing PMMA, the modified PMMA formed using this composition exhibits superior vapor barrier properties, weather resistance, abrasion resistance, and tensile strength.

[0024] Because the interlayer spacing of mica powder increases in water, it can undergo intercalation modification. This can be prepared using methods commonly used in the art, such as mixing a modifier with mica powder in water, followed by filtration and drying to obtain the desired intercalated mica powder. The specific type of modifier, dosage, reaction temperature, and other conditions can be adjusted according to actual needs.

[0025] To further improve the water vapor barrier properties and wear resistance of the above-mentioned composition and film layer, the intercalated modified mica powder preferably has a flaky structure, and the average flake thickness of the intercalated modified mica powder is 1 to 10 nm and the diameter is 0.1 to 1 μm. More preferably, the average flake thickness of the intercalated modified mica powder is 8 to 10 nm and the diameter is 0.3 to 0.5 μm.

[0026] Preferably, as shown in formula (I), the intercalated modified mica powder includes but is not limited to C 10～18 Alkyl ammonium bromide modified mica powder; wherein R1 includes but is not limited to C 10～18 R2, R3 and R4 independently include but are not limited to C 1～3 Alkyl;

[0027]

[0028] In order to further enhance the affinity between the intercalated modified mica powder and the resin molecular chain and give full play to the advantages of the wear resistance and water vapor barrier properties of the above-mentioned intercalated modified mica powder, more preferably, the intercalated modified mica powder includes but is not limited to one or more of the group consisting of dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide and octadecyltrimethylammonium bromide.

[0029] In a preferred embodiment, the modified polymethyl methacrylate composition comprises, by weight, 60-80 parts polymethyl methacrylate resin, 5-20 parts polyketone resin, and 1-5 parts intercalated modified mica powder. Compared to other usage ranges, limiting the usage of polymethyl methacrylate resin, polyketone resin, and intercalated modified mica powder within the aforementioned range not only ensures a more suitable viscosity after mixing, facilitating the formation of a uniform film layer, but also further reduces the water vapor transmission rate of the modified PMMA formed, while improving its wear resistance, thereby further enhancing the water vapor barrier performance and service life of the resulting film layer.

[0030] In a preferred embodiment, the weight-average molecular weight of the polymethyl methacrylate resin is 200,000 to 300,000; the weight-average molecular weight of the polyketone resin is 400,000 to 600,000. Compared to other molecular weight ranges, polymethyl methacrylate resins with this molecular weight exhibit better impact resistance, abrasion resistance, and light transmittance, while polyketone resins with this molecular weight exhibit a more suitable viscosity. Using these two resins facilitates adjusting the viscosity of the composition, improving the processing properties of the raw materials and facilitating subsequent melt extrusion and biaxial stretching. Furthermore, selecting organic resins with this molecular weight also improves the density, impact resistance, abrasion resistance, and light transmittance of the resulting modified PMMA, while reducing costs. This results in a more economical modified PMMA material with improved water vapor barrier properties.

[0031] Talc is a polar, water-insoluble substance. When dispersed in a low-polarity organic polymer resin, the difference in polarity between the two leads to poor compatibility, which can cause the mechanical properties of the resin material obtained by directly adding talc to decrease. In order to change the surface properties of talc, improve its compatibility in the resin, and the wear resistance of the subsequently formed film, the composition forming the modified polymethyl methacrylate preferably also includes talc modified with a coupling agent. To further improve the compatibility between the two and the wear resistance of the film, more preferably, the composition forming the modified polymethyl methacrylate also includes 1 to 5 parts by weight of talc modified with a coupling agent.

[0032] In order to better mix the raw materials in the composition and form a uniform and stable composition during subsequent processing, in a preferred embodiment, the composition for forming the modified polymethyl methacrylate also includes a compatibilizer. The addition of a compatibilizer helps improve the mixing uniformity of the inorganic material and the organic resin, thereby helping the modified PMMA to have more stable and uniform overall properties. To ensure more stable and uniform overall properties of the modified PMMA, the composition for forming the modified polymethyl methacrylate preferably also includes 1 to 10 parts by weight of a compatibilizer.

[0033] In a preferred embodiment, compatibilizers include, but are not limited to, polymethyl methacrylate grafted with maleic anhydride and / or ethylene octene copolymer grafted with maleic anhydride. Compared to other compatibilizers, PMMA grafted with maleic anhydride or POE grafted with maleic anhydride, through the bridging effect of maleic anhydride, helps improve the dispersion of inorganic powder materials such as modified mica powder and coupling agent-modified talc in the resin, facilitates the formation of a stable and uniform homogeneous system, and enhances the processability of the mixed raw material system. This results in improved uniformity and surface smoothness of the high-barrier water vapor reflective film ultimately produced from the above composition, thereby enhancing its water vapor barrier performance, wear resistance, and impact resistance.

[0034] To further improve the dispersibility of coupling-agent-modified talc in the resin, modify its surface properties, and enhance its water vapor barrier performance, the coupling agents used in the preparation of the coupling-agent-modified talc preferably include, but are not limited to, one or more of the group consisting of silane coupling agents, titanate coupling agents, and aluminate coupling agents. Using a silane coupling agent to surface-modify the talc further improves its dispersibility during the blending process, significantly enhancing the wear resistance of the modified PMMA. Using a titanate coupling agent to modify talc forms a monomolecular coating on the surface of the unmodified talc, altering its original hydrophilicity and fundamentally changing its surface properties, thereby further enhancing the water vapor barrier performance of the modified PMMA. Due to the unique structure of titanate coupling agents, they enable excellent coupling between talc and organic matter, further enhancing the dispersibility of the talc during mixing and improving the mechanical and water vapor barrier properties of the resulting modified PMMA. Compared with unmodified talc, talc modified with aluminate coupling agents has better hydrophobicity. Therefore, using it to prepare modified PMMA can reduce the contact area between PMMA and water vapor, thereby improving its water vapor barrier performance.

[0035] To reduce environmental and UV damage to the composition and film, an antioxidant can be added to the composition to improve the aging resistance of the modified PMMA. The antioxidant protects the modified polymethyl methacrylate and film from environmental and UV damage during processing and use, improving the aging resistance and weather resistance of the modified polymethyl methacrylate and film. In a preferred embodiment, the composition forming the modified polymethyl methacrylate further comprises, by weight, 0.1 to 1 parts of an antioxidant and 1 to 6 parts of a plasticizer. The antioxidant can be a composite antioxidant, including but not limited to a phosphite / hindered phenol composite antioxidant. The antioxidant exhibits enhanced aging resistance when the weight ratio of phosphite to hindered phenol is 1:1.

[0036] The addition of a plasticizer can facilitate subsequent melt extrusion, biaxial stretching, and heat setting processes of the composition, and the resulting modified polymethyl methacrylate has improved wear resistance and flexibility. Preferably, the plasticizer includes, but is not limited to, a blend of one or more selected from the group consisting of tri-n-butyl citrate, epoxidized soybean oil, triacetin, and epoxy fatty acid methyl esters.

[0037] Compared with other dosage ranges, limiting the dosage of the above-mentioned antioxidants and plasticizers to the above-mentioned range is beneficial to further improve the anti-aging ability of the modified PMMA and the flexibility of the high water vapor barrier film, and extend its service life and weather resistance and other comprehensive properties.

[0038] In a second aspect, the present application provides a modified polymethyl methacrylate, which is prepared by using the above-mentioned composition for forming polymethyl methacrylate as a raw material, and sequentially undergoing melt extrusion, biaxial stretching and heat setting.

[0039] By blending inorganic intercalated modified mica powder with polymethyl methacrylate resin and polyketone resin, the resulting modified polymethyl methacrylate (modified PMMA) exhibits superior weather resistance, compactness, abrasion resistance, and tensile strength, while also reducing the risk of breakage and pulverization. Furthermore, the incorporation of the polyketone resin, which exhibits enhanced vapor barrier properties, also imparts excellent vapor barrier properties to the modified PMMA, extending its service life. Consequently, compared to existing PMMA, the modified PMMA formed using this composition exhibits superior vapor barrier properties, weather resistance, abrasion resistance, and tensile strength.

[0040] The third aspect of the present application provides a high-barrier water vapor reflective film, comprising a substrate layer and a pattern layer arranged on the surface of the substrate layer, wherein the substrate layer comprises a film layer formed of the above-mentioned modified polymethyl methacrylate.

[0041] Since the modified PMMA provided in this application has excellent water vapor barrier properties, weather resistance, wear resistance and tensile strength, it can also obtain good water vapor barrier properties after being made into a high-barrier water vapor reflective film. It has good climate adaptability and can cope with the erosion of the film itself in humid environments such as rain and snow. It has a long service life and its light reflection performance is more stable. At the same time, the above-mentioned reflective film also has good wear resistance.

[0042] The fourth aspect of the present application further provides a preferred method for preparing a high barrier water vapor reflective film:

[0043] (1) adding modified talc powder, intercalated modified mica powder, an optional antioxidant, and an optional plasticizer to PMMA resin and stirring in a three-dimensional mixer for 3 to 10 minutes until the materials are fully mixed, then adding to a mixer and mixing at 160 to 180° C. for 20 minutes, and granulating with an extruder to obtain composition 1;

[0044] (2) adding the above composition 1, polyketone resin, and optional compatibilizer into a high-speed mixer, and mixing at a speed of 1000-2000 r / min for 30 min to obtain composition 2;

[0045] (3) granulating composition 2 in a granulator to obtain composition 3, setting the following process parameters: zone 1 temperature, zone 2 temperature, zone 3 temperature, zone 4 temperature, mold zone 1 temperature, mold zone 2 temperature, mold zone 3 temperature, screw length-to-diameter ratio L / D of 40-50, setting the extrusion pressure of the extruder to 6-8 MPa and the screw speed to 12-15 r / min;

[0046] (4) The pellets of composition 3 are extruded in an extruder and biaxially stretched, and then heat-set and slit to obtain a film with high water vapor barrier.

[0047] The present application is further described in detail below with reference to specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0048] It should be noted that the performance testing methods used in the examples and comparative examples of the present application are as follows:

[0049] The water vapor transmission rate test is carried out in accordance with the method specified in GB / T 21529-2008;

[0050] The wear resistance test is carried out in accordance with the method specified in GB / T 5478-2008;

[0051] Tensile strength is tested according to the method specified in ISO 1184-1983;

[0052] The solvent resistance test is carried out in accordance with the method specified in GB / T 18833-2012; based on the experimental results, it is divided into five levels from 0 to 5, with level 0 being the worst solvent resistance and level 5 being the best solvent resistance.

[0053] The proportions of the components in the examples and comparative examples are shown in Table 1 (parts by weight).

[0054] Table 1

[0055]

[0056] Example 1

[0057] The composition for forming modified PMMA includes, by weight: 70 parts of PMMA resin (LG Company; brand IF850), 15 parts of polyketone resin (Hyosung Company; brand M330), 3 parts of intercalated modified mica powder (self-made), 2 parts of modified talc powder (Shenzhen Haiyang Powder Technology Co., Ltd.; model TY88-20-C), 5 parts of compatibilizer (ethylene octene copolymer grafted with maleic anhydride, DuPont Dow Specialty Polymers Company; model ENGAGE8220), 0.5 parts of antioxidant (phosphite / hindered phenol composite anti-aging agent, Foshan Jieke New Materials Co., Ltd.; model B215) and 4.5 parts of plasticizer (tri-n-butyl citrate).

[0058] The intercalated mica powder is hexadecyltrimethylammonium bromide (HDTMA) intercalated mica powder. The preparation process is as follows: HDTMA (HDTMA:mica powder weight ratio of 1:2) is added dropwise to a suspension of mica powder (Shenzhen Haiyang Powder Technology Co., Ltd.; model HY-TM1) at 35°C with stirring. After 2 hours, the mixture is filtered, and the mica powder is removed. The powder is then washed three times with distilled water, dried under vacuum at 60°C for 3 hours, and ground to obtain the dried intercalated mica powder. Testing indicates that the average flake thickness of the hexadecyltrimethylammonium bromide intercalated mica powder is 8-10 nm, and the diameter is 0.3-0.5 μm.

[0059] The preparation method comprises:

[0060] (1) The modified talc powder, intercalated modified mica powder, antioxidant, and plasticizer in the above-mentioned parts by weight were added to PMMA resin and stirred in a three-dimensional mixer for 60 minutes until the materials were fully mixed. Then, the mixture was added to a mixer and mixed at 180° C. for 20 minutes, and granulated using an extruder to obtain composition 1.

[0061] (2) Add the above composition 1, polyketone resin, and optional compatibilizer into a high-speed mixer and mix at a speed of 2000 r / min for 30 minutes to obtain composition 2.

[0062] (3) Composition 2 was granulated in a granulator to obtain composition 3. The process parameters were set as follows: zone 1 temperature of 120°C, zone 2 temperature of 170°C, zone 3 temperature of 180°C, zone 4 temperature of 200°C, mold zone 1 temperature of 210°C, mold zone 2 temperature of 220°C, mold zone 3 temperature of 220°C, screw aspect ratio L / D of 50, extrusion pressure of 8 MPa, and screw speed of 15 r / min.

[0063] (4) The pellets obtained by the granulation of composition 3 are extruded in an extruder and biaxially stretched, and then heat-set and slit to obtain a high-barrier water vapor reflective film.

[0064] The water vapor permeability of the film was measured to be 6 (m / g224h), the abrasion resistance was 0.03 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 28.8MPa.

[0065] Example 2

[0066] The difference from Example 1 is that the modified PMMA composition includes, by mass, 80 parts PMMA resin, 5 parts polyketone resin, 3 parts intercalated modified mica powder, 2 parts modified talc, 5 parts compatibilizer, 0.5 parts antioxidant, and 4.5 parts plasticizer. The preparation method is the same as that of Example 1.

[0067] The water vapor permeability of the film was measured to be 9 (m / g224h), the abrasion resistance was 0.03 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 27.5MPa.

[0068] Example 3

[0069] The difference from Example 1 is that the modified PMMA composition comprises, by mass fraction, 70 parts PMMA resin, 15 parts polyketone resin, 1 part intercalated modified mica powder, 1 part modified talc powder, 5 parts compatibilizer, 0.5 parts antioxidant, and 3 parts plasticizer. The preparation method is the same as that of Example 1.

[0070] The water vapor permeability of the film was measured to be 10 (m / g224h), the abrasion resistance was 0.08 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 26.4MPa.

[0071] Example 4

[0072] The difference from Example 1 is that, by weight, the composition for forming the modified PMMA includes: 60 parts PMMA resin, 20 parts polyketone resin, 3 parts intercalated modified mica powder, 2 parts modified talc, 5 parts compatibilizer, 0.5 parts antioxidant, and 4.5 parts plasticizer. The preparation method is the same as that of Example 1.

[0073] The water vapor permeability of the film was measured to be 16 (m / g224h), the abrasion resistance was 0.15 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 24.4MPa.

[0074] Example 5

[0075] The difference from Example 1 is that the number of parts of PMMA resin is 50. The preparation method is the same as that of Example 1.

[0076] The water vapor permeability of the film was measured to be 22 (m / g224h), the abrasion resistance was 0.35 (500g, 600r), the solvent resistance level was 3, and the tensile strength was 22.5MPa.

[0077] Example 6

[0078] The difference from Example 1 is that the amount of polyketone resin (Hyosung Corporation; brand M330) is 2 parts. The preparation method is the same as that of Example 1.

[0079] The water vapor permeability of the film was measured to be 18 (m / g224h), the abrasion resistance was 0.18 (500g, 600r), the solvent resistance level was level 3, and the tensile strength was 25.1 MPa.

[0080] Example 7

[0081] The difference from Example 1 is that the amount of intercalated modified mica powder added is 5 parts. The preparation method is the same as that of Example 1.

[0082] The water vapor permeability of the film was measured to be 19 (m / g224h), the abrasion resistance was 0.11 (500g, 600r), the solvent resistance level was 4, and the tensile strength was 23.1 MPa.

[0083] Example 8

[0084] The difference from Example 1 is that the amount of intercalated mica powder added is 0.5 parts. The preparation method is the same as that of Example 1.

[0085] The water vapor permeability of the film was measured to be 32 (m / g224h), the abrasion resistance was 0.09 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 27.1 MPa.

[0086] Example 9

[0087] The difference from Example 1 is that the added intercalated modified mica powder is dodecyltrimethylammonium bromide intercalated modified mica powder. The preparation method is the same as that of Example 1.

[0088] The water vapor permeability of the film was measured to be 7 (m / g224h), the abrasion resistance was 0.04 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 28.1 MPa.

[0089] Example 10

[0090] The difference from Example 1 is that the added intercalation modified mica powder is hexadecyltrimethylammonium bromide intercalation modified mica powder. The preparation method is the same as that of Example 1.

[0091] The water vapor permeability of the film was measured to be 6 (m / g224h), the abrasion resistance was 0.03 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 28.6MPa.

[0092] Example 11

[0093] The difference from Example 1 is that the added intercalated modified mica powder is eicosyltrimethylammonium bromide intercalated modified mica powder. The preparation method is the same as that of Example 1.

[0094] The water vapor permeability of the film was measured to be 9 (m / g224h), the abrasion resistance was 0.06 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 27.3MPa.

[0095] Example 12

[0096] The difference from Example 1 is that the weight average molecular weight of the polymethyl methacrylate resin is 200,000, the manufacturer is LG Company, and the brand is IF850. The preparation method is the same as that of Example 1.

[0097] The water vapor permeability of the film was measured to be 7 (m / g224h), the abrasion resistance was 0.05 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 28.8MPa.

[0098] Example 13

[0099] The difference from Example 1 is that the weight average molecular weight of the polymethyl methacrylate resin is 600,000, the manufacturer is Degussa, and the brand is 8809.) The preparation method is the same as that of Example 1.

[0100] The water vapor permeability of the film was measured to be 8 (m / g224h), the abrasion resistance was 0.12 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 24.5MPa.

[0101] Example 14

[0102] The difference from Example 1 is that the brand of polyketone resin is M330, the molecular weight is 500,000, and the manufacturer is Hyosung Corporation. The preparation method is the same as that of Example 1.

[0103] The water vapor permeability of the film was measured to be 7 (m / g224h), the abrasion resistance was 0.04 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 28.2MPa.

[0104] Example 15

[0105] The difference from Example 1 is that the brand of polyketone resin is M730, the molecular weight is 150,000, and the manufacturer is Hyosung Corporation. The preparation method is the same as that of Example 1.

[0106] The water vapor permeability of the film was measured to be 10 (m / g224h), the abrasion resistance was 0.12 (500g, 600r), the solvent resistance level was 4, and the tensile strength was 23.1 MPa.

[0107] Example 16

[0108] The difference from Example 1 is that the amount of talc powder modified with a coupling agent added is 5 parts. The preparation method is the same as that of Example 1.

[0109] The water vapor permeability of the film was measured to be 8 (m / g224h), the abrasion resistance was 0.11 (500g, 600r), the solvent resistance level was 4, and the tensile strength was 24.5MPa.

[0110] Example 17

[0111] The difference from Example 1 is that the amount of talc powder modified with a coupling agent added is 0.5 parts. The preparation method is the same as that of Example 1.

[0112] The water vapor permeability of the film was measured to be 22 (m / g224h), the abrasion resistance was 0.10 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 21.6MPa.

[0113] Example 18

[0114] The difference from Example 1 is that 10 parts of ethylene octene copolymer grafted with maleic anhydride are added. The preparation method is the same as that of Example 1.

[0115] The water vapor permeability of the film was measured to be 8 (m / g224h), the abrasion resistance was 0.06 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 27.6MPa.

[0116] Example 19

[0117] The difference from Example 1 is that 0.2 parts of ethylene octene copolymer grafted with maleic anhydride is added. The preparation method is the same as that of Example 1.

[0118] The water vapor permeability of the film was measured to be 16 (m / g224h), the abrasion resistance was 0.19 (500g, 600r), the solvent resistance level was level 3, and the tensile strength was 23.6MPa.

[0119] Example 20

[0120] The difference from Example 1 is that 0.1 parts of antioxidant and 6 parts of plasticizer are added. The preparation method is the same as that of Example 1.

[0121] The water vapor permeability of the film was measured to be 7 (m / g224h), the abrasion resistance was 0.04 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 28.2MPa.

[0122] Example 21

[0123] The difference from Example 1 is that 1 part of antioxidant and 1 part of plasticizer are added. The preparation method is the same as that of Example 1.

[0124] The water vapor permeability of the film was measured to be 7 (m / g224h), the abrasion resistance was 0.04 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 28.4MPa.

[0125] Example 22

[0126] The difference from Example 1 is that 0.05 parts of antioxidant and 0.5 parts of plasticizer are added. The preparation method is the same as that of Example 1.

[0127] The water vapor permeability of the film was measured to be 8 (m / g224h), the abrasion resistance was 0.06 (500g, 600r), the solvent resistance level was 5, and the tensile strength was 28.3MPa.

[0128] Comparative Example 1

[0129] Pure polymethyl methacrylate film material purchased from the market (Sichuan Longhua Optoelectronics Film Co., Ltd., model PMMA-813) was selected.

[0130] The water vapor permeability of the film was measured to be 44 (m / g224h), the abrasion resistance was 0.24 (500g, 600r), the solvent resistance level was 4, and the tensile strength was 18.9 MPa.

[0131] Comparative Example 2

[0132] The difference from Example 1 is that the intercalated modified mica powder is not added. The preparation method is the same as that of Example 1.

[0133] The water vapor permeability of the film was measured to be 26 (m / g224h), the abrasion resistance was 0.35 (500g, 600r), the solvent resistance level was level 3, and the tensile strength was 19.5MPa.

[0134] Comparative Example 3

[0135] The difference from Example 1 is that no polyketone resin is added. The preparation method is the same as that of Example 1.

[0136] The water vapor permeability of the film was measured to be 19 (m / g224h), the abrasion resistance was 0.15 (500g, 600r), the solvent resistance level was 4, and the tensile strength was 22.3MPa.

[0137] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0138] Comparison of Examples 1 to 22 with Comparative Examples 1 to 3 shows that, compared with existing PMMA, the modified PMMA formed using the composition provided in this application has excellent water vapor barrier properties, weather resistance, wear resistance and tensile strength.

[0139] Comparing Examples 1 to 8, it can be seen that limiting the amounts of polymethyl methacrylate resin, polyketone resin, and intercalated modified mica powder to the preferred range of the present application can, on the one hand, enable the above-mentioned composition to have a more suitable viscosity after mixing, thereby facilitating the formation of a film layer with uniform properties; on the other hand, it can further reduce the water vapor permeability of the modified PMMA formed thereby, while improving its wear resistance, thereby further improving the water vapor barrier performance and service life of the film layer formed thereby.

[0140] Comparing Examples 1, 9 to 11, it can be seen that limiting the type of the above-mentioned intercalated modified mica powder to the preferred range of this application is beneficial to enhancing the affinity between the intercalated modified mica powder and the resin molecular chain, and giving full play to the advantages of the wear resistance and water vapor barrier properties of the above-mentioned intercalated modified mica powder.

[0141] Comparing Examples 1 and 12 to 15, it can be seen that limiting the molecular weight of the polymethyl methacrylate resin and the polyketone resin to the preferred range of this application is beneficial to further improving the impact resistance, wear resistance and light transmittance of the modified PMMA, and the polyketone resin with the above molecular weight has a more suitable viscosity.

[0142] Comparing Examples 1, 16 and 17, it can be seen that limiting the amount of coupling agent-modified talc to the preferred range of this application can improve the compatibility of the coupling agent-modified talc in the resin and the wear resistance of the subsequently formed film layer.

[0143] By comparing Examples 1, 18, and 19, it can be seen that limiting the amount of the compatibilizer to the preferred range of the present application is beneficial to significantly improve the dispersion effect of inorganic powder raw materials such as intercalated modified mica powder and coupling agent-modified talc powder in the above-mentioned resin, which is beneficial to forming a stable and uniform cross-linked resin system, improving the processability of the mixed raw material system, and making the high-barrier water vapor reflective film finally prepared from the above-mentioned composition have better uniformity and film surface smoothness, which is beneficial to improving its water vapor barrier performance, wear resistance, and impact resistance.

[0144] Comparison of Examples 1 and 20 to 22 shows that the addition of antioxidants and plasticizers is beneficial to further improving the anti-aging ability of the modified PMMA and the flexibility of the high water vapor barrier film, thereby extending its service life and weather resistance and other comprehensive properties.

[0145] It should be noted that the terms "first," "second," and the like in the specification and claims of this application are used to distinguish similar objects, and are not necessarily used to describe a specific order or precedence. It should be understood that the terms used in this manner are interchangeable where appropriate, so that the embodiments of the application described herein can, for example, be implemented in an order other than that described herein.

[0146] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A composition for forming modified polymethyl methacrylate, characterized in that: The composition for forming modified polymethyl methacrylate comprises, by weight, 60 to 80 parts of polymethyl methacrylate resin, 5 to 20 parts of polyketone resin, 1 to 5 parts of intercalated modified mica powder, and 1 to 10 parts of a compatibilizer; The intercalation modified mica powder is selected from the mica powder intercalation modified by the intercalation modifier shown in formula (I), wherein R1 is selected from C 10～18 R2, R3 and R4 are independently selected from C 1～3 Alkyl; （I）。 2. The composition for forming modified polymethyl methacrylate according to claim 1, wherein The intercalation modifier represented by formula (I) is one or more selected from the group consisting of dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide and octadecyltrimethylammonium bromide.

3. The composition for forming modified polymethyl methacrylate according to claim 1, characterized in that The weight average molecular weight of the polymethyl methacrylate resin is 200,000 to 300,000; the weight average molecular weight of the polyketone resin is 400,000 to 600,000.

4. The composition for forming modified polymethyl methacrylate according to any one of claims 1 to 3, characterized in that The composition for forming modified polymethyl methacrylate further comprises talc modified with a coupling agent.

5. The composition for forming modified polymethyl methacrylate according to claim 4, characterized in that The composition for forming modified polymethyl methacrylate further comprises 1 to 5 parts of talc powder modified with the coupling agent, in parts by weight.

6. The composition for forming modified polymethyl methacrylate according to claim 4, characterized in that The coupling agent used in the preparation process of the coupling agent-modified talc is selected from one or more of the group consisting of silane coupling agents, titanate coupling agents and aluminate coupling agents.

7. The composition for forming modified polymethyl methacrylate according to claim 1, characterized in that The compatibilizer is selected from polymethyl methacrylate grafted with maleic anhydride and / or ethylene octene copolymer grafted with maleic anhydride.

8. The composition for forming modified polymethyl methacrylate according to any one of claims 1 to 3, characterized in that The composition for forming modified polymethyl methacrylate further comprises, by weight: 0.1 to 1 parts of antioxidant and 1 to 6 parts of plasticizer.

9. The composition for forming modified polymethyl methacrylate according to claim 1 or 2, characterized in that The intercalated modified mica powder has a flaky structure, and the average flaky thickness of the intercalated modified mica powder is 1 to 10 nm, and the diameter is 0.1 to 1 μm.

10. A modified polymethyl methacrylate, characterized in that: The modified polymethyl methacrylate is prepared by using the composition for forming modified polymethyl methacrylate according to any one of claims 1 to 9 as a raw material, and sequentially undergoing melt extrusion, biaxial stretching and heat setting.

11. A high barrier water vapor reflective film comprising a substrate layer and a pattern layer disposed on the surface of the substrate layer, characterized in that: The substrate layer includes a film layer formed of the modified polymethyl methacrylate according to claim 10.

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