Composition with matting effect, matt film layer and decorative film

Abstract

The present invention relates to a composition having a matting effect, the composition including, as a core, microspheres modified with a silane coupling agent, and as a shell, silica modified with a silane coupling agent, the composition including: (1) the silica having an average particle diameter of 50 nm to 300 nm and a specific surface area of 100 to 400 m2 / g; (2) the microspheres composed of inorganic microspheres having an average particle diameter of 0.4 to 1.0 μm and organic microspheres having an average particle diameter of 0.01 to 0.1 μm; and (3) a silicone resin-based adhesive. The present invention also relates to a matte film layer prepared using the above composition. The present invention also relates to a decorative film including the above matte film layer.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, and in particular to a composition having a matte effect, a matte film layer prepared using the composition, and a decorative film comprising the matte film layer. Background Technology

[0002] This section provides background information relevant to this application, which does not necessarily constitute prior art.

[0003] In the aviation industry, decorative films are needed to protect and decorate the side panels, ceilings, and other parts of aircraft. Decorative films used in aviation generally need to be lightweight, flame-retardant, and easy to replace, while also possessing good mechanical properties. The base film layer of decorative films typically uses soft materials such as OPP, BOPP, PP, and PVC. However, these soft materials suffer from low surface hardness and poor scratch resistance. To overcome these problems, a common approach is to add a functional film layer to the surface of the base film layer. Existing decorative films used in the aviation industry face the following technical challenges:

[0004] When an aircraft takes off and reaches a certain altitude, it will be exposed to intense sunlight, especially when the aircraft is flying in the stratosphere. When sunlight enters the cabin, if the decorative film does not have excellent anti-glare properties, it will concentrate the reflection of sunlight, creating high brightness. This will have a great impact on the eyesight of the aircraft pilot. Therefore, the surface of the decorative film needs to have anti-glare function.

[0005] Weather resistance and resistance to yellowing are also required. Generally speaking, fluorinated membrane materials such as PVDF have good weather resistance. However, the compatibility of fluorinated materials with general carbon-based polymers is limited. Relatively speaking, organosilicon polymers have better compatibility with fluorinated membrane materials.

[0006] Terminology Explanation

[0007] The term "relative reflectance" is a value measured at 60° using a miniature TRI gloss meter, according to the "Standard Test Method for Specular Gloss" described in ASTM D523-14. A film with a relative reflectance of less than 30 is considered to have "low gloss".

[0008] The term "sparkling index" is a value measured at 15° using a multi-angle spectrophotometer according to the test method described in ASTM E 284-13b. A sparkling index less than 10 indicates that when observed in direct sunlight, the observer will perceive little or no specular reflection or that the test material has almost no "sparkling".

[0009] The term "diffuse filler" refers to spherical or non-spherical porous or non-porous particles with a refractive index less than or equal to 2, particularly less than or equal to 1.8, preferably 1.3 to 1.6, whose refractive index can be evaluated by the contrast elimination method. The extinction ability of compositions containing diffuse fillers is characterized by applying the test composition to a film using a mechanical coating machine at a concentration of 2 mg / cm². 2 The ratio was spread on a comparison card, and the composition was then dried at 37°C for no less than 12 hours. Its reflection was then measured using a corner reflectometer, and the intensity of specular reflection at 30° and diffuse reflection at 90° were measured successively. The result is the ratio R between the intensity of specular reflection and the intensity of diffuse reflection. The smaller the R value, the greater the extinction effect provided by the diffuse filler. An R value less than or equal to 2 usually indicates an extinction effect.

[0010] The term "average particle size of silica" refers to the value obtained by measuring silica particles in a water-alcohol medium using a laser diffraction / scattering particle size analyzer.

[0011] The term "average particle size of microspheres" refers to the size of the microsphere monomer particles before they are added to the composition, which is the volume average particle size determined by a laser diffraction scattering method. Summary of the Invention

[0012] The present invention aims to provide a composition with a matte effect. The surface of the matte film layer prepared using the composition can generate diffuse reflection interference, thereby having an anti-glare function. Placing the matte film layer on the surface of the decorative film can endow the decorative film with anti-glare function and at the same time improve the weather resistance of the decorative film.

[0013] To achieve the above objectives, the present invention adopts the following technical solution: a composition with a matting effect, wherein the composition uses microspheres modified with a silane coupling agent as the core and silica modified with a silane coupling agent as the shell. This core-shell structure significantly improves the physical strength of the composition while enhancing its matting effect. Modifying the microspheres and silica with a silane coupling agent increases the affinity between the microspheres and silica, which is beneficial for improving the stability of the composition and for ensuring uniform dispersion of silica on the surface of the microspheres. When adding microspheres to the composition, it is preferable to use expanded microspheres obtained by pre-expanding unexpanded microspheres through heat treatment or the like.

[0014] The composition comprises:

[0015] (1) The average particle size is 50 nm to 300 nm and the specific surface area is 100-400 nm. 2 / g of the silicon dioxide;

[0016] (2) The microspheres are composed of inorganic microspheres with an average particle size of 0.4-1.0 μm and organic microspheres with an average particle size of 0.01-0.1 μm;

[0017] (3) Organosilicon resin adhesives.

[0018] Among them, silica, inorganic microspheres and organic microspheres are all diffuse fillers.

[0019] The average particle size of silica affects the loading of silica on the surface of microspheres. If the average particle size is less than 50 nm, silica particles are prone to agglomerate. If it exceeds 300 nm, the loading of silica on the surface of microspheres will be reduced, thereby reducing the matting effect of the composition.

[0020] The specific surface area of ​​silica affects the adhesion stability of silica on the surface of microspheres. If the specific surface area is less than 100 m², the adhesion stability will be affected. 2 If the density is / g, it is difficult to maintain strong adhesion between silica particles and microspheres for a long time; however, if it exceeds 400m... 2 If the surface area is less than 1 g, aggregates of silica particles are easily formed. In one or more embodiments, the composition comprises two types of silica with different specific surface areas, one of which has a specific surface area close to 100 μm. 2 / g, another type of silica has a specific surface area close to 400m². 2 / g.

[0021] The shape of the microspheres is not particularly limited and can be appropriately selected according to the purpose. Examples include spherical, elliptical, polygonal, cubic, rod-shaped, needle-shaped, plate-shaped, scale-shaped, or amorphous shapes.

[0022] The inorganic microspheres are selected from at least one of alumina microspheres, magnesium oxide microspheres, glass microspheres, ceramic microspheres, and silica microspheres. Preferably, the inorganic microspheres are silica microspheres.

[0023] The organic microspheres are cross-linked polymer microspheres or sulfur-containing resin microspheres. Preferably, the organic microspheres are phenyl polysilsesquioxane microspheres.

[0024] The silicone resin adhesive can be selected from MQ, MQOH, MDViQ, MMVi, or MMViQ resins or mixtures thereof. Preferably, the silicone resin adhesive is methyl MQ silicone resin, and using methyl MQ silicone resin as an adhesive can improve the stability and physical strength of the core-shell structure of the composition.

[0025] In one or more embodiments, both the microspheres and the silica are modified with a silane coupling agent, which may be selected from organosilanes, alkylsilanes, fluorinated silanes, disilazanes, etc. Preferably, the silane coupling agent is selected from at least one of γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-diethylenetriaminepropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane (KH-560), trifluoropropylmethyldimethoxysilane, perfluorooctyltriethoxysilane, hexadecyltrimethoxysilane, and octyltrimethoxysilane.

[0026] Preferably, based on the weight of the composition, the content of silica is 15% to 20% by weight, the content of microspheres is 75% to 85% by weight, and the content of the silicone resin adhesive is 1% to 10% by weight. Within the above content range, the composition produces an R value of less than or equal to 1.5. It was unexpectedly found that within the above content range, if the following conditions are met: (1) the mass ratio of silica to microspheres is 1:4-5; (2) the mass ratio of organic microspheres to inorganic microspheres is 1:5-7, the composition produces an R value of less than or equal to 1.

[0027] Without affecting the technical effects achievable by the compositions described in this invention, the compositions of this invention may contain additives other than silica, inorganic microspheres, organic microspheres, and organosilicon resin binders. Examples include known additives such as inorganic and organic particles. Preferably, these are inorganic particles such as titanium dioxide, alumina, cerium oxide, strontium titanate, calcium carbonate, magnesium carbonate, and calcium phosphate, and organic resin particles such as fluorinated resin particles, silicone resin particles, and nitrogen-containing resin particles. Furthermore, for hydrophobic purposes, the surface of the additives may be surface-treated using alkylsilane coupling agents, etc. The additives are preferably titanium dioxide particles, more preferably titanium dioxide particles surface-treated with alkylsilane coupling agents, and even more preferably titanium dioxide particles surface-treated with decylsilane coupling agents. The number-average particle size of the additives is preferably from 5 nm to 100 nm, more preferably from 5 nm to less than 60 nm.

[0028] On the other hand, the present invention also provides a matte film layer prepared using the above-described composition, the matte film layer being based on a fluoropolymer, wherein the composition is substantially uniformly dispersed in a fluoropolymer matrix. The matte film layer exhibits excellent outdoor durability, scratch resistance, low gloss, elongation at break, and tensile strength. The composition exhibits excellent compatibility with the fluoropolymer matrix, and the addition of the composition results in a matte film with high light transmittance and low gloss.

[0029] The matte film surface has a relative light reflectance coefficient of less than 10, preferably less than 9, more preferably less than 8, and the matte film surface has a flash index of less than 10, preferably less than 8, more preferably less than 6.

[0030] The inorganic microspheres in the composition have an average particle size of 0.4-1.0 μm, and the organic microspheres in the composition have an average particle size of 0.01-0.1 μm. It is believed that if the composition containing inorganic microspheres with a specified average particle size is present in the matte film layer, numerous cavities or shear yielding will be generated near the inorganic microspheres dispersed in the fluoropolymer matrix, absorbing energy during impact and thus improving impact resistance. However, it has been found that using only inorganic microspheres in the composition affects the dispersion uniformity of the composition in the fluoropolymer matrix. However, if organic microspheres with a lower average particle size and inorganic microspheres with a higher average particle size are added to the composition in combination, high impact resistance can be maintained while improving the dispersion uniformity of the composition in the fluoropolymer matrix. The mechanism is not yet certain, but it is speculated that the presence of inorganic microspheres and organic microspheres with different particle sizes and materials mutually inhibits the aggregation of inorganic microspheres or organic microspheres, resulting in a better dispersion of the composition in the fluoropolymer matrix.

[0031] The exact composition of the polymer matrix in the matte film layer can be adjusted depending on the intended use of the matte film layer. Preferably, based on the weight of the matte film layer, the content of the fluoropolymer is typically 70% to 90% by weight, and the content of the composition is typically 10% to 30% by weight, within which a matte film layer with particularly good weather resistance can be obtained.

[0032] The fluoropolymer may be selected from polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polyethylene-tetrafluoroethylene (ETFE), fluorinated ethylene-propylene (FEP), or mixtures thereof. Preferably, the fluoropolymer is a combination of polyvinylidene fluoride and polyvinyl fluoride, wherein the PVDF polymer used is a transparent, semi-crystalline thermoplastic fluoroplastic, and the PVDF has a high crystalline melting point. When the crystalline melting point of the PVDF is at least 150°C, and more preferably at least 160°C, the heat resistance of the matte film layer is particularly high. Further preferably, the weight-average molecular weight Mw of the PVDF is in the range of 50,000 to 300,000 g / mol, and more preferably 80,000 to 250,000 g / mol.

[0033] The thickness of the matte film layer can be determined by mechanical scanning according to standard ISO 4593-1993, or by scanning electron microscopy. In one or more embodiments, the matte film layer has a total thickness between 1 μm and 300 μm, more preferably between 1 μm and 200 μm, and even more preferably between 5 μm and 100 μm.

[0034] The matte film layer can be prepared at any desired thickness. It can be prepared by dry mixing components in powder, granular, or preferably granulated form, or by melting and mixing the components in a molten state, or by melting a dried premix of the components. The preparation process can be carried out in a single-screw or twin-screw extruder. Conventional additives (e.g., light stabilizers, heat stabilizers, UV absorbers, free radical scavengers, crosslinking agents, thickeners, leveling agents, rheology modifiers, surfactants, defoamers, dispersants, wetting agents, etc.), auxiliaries, and / or fillers can be directly blended or added subsequently as needed.

[0035] On the other hand, the present invention also provides a decorative film comprising the above-mentioned matte film layer.

[0036] The decorative film includes a substrate film layer and a matte film layer. The matte film layer is disposed on the surface of the decorative film, giving it a low-gloss surface appearance, mechanical stability, and very high resistance to weathering and mechanical protection. Without particular limitation, other layers may be appropriately disposed between the substrate film layer and the matte film layer, depending on the purpose; examples include antistatic layers, non-flammable layers, decorative layers, and thermally conductive layers.

[0037] The substrate layer of the decorative film typically comprises: (1) a pigment or pigment dispersion; (2) a copolymer or copolymer dispersion; and (3) polyvinyl chloride (PVC) or a PVC dispersion. The specific proportions of each component can vary. For many embodiments, the film layer comprises about 10% to about 35% pigment dispersion, about 10% to about 20% copolymer dispersion, and about 50% to about 75% PVC dispersion. The pigment dispersion typically includes a plasticizer and may include a solvent. The copolymer dispersion typically includes a solvent. The PVC dispersion typically includes a solvent, plasticizer, and stabilizer to reduce or prevent harmful effects caused by exposure to light and / or heat.

[0038] The components used in the copolymer or copolymer dispersion can be selected from a variety of polymers. Non-limiting examples include polyethylene and / or polypropylene. In addition to polyethylene and / or polypropylene, or as a substitute for polyethylene and / or polypropylene, the polymer may also include polyolefins other than polyethylene or polypropylene, copolymers of olefin unsaturated carboxylic acids or unsaturated carboxylic acid derivatives, styrene-based polymers or copolymers, polyurethanes, polycarbonates, polyamides, fluoroplastics, poly(meth)acrylates, polyacrylonitrile, polyesters, or mixtures of any of the above polymers. In some forms, the film layer comprises one or more ethylene vinyl acetate (EVA) copolymers.

[0039] Although most embodiments of decorative films include one or more pigments or other colorants or inks in their substrate film layer, it should be noted that decorative films also include those using a substrate film layer that is pigment-free or substantially pigment-free, and such pigment-free substrate film layer is typically transparent or substantially transparent.

[0040] In one or more embodiments, the matte film layer is applied to the substrate film layer by a co-extrusion process or a lamination process, or by an extrusion-lamination process, to obtain the decorative film.

[0041] In one or more embodiments, the decorative film includes:

[0042] (1) Polyvinyl chloride (PVC) film layer;

[0043] (2) An adhesive layer, such as a pressure-sensitive adhesive (PSA) layer, on one side of a PVC film;

[0044] (3) The matte film layer connected by an adhesive layer and a PVC film.

[0045] When a matte film layer is applied to a substrate film layer using an adhesive, the adhesive may include random copolymer adhesives and / or block copolymer adhesives, as well as natural and synthetic rubber adhesives. Random copolymer adhesives include those based on acrylic and / or methacrylic acid copolymers, α-olefin copolymers, siloxane copolymers, chloroprene / acrylonitrile copolymers, etc.; block copolymer adhesives may include those based on linear block copolymers (i.e., AB and ABA types), branched block copolymers, star-shaped block copolymers, grafted or radial block copolymers, etc. Preferably, the adhesive is an optically transparent pressure-sensitive adhesive.

[0046] In the aerospace field, the decorative film provided by this invention can be used as a protective film laminated on the main body. The decorative film provided by this invention can also be applied to other fields, such as electronic equipment, construction, labeling, and automotive.

[0047] This application has the following beneficial effects:

[0048] The composition provided by this invention overcomes the problems of low thermal stability and poor compatibility with polymer matrix of existing matting agents. The matte film layer prepared using the composition provided by this invention has excellent matting effect, and also has high mechanical strength, excellent thermal stability and weather resistance.

[0049] The following description is based on specific embodiments. Detailed Implementation

[0050] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0051] Silicon dioxide

[0052] The silica used in this invention is not particularly limited, and examples include fuming silica obtained by combustion, sol-gel silica obtained by wet granulation of alkoxysilanes by adding ammonia to water-alcohol, and hydrophilic or hydrophobic treated fumed silica. However, fumed silica is preferred. The silica used in the embodiments of this invention is spherical fumed silica, and its preparation method includes the following steps: (1) synthesizing silanes SiHCl3 and SiCl4 using conventional methods; (2) fumed silica synthesis: using SiHCl3 and SiCl4 as main raw materials, fumed silica is synthesized using conventional methods. The average particle size of the silica used in the embodiments of this invention is about 180 nm to about 200 nm.

[0053] [Inorganic microspheres]

[0054] The inorganic microspheres used in this embodiment of the invention are commercially available hollow mesoporous microspheres with a spherical structure, which can provide satisfactory mechanical strength, especially high compressive strength, which is greater than 1 MPa / m. 2 Furthermore, the loading of the inorganic microspheres with silica particles is 40%-50%.

[0055] [Phenyl polysilsesquioxane microspheres]

[0056] The phenyl polysilsesquioxane microspheres used in the embodiments of the present invention exhibit excellent thermal stability, with an initial decomposition temperature of 480-500°C in air. They are formed by the hydrolysis and condensation of phenyltrichlorosilane or phenyltrialkoxysilane under the catalysis of acid or alkali. Furthermore, the average particle size of the phenyl polysilsesquioxane microspheres is approximately 0.04 μm to approximately 0.05 μm.

[0057] [Methyl MQ silicone resin]

[0058] The methyl MQ silicone resin used in this embodiment of the invention has an M / Q of 0.8 and a weight-average molecular weight of 2000 g / mol.

[0059] [Example 1]

[0060] This embodiment provides a composition prepared by the following method:

[0061] Step 1: Under nitrogen protection, 9.6 parts by weight of a specific surface area of ​​100 m² 2 / g of fumed silica, 2.4 parts by weight of a specific surface area of ​​400m² 2 / g of fumed silica, 12 parts by weight of glass microspheres with an average particle size of 0.4μm, 36 parts by weight of alumina microspheres with an average particle size of 1.0μm, 8 parts by weight of phenyl polysilsesquioxane microspheres, and 2 parts by weight of methyl MQ silicone resin were mixed evenly. The reaction temperature was increased to 60℃ and the reaction was carried out for 4 hours. Then, the semi-finished product was obtained by spray drying.

[0062] Step 2: Under nitrogen protection, a mixed solution of KH-560 and trifluoropropylmethyldimethoxysilane (solvent is toluene, the total mass of the mixed solution is 0.5, of which the mass of KH-560 is 0.1 and the mass of trifluoropropylmethyldimethoxysilane is 0.2) and the semi-finished product obtained in Step 1 are mixed evenly, the reaction temperature is raised to 60°C, the reaction is carried out for 80 minutes, and then cooled to room temperature to obtain the composition.

[0063] [Example 2]

[0064] This embodiment provides a composition prepared by the following method:

[0065] Step 1: Under nitrogen protection, 12 parts by weight of a specific surface area of ​​200 m² / g... 2 / g of fumed silica, 36 parts by weight of ceramic microspheres with an average particle size of 0.4μm, 12 parts by weight of magnesium oxide microspheres with an average particle size of 1.0μm, 8 parts by weight of phenyl polysilsesquioxane microspheres, and 2 parts by weight of methyl MQ silicone resin were mixed evenly, and the reaction temperature was increased to 60℃ and the reaction was carried out for 4 hours. Then, the semi-finished product was obtained by spray drying.

[0066] Step 2: Under nitrogen protection, a mixed solution of KH-560 and trifluoropropylmethyldimethoxysilane (solvent is toluene, the total mass of the mixed solution is 0.5, of which the mass of KH-560 is 0.1 and the mass of trifluoropropylmethyldimethoxysilane is 0.2) and the semi-finished product obtained in Step 1 are mixed evenly, the reaction temperature is raised to 60°C, the reaction is carried out for 80 minutes, and then cooled to room temperature to obtain the composition.

[0067] [Example 3]

[0068] This embodiment provides a composition prepared by the following method:

[0069] Step 1: Under nitrogen protection, 11 parts by weight of a specific surface area of ​​300 m² / g... 2 / g of fumed silica, 44 parts by weight of silica microspheres with an average particle size of 0.8μm, 8.8 parts by weight of phenyl polysilsesquioxane microspheres, and 3.2 parts by weight of methyl MQ silicone resin were mixed evenly, and the reaction temperature was increased to 60℃ and the reaction was carried out for 3 hours. Then, the semi-finished product was obtained by spray drying.

[0070] Step 2: Under nitrogen protection, a mixed solution of KH-560 and trifluoropropylmethyldimethoxysilane (solvent is toluene, the total mass of the mixed solution is 0.5, of which the mass of KH-560 is 0.1 and the mass of trifluoropropylmethyldimethoxysilane is 0.2) and the semi-finished product obtained in Step 1 are mixed evenly, the reaction temperature is raised to 60°C, the reaction is carried out for 80 minutes, and then cooled to room temperature to obtain the composition.

[0071] [Example 4]

[0072] This embodiment provides a composition prepared by the following method:

[0073] Step 1: Under nitrogen protection, 12 parts by weight of a specific surface area of ​​300 m² / g... 2 / g of fumed silica, 49 parts by weight of silica microspheres with an average particle size of 0.5μm, 7 parts by weight of phenyl polysilsesquioxane microspheres, and 3 parts by weight of methyl MQ silicone resin were mixed evenly, and the reaction temperature was increased to 60℃ and the reaction was carried out for 3 hours. Then, the semi-finished product was obtained by spray drying.

[0074] Step 2: Under nitrogen protection, a mixed solution of KH-560 and trifluoropropylmethyldimethoxysilane (solvent is toluene, the total mass of the mixed solution is 0.5, of which the mass of KH-560 is 0.1 and the mass of trifluoropropylmethyldimethoxysilane is 0.2) and the semi-finished product obtained in Step 1 are mixed evenly, the reaction temperature is raised to 60°C, the reaction is carried out for 80 minutes, and then cooled to room temperature to obtain the composition.

[0075] [Example 5]

[0076] This embodiment provides a composition comprising microspheres modified with a silane coupling agent (the microspheres are composed of silica microspheres and phenyl polysilsesquioxane microspheres) as a core, and silica modified with a silane coupling agent as a shell, wherein the silica is loaded onto the microspheres with methyl MQ silicone resin. Based on the weight of the composition, the composition comprises:

[0077] (1) 15% by weight of fumed silica, with a specific surface area of ​​200 m². 2 / g;

[0078] (2) 62.5% by weight of silica microspheres, with an average particle size of 0.6 μm;

[0079] (3) 12.5% ​​by weight of phenyl polysilsesquioxane microspheres;

[0080] (4) 10% by weight of methyl MQ silicone resin.

[0081] In this embodiment, both silica and microspheres are first modified with a silane coupling agent before forming a composition. The composition is prepared by the following method: under nitrogen protection, fumed silica, silica microspheres, phenyl polysilsesquioxane microspheres and methyl MQ silicone resin are mixed evenly, the reaction temperature is increased to 60°C, the reaction is carried out for 4 hours, and then the composition is obtained by spray drying.

[0082] In this embodiment, both fumed silica and microspheres are modified with silane coupling agents through the following steps: fumed silica (or microspheres) are placed in a mixer, and silane treatment agents (hexadecyltrimethoxysilane and octyltrimethoxysilane dissolved in ethanol) are added under stirring and mixing. The mixture is mixed for 15 to 30 minutes, and then tempered at 100 to 120°C for 1 to 3 hours under a nitrogen protective atmosphere. After cooling to room temperature, the structural modification is completed.

[0083] [Example 6]

[0084] The content of the fluoropolymer is typically 70% to 90% by weight, and the content of the composition is typically 10% to 30% by weight, within which a matte film layer with particularly good weather resistance can be obtained.

[0085] This embodiment provides a matte film layer, which is prepared using the composition provided in Example 1. The preparation method includes the following steps:

[0086] Add 300 parts by weight of organic mixed solvent (the organic mixed solvent is obtained by compounding dimethylformamide and butanone in a mass ratio of 3:1) to a mixer, add 70 parts by weight of PVF granules to the organic mixed solvent, heat slowly until the PVF granules are completely dissolved, then add 30 parts by weight of the composition, mix evenly, heat to 70°C, maintain for 40 min, and then extrude by film calendering to obtain a matte film layer with a thickness of 20 μm.

[0087] [Example 7]

[0088] This embodiment provides a matte film layer, which is prepared using the composition provided in Example 2. The preparation method includes the following steps:

[0089] Add 300 parts by weight of organic mixed solvent (the organic mixed solvent is obtained by compounding dimethylformamide and butanone in a mass ratio of 3:1) to a mixer, add 90 parts by weight of PVDF granules into the organic mixed solvent, heat slowly until the PVDF granules are completely dissolved, then add 10 parts by weight of the composition, mix evenly, heat to 70°C, maintain for 50 min, and then extrude by film calendering to obtain a matte film layer with a thickness of 20 μm.

[0090] [Example 8]

[0091] This embodiment provides a matte film layer, which is prepared using the composition provided in Example 3. The preparation method includes the following steps:

[0092] Add 300 parts by weight of an organic mixed solvent (the organic mixed solvent is obtained by compounding dimethylformamide and butanone in a mass ratio of 3:1) to a mixer. Add 55 parts by weight of PVF granules and 30 parts by weight of PVDF granules to the organic mixed solvent. Slowly heat until the PVF granules and PVDF granules are completely dissolved. Then add 15 parts by weight of the composition, mix evenly, heat to 70°C, and maintain for 40 minutes. Then extrude the mixture through film calendering to obtain a matte film layer with a thickness of 30 μm.

[0093] [Example 9]

[0094] This embodiment provides a matte film layer, which is prepared using the composition provided in Example 4. The preparation method includes the following steps:

[0095] Add 300 parts by weight of an organic mixed solvent (the organic mixed solvent is obtained by compounding dimethylformamide and butanone in a mass ratio of 3:1) to a mixer. Add 30 parts by weight of PVF granules and 50 parts by weight of PVDF granules to the organic mixed solvent. Slowly heat until the PVF granules and PVDF granules are completely dissolved. Then add 20 parts by weight of the composition, mix evenly, heat to 70°C, and maintain for 50 minutes. Then extrude the mixture through film calendering to obtain a matte film layer with a thickness of 30 μm.

[0096] [Example 10]

[0097] This embodiment provides a matte film layer, which is prepared using the composition provided in Example 5. The preparation method includes the following steps:

[0098] Add 300 parts by weight of an organic mixed solvent (the organic mixed solvent is obtained by compounding dimethylformamide and butanone in a mass ratio of 3:1) to a mixer. Add 30 parts by weight of PVF granules and 50 parts by weight of PVDF granules to the organic mixed solvent. Slowly heat until the PVF granules and PVDF granules are completely dissolved. Then add 25 parts by weight of the composition, mix evenly, heat to 70°C, and maintain for 50 minutes. Then extrude the mixture through film calendering to obtain a matte film layer with a thickness of 25 μm.

[0099] [Example 11]

[0100] This embodiment provides a decorative film, which includes the matte film layer provided in Embodiment 8. The decorative film includes a matte film layer, an adhesive layer, a substrate layer, an adhesive layer and a white base layer stacked sequentially from top to bottom. The matte film layer is connected to the substrate layer through the adhesive layer.

[0101] More specifically, the decorative film includes:

[0102] (1) Matte film layer;

[0103] (2) Adhesive layer, namely pressure-sensitive adhesive (PSA) layer, the thickness of pressure-sensitive adhesive (PSA) layer is 5-10μm;

[0104] (3) Substrate layer, i.e. PVC layer, the thickness of which is 50-100μm;

[0105] (4) Adhesive layer, namely pressure-sensitive adhesive (PSA) layer, the thickness of which is 5-10 μm;

[0106] (5) White base layer: The white base layer is used to cover the base color and can reflect external light to protect the substrate layer. The thickness of the white base layer is 20-30μm.

[0107] [Comparative Examples 1-7]

[0108] Comparative Examples 1-6 each provide a composition, and the specific component parameters are shown in Table 1. The preparation methods of the compositions provided in Comparative Examples 1-6 are the same as those of the composition provided in Example 4. The compositions provided in Examples 1-5 all produce an R value of less than or equal to 1, the compositions provided in Comparative Examples 2-3 all produce an R value of 1.6-1.7, and the compositions provided in Comparative Examples 1 and Comparative Examples 5-6 produce an R value of 1.9-2.

[0109] Comparative Example 7 uses OK500 matting powder manufactured by DEGUSS.

[0110] Table 1

[0111]

[0112] [Comparative Examples 8-14]

[0113] Comparative Examples 8-14 all provide a matte film layer. The preparation method of the matte film layer provided in Comparative Examples 8-14 is the same as that of the matte film layer provided in Example 9. The only difference between Comparative Examples 8-14 and Example 9 is that:

[0114] The matte film layer provided in Comparative Example 8 uses the composition provided in Comparative Example 1 instead of the composition provided in Example 4;

[0115] The matte film layer provided in Comparative Example 9 uses the composition provided in Comparative Example 2 instead of the composition provided in Example 4;

[0116] The matte film layer provided in Comparative Example 10 uses the composition provided in Comparative Example 3 instead of the composition provided in Example 4;

[0117] The matte film layer provided in Comparative Example 11 uses the composition provided in Comparative Example 4 instead of the composition provided in Example 4;

[0118] The matte film layer provided in Comparative Example 12 uses the composition provided in Comparative Example 5 instead of the composition provided in Example 4;

[0119] The matte film layer provided in Comparative Example 13 uses the composition provided in Comparative Example 6 instead of the composition provided in Example 4;

[0120] The matte film layer provided in Comparative Example 14 uses the matting powder OK500 provided in Comparative Example 7 instead of the composition provided in Example 4.

[0121] The matte film layers provided in Examples 6-10 and Comparative Examples 8-14 were subjected to the following tests:

[0122] (1) Determination of tensile strength of matte film layer

[0123] The matte film was cut into dumbbell shapes with a marked length of 20 mm and a width of 5 mm. Under the conditions of 25°C and 50% RH, it was stretched along its length using an RTF-1210 tensile testing machine at a tensile speed of 500 mm / min to determine the tensile strength of the matte film. The results are shown in Table 2.

[0124] (2) Determination of the impact resistance of matte film layer

[0125] The impact strength of the matte film layer was tested according to the test method described in GB / T 1043.1-2008 Determination of Impact Properties of Simply Supported Beams of Plastics Part 1 (unnotched specimen). The results are shown in Table 2.

[0126] (3) Measurement of the transmittance of matte film layer

[0127] The light transmittance of the matte film layer was tested according to the test method described in GB / T 2410-2008 Determination of Light Transmittance and Haze of Transparent Plastics. The results are shown in Table 2.

[0128] (4) Determination of the relative light reflectance of matte film layer

[0129] The relative reflectance was measured using a BYK Gardiner miniature TRI gloss meter according to the test method described in ASTM D523-14, with the relative reflectance values ​​measured at 60°. The results are shown in Table 2.

[0130] (5) Determination of the flash index of matte film layer

[0131] The flash index was measured using a BYK-mac multi-angle spectrophotometer according to the test method described in ASTM E284-13b, with the flash index value measured at 15°. The results are shown in Table 2.

[0132] Table 2

[0133] Tensile strength (MPa) <![CDATA[Impact resistance (KJ / m 2 )]]> Light transmittance (%) Relative light reflectance Flash Index Example 6 175 53 95.8 7.7 5.2 Example 7 171 55 94.9 7.6 4.8 Example 8 173 50 93.6 7.3 4.3 Example 9 180 58 94.8 7.5 4.7 Example 10 169 50 92.5 6.8 4.0 Comparative Example 8 164 48 79.8 16.5 15.4 Comparative Example 9 150 41 82.5 9.9 9.6 Comparative Example 10 153 43 84.7 9.7 9.9 Comparative Example 11 105 28 88.2 8.1 7.8 Comparative Example 12 131 46 77.1 19.5 16.8 Comparative Example 13 134 42 80.6 14.3 12.6 Comparative Example 14 102 26 90.8 9.4 9.1

[0134] Based on the results in Table 2, it can be determined that the matte film layer prepared using the composition provided by the present invention has excellent matting effect while having high light transmittance, and also has excellent mechanical properties. This is the result of the synergistic effect of the components in the composition.

[0135] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0136] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A matte film layer, characterized in that, The matte film layer comprises a composition having a matting effect, the matte film layer is based on a fluoropolymer, and the composition is uniformly dispersed in a fluoropolymer matrix; The composition comprises microspheres modified with silane coupling agent as the core and silica modified with silane coupling agent as the shell, and includes: The average particle size is 50 nm to 300 nm and the specific surface area is 100-400 m². 2 / g of the silicon dioxide; The microspheres are composed of inorganic microspheres with an average particle size of 0.4-1.0 μm and organic microspheres with an average particle size of 0.01-0.1 μm, wherein the inorganic microspheres are hollow mesoporous microspheres with a spherical structure and the organic microspheres are phenyl polysilsesquioxane microspheres; Organosilicon resin adhesives.

2. The matte film layer according to claim 1, characterized in that, Based on the total weight of the composition, the content of silica is 15% to 20% by weight, the content of microspheres is 75% to 85% by weight, and the content of silicone resin binder is 1% to 10% by weight; the total content of silica, microspheres and silicone resin binder is 100% by weight.

3. The matte film layer according to claim 2, characterized in that, The mass ratio of silica to microspheres is 1:4-5, and the mass ratio of organic microspheres to inorganic microspheres is 1:5-7.

4. The matte film layer according to claim 1, characterized in that, The silica is spherical fumed silica.

5. The matte film layer according to claim 1, characterized in that, The inorganic microspheres are selected from at least one of aluminum oxide microspheres, magnesium oxide microspheres, glass microspheres, ceramic microspheres, and silicon dioxide microspheres.

6. The matte film layer according to claim 1, characterized in that, The silicone resin adhesive is methyl MQ silicone resin.

7. The matte film layer according to claim 1, characterized in that, The fluoropolymer may be selected from polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene, polyethylene-tetrafluoroethylene, fluorinated ethylene-propylene, or mixtures thereof.

8. A decorative film, characterized in that, Includes the matte film layer as described in claim 1 or 7.

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