Composition with matting effect, matte film layer and decorative film

Abstract

The invention relates to a composition with a matting effect, the composition takes microspheres modified by a silane coupling agent as a core and silicon dioxide modified by the silane coupling agent as a shell, and the composition comprises: (1) silicon dioxide with an average particle size of 50-300 nm and a specific surface area of 100-400 m < 2 > / g; (2) microspheres composed of inorganic microspheres with an average particle size of 0.4-1.0 [mu] m and organic microspheres with an average particle size of 0.01-0.1 [mu] m; and (3) an organic silicon resin adhesive. The invention also relates to a matte film layer prepared from the composition. The invention also relates to a decorative film comprising the matte film layer.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, in particular to a composition with matte effect, a matte film layer prepared by using the composition, and a decorative film comprising the matte film layer. Background Art

[0002] This section provides background information related to the present application which does not necessarily constitute prior art.

[0003] In the aviation field, decorative films are needed to protect and decorate the side panels, ceilings and other parts of aircraft. Decorative films used in the aviation field generally need to have properties such as lightweight, flame retardant, and easy to replace, and also need to have good mechanical properties. The base film layer of the decorative film generally uses soft materials such as OPP, BOPP, PP, and PVC, but the above soft materials have problems such as low surface hardness and poor scratch resistance. In order to overcome these problems, the commonly used treatment method is to add a functional film layer on the surface of the base film layer. The existing decorative films used in the aviation field have the following technical problems:

[0004] When an aircraft takes off to a certain altitude, it will face strong sunlight exposure, especially when the aircraft is flying in the stratosphere, the sunlight will shine into the cabin. If the decorative film does not have excellent anti-glare performance, it will concentrate and reflect the sunlight to form a highlight, which has a great impact on the vision of the aircraft pilot. Therefore, the surface of the decorative film is required to have an anti-glare function.

[0005] It also needs to be weather-resistant and yellowing-resistant. Generally speaking, fluorine-containing membrane materials such as PVDF have good weather resistance. However, the compatibility of fluorine-containing materials with general carbon-based polymer materials is limited. Relatively speaking, silicone polymer materials have better compatibility with fluorine-containing membrane materials.

[0006] Terminology

[0007] The term "relative light reflectance" is a value measured at 60° using a micro TRI gloss meter according to the "Standard Test Method for Specular Gloss" in ASTM D523-14. If a film has a relative light reflectance of less than 30, it means that the film has "low gloss".

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

[0009] The term "diffusing filler" refers to spherical or non-spherical porous or non-porous particles with a refractive index less than or equal to 2, in particular less than or equal to 1.8, preferably 1.3 to 1.6, which can be evaluated by contrast elimination. The diffusing fillers are characterized by the following method for the matting ability of the composition containing them: the test composition is coated with a mechanical film applicator at a temperature of 2 mg / cm 2 The composition is spread on a contrast card, and the composition is then dried at 37°C for not less than 12 hours. Its reflection is then measured using a goniometer, and the intensity of the specular reflection at 30° and the intensity of the diffuse reflection at 90° are measured successively. The result is the ratio R between the intensity of the specular reflection and the intensity of the diffuse reflection. The smaller the R value, the greater the proportion of the matting effect provided by the diffuse filler. An R value of less than or equal to 2 generally indicates a matting effect.

[0010] The term "average particle size of silica" refers to a 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 particles of microspheres alone before being added to the composition, and is a volume average particle size measured by a measuring instrument using 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 a matte film layer prepared using the composition can produce diffuse reflection interference and thus have an anti-glare function. Arranging the matte film layer on the surface of a decorative film can give the decorative film an anti-glare function and simultaneously improve the weather resistance of the decorative film.

[0013] To achieve the above object, the present invention adopts the following technical scheme: a composition with a matte effect, wherein the composition has microspheres modified by a silane coupling agent as a core and silicon dioxide modified by a silane coupling agent as a shell, and the core-shell structure can significantly improve the physical strength of the composition while improving the matte effect of the composition. The microspheres and silicon dioxide are modified by a silane coupling agent, which can increase the affinity of the microspheres and silicon dioxide, which is beneficial to improving the stability of the composition and is beneficial to the uniformity of the dispersion of silicon dioxide on the surface of the microspheres. When the microspheres are added to the composition, it is preferred to use expanded microspheres obtained by pre-expanding the unexpanded microspheres by heat treatment or the like.

[0014] The composition comprises:

[0015] (1) The average particle size is 50nm to 300nm and the specific surface area is 100-400m 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) Silicone resin adhesive.

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

[0019] The average particle size of silica affects the loading amount of silica on the surface of the microspheres. If the average particle size is less than 50 nm, agglomerates of silica particles are easily generated. If it exceeds 300 nm, the loading amount of silica on the surface of the microspheres is reduced, thereby reducing the matte effect of the composition.

[0020] The specific surface area of ​​silica will affect the adhesion stability of silica on the surface of microspheres. If the specific surface area is less than 100 m 2 / g, it is difficult to maintain strong adhesion between silica particles and microspheres for a long time, but if it exceeds 400m 2 In one or more embodiments, the composition includes two silicas with different specific surface areas, one of which has a specific surface area of ​​approximately 100 m 2 / g, another silica has a specific surface area of ​​nearly 400m 2 / g.

[0021] The shape of the microspheres is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include spherical, elliptical, polygonal, cubic, rod-like, needle-like, flat, flaky, or amorphous shapes.

[0022] The inorganic microspheres are selected from at least one of aluminum oxide microspheres, magnesium oxide microspheres, glass microspheres, ceramic microspheres, and silicon dioxide microspheres. Preferably, the inorganic microspheres are silicon dioxide 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. 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, the microspheres and silica are modified by a silane coupling agent, and the silane coupling agent can be selected from organic silanes, alkyl silanes, fluorinated silanes, disilazane, etc. Preferably, the silane coupling agent is selected from at least one of γ-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, γ-diethylene triaminopropyl methyl dimethoxysilane, N-2-aminoethyl-3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyl diethoxysilane, γ-glycidyl ether oxygen propyl trimethoxysilane (KH-560), trifluoropropyl methyl dimethoxysilane, perfluorooctyl triethoxysilane, hexadecyl trimethoxysilane, and octyl trimethoxysilane.

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

[0027] Without affecting the technical effects that can be achieved by the composition described in the present invention, the composition of the present invention may contain other external additives other than silicon dioxide, inorganic microspheres, organic microspheres and silicone resin adhesives, examples of which include known external additives such as inorganic particles and organic particles. Among them, preferred are inorganic particles such as titanium dioxide, aluminum oxide, cerium oxide, strontium titanate, calcium carbonate, magnesium carbonate and calcium phosphate, and organic resin particles such as fluorine-containing resin particles, silicone resin particles, and nitrogen-containing resin particles. In addition, for the purpose of hydrophobization, the surface of the external additive can be surface treated with an alkylsilane coupling agent or the like. The external additive is preferably titanium dioxide particles, more preferably titanium dioxide particles surface treated with an alkylsilane coupling agent, and further preferably titanium dioxide particles surface treated with a decylsilane coupling agent. The number average particle size of the external additive is preferably 5nm to 100nm, more preferably 5nm to less than 60nm.

[0028] On the other hand, the present invention also provides a matte film layer prepared by using the above composition, wherein the matte film layer is 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, tensile elongation and tensile strength. The composition has excellent compatibility with the fluoropolymer matrix, and the matte film has high light transmittance and low gloss by adding the composition.

[0029] The matte film layer surface has a relative light reflectance of less than 10, preferably less than 9, more preferably less than 8, and the matte film layer 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 a composition containing inorganic microspheres having a specified average particle size is present in the matte film layer, a large number of cavities or shear yields are generated near the inorganic microspheres dispersed in the fluoropolymer matrix to absorb the energy during impact, so the impact resistance is improved. However, it is found that if only inorganic microspheres are used in the composition, the dispersion uniformity of the composition in the fluoropolymer matrix will be affected. However, if organic microspheres with a lower average particle size and inorganic microspheres with a higher average particle size are used and added to the composition, it is possible to maintain high impact resistance while improving the dispersion uniformity of the composition in the fluoropolymer matrix. The mechanism is still uncertain, and it is speculated as follows: when inorganic microspheres and organic microspheres of different particle sizes and materials are mixed, the agglomeration of inorganic microspheres or organic microspheres is mutually suppressed, and the dispersion state of the composition in the fluoropolymer matrix becomes good.

[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 generally 70 wt % to 90 wt %, and the content of the composition is generally 10 wt % to 30 wt %, within which range a matte film layer with particularly good weather resistance can be obtained.

[0032] Wherein, the fluorine-containing polymer can be selected from polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polyethylene-tetrafluoroethylene (ETFE), fluorinated ethylene-propylene (FEP) or a mixture thereof. Preferably, the fluorine-containing polymer 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. It is further preferred that the weight average molecular weight Mw of the PVDF ranges from 50,000 to 300,000 g / mol, and more preferably from 80,000 to 250,000 g / mol.

[0033] The thickness of the matte film layer can be measured by mechanical scanning according to standard ISO 4593-1993, or by using a scanning electron microscope. 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. The matte film layer can be prepared by dry mixing the components in powder, granular or preferably granulated form, or by melting and mixing the components in a molten state or by melting the dry premix of the components. The preparation process can be carried out in a single-screw or twin-screw extruder, and conventional additives (such as light stabilizers, heat stabilizers, ultraviolet absorbers, free radical scavengers, crosslinking agents, thickeners, leveling agents, rheology modifiers, surfactants, defoamers, dispersants, wetting agents, etc.), auxiliary agents and / or fillers can be directly blended or added later 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, wherein the matte film layer is disposed on the surface of the decorative film, and the matte film layer gives the decorative film a "low gloss" surface appearance, mechanical stability, and very high weathering resistance and mechanical protection. There is no particular limitation, and other layers may be appropriately disposed between the substrate film layer and the matte film layer according to the purpose, such as an antistatic layer, a non-combustible layer, a decorative layer, a heat-conducting layer, etc.

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

[0038] The composition for copolymer or copolymer dispersion can be selected from multiple polymers. Non-limiting examples include polyethylene and / or polypropylene. Except polyethylene and / or polypropylene, or as a replacement of polyethylene and / or polypropylene, this polymer can also include a copolymer, styrene-based polymer or copolymer, polyurethane, polycarbonate, polyamide, fluoroplastic, poly (methyl) acrylate, polyacrylonitrile, polyester or any mixture of the above-mentioned polymers of polyolefin, olefin unsaturated carboxylic acid or unsaturated carboxylic acid derivative outside polyethylene or polypropylene. In some forms, the rete includes one or more ethylene vinyl acetate (EVA) copolymers.

[0039] Although most embodiments of the decorative film include one or more pigments or other colorants or inks in its substrate film layer, it should be noted that the decorative film also includes the use of a substrate film layer that is free of pigment or substantially free of pigment. Such a substrate film layer that is free of pigment is generally transparent or substantially transparent.

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

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

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

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

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

[0045] When the matte film layer is applied to the substrate film layer by an adhesive, the adhesive may include a random copolymer adhesive and / or a block copolymer adhesive, and the adhesive may include a random copolymer adhesive and / or a block copolymer adhesive, as well as natural and synthetic rubber adhesives. Random copolymer adhesives include those based on acrylic acid 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 block copolymers, grafted or radial block copolymers, etc. Preferably, the adhesive is an optically transparent pressure-sensitive adhesive,

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

[0047] This application has the following beneficial effects:

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

[0049] The following describes the invention in conjunction with specific embodiments. DETAILED DESCRIPTION

[0050] It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention.

[0051] [Silicon dioxide]

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

[0053] [Inorganic microspheres]

[0054] The inorganic microspheres used in the embodiments of the present 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 , and the loading amount of the inorganic microspheres loaded with silica particles is 40%-50%.

[0055] [Phenyl polysilsesquioxane microspheres]

[0056] The phenyl polysilsesquioxane microspheres used in the embodiment of the present invention have excellent thermal stability, with an initial decomposition temperature of 480-500° C. in air, and are formed by hydrolysis and polycondensation of phenyl trichlorosilane or phenyl trialkoxysilane under the catalysis of acid or base. The average particle size of the phenyl polysilsesquioxane microspheres is about 0.04 μm to about 0.05 μm.

[0057] [Methyl MQ silicone resin]

[0058] The methyl MQ silicone resin used in the embodiment of the present 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, which is prepared by the following method:

[0061] Step 1: Under nitrogen protection, 9.6 parts by weight of a 2 / g of fumed silica, 2.4 parts by weight of a specific surface area of ​​400m 2 / g of fumed silica, 12 parts by weight of glass microspheres with an average particle size of 0.4 μm, 36 parts by weight of aluminum oxide microspheres with an average particle size of 1.0 μm, 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 raised to 60°C, the reaction was carried out for 4 hours, and then a semi-finished product was obtained by spray drying.

[0062] Step 2: Under nitrogen protection, a mixed solution of KH-560 and trifluoropropylmethyldimethoxysilane (the solvent is toluene, the total weight part of the mixed solution is 0.5, of which the weight part of KH-560 is 0.1, and the weight part of trifluoropropylmethyldimethoxysilane is 0.2) and the semi-finished product obtained in step 1 are evenly mixed, the reaction temperature is increased 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, which is prepared by the following method:

[0065] Step 1: Under nitrogen protection, 12 parts by weight of a 2 / g of fumed silica, 36 parts by weight of ceramic microspheres with an average particle size of 0.4 μm, 12 parts by weight of magnesium oxide microspheres with an average particle size of 1.0 μm, 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°C, the reaction was carried out for 4 hours, and then a semi-finished product was obtained by spray drying.

[0066] Step 2: Under nitrogen protection, a mixed solution of KH-560 and trifluoropropylmethyldimethoxysilane (the solvent is toluene, the total weight part of the mixed solution is 0.5, of which the weight part of KH-560 is 0.1, and the weight part of trifluoropropylmethyldimethoxysilane is 0.2) and the semi-finished product obtained in step 1 are evenly mixed, the reaction temperature is increased 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, which is prepared by the following method:

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

[0070] Step 2: Under nitrogen protection, a mixed solution of KH-560 and trifluoropropylmethyldimethoxysilane (the solvent is toluene, the total weight part of the mixed solution is 0.5, of which the weight part of KH-560 is 0.1, and the weight part of trifluoropropylmethyldimethoxysilane is 0.2) and the semi-finished product obtained in step 1 are evenly mixed, the reaction temperature is increased 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, which is prepared by the following method:

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

[0074] Step 2: Under nitrogen protection, a mixed solution of KH-560 and trifluoropropylmethyldimethoxysilane (the solvent is toluene, the total weight part of the mixed solution is 0.5, of which the weight part of KH-560 is 0.1, and the weight part of trifluoropropylmethyldimethoxysilane is 0.2) and the semi-finished product obtained in step 1 are evenly mixed, the reaction temperature is increased 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, which uses microspheres modified by a silane coupling agent (the microspheres are composed of silica microspheres and phenyl polysilsesquioxane microspheres) as cores, and silica modified by a silane coupling agent as shells, and the silica is loaded on the microspheres by methyl MQ silicone resin. Based on the weight of the composition, the composition includes:

[0077] (1) 15 wt% fumed silica, the specific surface area of ​​the fumed silica is 200 m 2 / g;

[0078] (2) 62.5 wt % silica microspheres, the average particle size of the silica microspheres being 0.6 μm;

[0079] (3) 12.5 wt % phenyl polysilsesquioxane microspheres;

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

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

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

[0083] [Example 6]

[0084] The content of the fluorine-containing polymer is usually 70% to 90% by weight, and the content of the composition is usually 10% to 30% by weight. Within this range, 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] 300 parts by weight of an organic mixed solvent (the organic mixed solvent is prepared by compounding dimethylformamide and butanone in a mass ratio of 3:1) is added to a mixer, 70 parts by weight of PVF pellets are put into the organic mixed solvent, and slowly heated until the PVF pellets are completely dissolved, and then 30 parts by weight of the composition are added, mixed evenly, heated to 70°C, maintained for 40 minutes, and then extruded by film calendaring 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, and the preparation method includes the following steps:

[0089] 300 parts by weight of an organic mixed solvent (the organic mixed solvent is prepared by compounding dimethylformamide and butanone in a mass ratio of 3:1) is added to a mixer, 90 parts by weight of PVDF pellets are put into the organic mixed solvent, and the mixture is slowly heated until the PVDF pellets are completely dissolved. Then, 10 parts by weight of the composition are added, mixed evenly, and heated to 70°C for 50 minutes. The mixture is then extruded 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] 300 parts by weight of an organic mixed solvent (the organic mixed solvent is prepared by compounding dimethylformamide and butanone in a mass ratio of 3:1) is added to a mixer, 55 parts by weight of PVF pellets and 30 parts by weight of PVDF pellets are put into the organic mixed solvent, and slowly heated until the PVF pellets and PVDF pellets are completely dissolved, and then 15 parts by weight of the composition are added, mixed evenly, and heated to 70°C, maintained for 40 minutes, and then extruded by film calendaring 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] 300 parts by weight of an organic mixed solvent (the organic mixed solvent is prepared by compounding dimethylformamide and butanone in a mass ratio of 3:1) is added to a mixer, 30 parts by weight of PVF pellets and 50 parts by weight of PVDF pellets are put into the organic mixed solvent, and slowly heated until the PVF pellets and PVDF pellets are completely dissolved, and then 20 parts by weight of the composition are added, mixed evenly, and heated to 70°C, maintained for 50 minutes, and then extruded by film calendaring 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, and the preparation method includes the following steps:

[0098] 300 parts by weight of an organic mixed solvent (the organic mixed solvent is prepared by compounding dimethylformamide and butanone in a mass ratio of 3:1) is added to a mixer, 30 parts by weight of PVF pellets and 50 parts by weight of PVDF pellets are put into the organic mixed solvent, and slowly heated until the PVF pellets and PVDF pellets are completely dissolved, and then 25 parts by weight of the composition are added, mixed evenly, and heated to 70°C, maintained for 50 minutes, and then extruded by film calendaring 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 Example 8. The decorative film includes a matte film layer, an adhesive layer, a substrate layer, an adhesive layer and a white bottom layer stacked in sequence from top to bottom, and the matte film layer is connected to the substrate layer through the adhesive layer.

[0101] More specifically, the decorative film comprises:

[0102] (1) Matt film layer;

[0103] (2) an adhesive layer, i.e., a pressure-sensitive adhesive (PSA) layer, wherein the thickness of the pressure-sensitive adhesive (PSA) layer is 5-10 μm;

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

[0105] (4) an adhesive layer, i.e., a pressure-sensitive adhesive (PSA) layer, wherein the thickness of the pressure-sensitive adhesive (PSA) layer is 5-10 μm;

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

[0107] [Comparative Examples 1-7]

[0108] Comparative Examples 1-6 all provide a composition, and the specific component parameters are shown in Table 1. The preparation method of the composition provided in Comparative Examples 1-6 is the same as the preparation method of the composition provided in Example 4. The compositions provided in Examples 1-5 all produce an R value 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 provides matting powder OK500 produced by DEGUSS Company.

[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 the preparation method of the matte film layer provided in Example 9. The difference between Comparative Examples 8-14 and Example 9 is only that:

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

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

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

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

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

[0119] The matte film layer provided in Comparative Example 13 uses the composition provided in Comparative Example 6 to replace 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 to replace the composition provided in Example 4.

[0121] The matte film layers provided in Examples 6-10 and the matte film layers provided in Comparative Examples 8-14 were tested as follows:

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

[0123] The matte film layer was cut into a dumbbell shape with a line length of 20 mm and a width of 5 mm, and stretched in the longitudinal direction at a stretching speed of 500 mm / min using a tensile testing machine model RTF-1210 under the conditions of a measuring atmosphere of 25°C and 50% RH to measure the tensile strength of the matte film layer. The results are shown in Table 2.

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

[0125] The matte film layer was tested for impact strength (unnotched specimen) according to the test method described in GB / T 1043.1-2008 Determination of impact properties of simply supported beams of plastics Part 1. The results are shown in Table 2.

[0126] (3) Determination of light transmittance of matte film

[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 relative light reflectance of matte film

[0129] The relative light reflectance is measured according to the test method described in ASTM D523-14 using a BYK Gardiner Micro TRI gloss meter, and the relative light reflectance value is measured at 60°. The results are shown in Table 2.

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

[0131] The guide number was measured using a BYK-mac multi-angle spectrophotometer according to the test method described in ASTM E284-13b, and the guide number value was 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 Guide Number 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] According to the results in Table 2, it can be judged that the matte film layer prepared by using the composition provided by the present invention has an excellent matte effect while having a high light transmittance, and has excellent mechanical properties, which is the result of the synergistic effect of the components in the composition.

[0135] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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 above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A composition with a matte effect, wherein the composition has microspheres modified by a silane coupling agent as a core and silicon dioxide modified by a silane coupling agent as a shell, characterized in that: The composition comprises: The average particle size is 50nm to 300nm and the specific surface area is 100-400m 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; Silicone resin adhesive.

2. The composition according to claim 1, characterized in that Based on the total weight of the composition, the content of the silicon dioxide is 15 wt % to 20 wt %, the content of the microsphere is 75 wt % to 85 wt %, and the content of the silicone resin-based binder is 1 wt % to 10 wt %.

3. The composition according to claim 2, characterized in that The mass ratio of the silicon dioxide to the microspheres is 1:4-5, and the mass ratio of the organic microspheres to the inorganic microspheres is 1:5-7.

4. The composition according to claim 1, characterized in that The silicon dioxide is spherical fumed silicon dioxide.

5. The composition 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 composition according to claim 1, characterized in that The organic microspheres are cross-linked polymer microspheres or sulfur-containing resin microspheres.

7. The composition according to claim 1, characterized in that The organic silicone resin adhesive is methyl MQ silicone resin.

8. A matte film layer, characterized in that: The matte film layer comprises the composition according to any one of claims 1 to 7, the matte film layer is based on a fluorine-containing polymer, and the composition is uniformly dispersed in a fluorine-containing polymer matrix.

9. The matte film layer according to claim 8, characterized in that: The fluorine-containing polymer may be selected from polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene, polyethylene-tetrafluoroethylene, fluorinated ethylene-propylene or a mixture thereof.

10. A decorative film, characterized in that: Comprising the matte film layer as described in claim 8 or 9.

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