WO2018196162A1 - 一种曲面保护膜及其涂布覆合方法和成型方法 - Google Patents

一种曲面保护膜及其涂布覆合方法和成型方法 Download PDF

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Publication number
WO2018196162A1
WO2018196162A1 PCT/CN2017/092080 CN2017092080W WO2018196162A1 WO 2018196162 A1 WO2018196162 A1 WO 2018196162A1 CN 2017092080 W CN2017092080 W CN 2017092080W WO 2018196162 A1 WO2018196162 A1 WO 2018196162A1
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layer
coating
mold
pet release
protective film
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PCT/CN2017/092080
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English (en)
French (fr)
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蓝志锋
施明
张建伟
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蓝志锋
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/723—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the invention relates to the technical field of protective films, in particular to a curved protective film, a coating coating method thereof and a molding method.
  • the popularity of 2.5D curved phones and 3D curved phones is getting higher and higher. From the latest machines released in 2015-2016, the arc-faced mobile phone occupancy rate is close to 90%. Moreover, from the increased data and some statistical information, it can be judged that the curved mobile phone is a trend of development, and the market share will continue to increase. With the rapid development of mobile phones, existing mobile phone protective films have become more and more difficult to meet the needs of consumers. In order to cater to the development of curved mobile phones, curved mobile phone protective films have appeared one after another.
  • the existing curved protective film mainly includes three categories: TPU+acrylic adhesive film, hot bending PET film, and hot bending tempered glass film.
  • TPU+Acrylic adhesive film TPU material belongs to soft film series, the whole is soft, not straight enough, resulting in inaccurate alignment during filming, high requirements on filming method; and, acrylic adhesive has high viscosity, poor fluidity, need for filming Auxiliary exhaust is assisted by the corresponding scratch card, which affects the overall film experience;
  • PET is used as the substrate, lacking other hardened layer design, the surface hardness of the product is low, the whole is less than 3H (test according to JIS 5600-5-4:1999), the product has poor durability;
  • Hot-bending tempered glass film high cost, easy to break the edge, due to the overall rigidity of the glass, the tolerance value existing in the hot bending process can not be compensated by the corresponding rubber layer, there will be no glue phenomenon in the middle of the product, affecting Control sensitivity.
  • one of the objects of the present invention is to provide a curved surface protective film which has high hardness and good stability after being attached to a curved mobile phone, and can be perfectly matched with a curved screen, and is durable and scratch resistant. Provides more stable, effective and comprehensive protection for curved phone screens; and easy to film and experience.
  • Another object of the present invention is to provide a coating and coating method for a curved surface protective film, which has the advantages of simple process, few steps and safe operation.
  • the third object of the present invention is to provide a method for forming a curved protective film, which is simple in process, safe in operation, and low in cost.
  • a curved protective film comprising a first PET release film, a first hardened layer, a substrate layer, a second hardened layer, a silica gel layer and a fluorinated silicone release layer laminated in this order from top to bottom;
  • the first PET release film includes a PET release film body and a first adhesive layer disposed under the PET release film body.
  • the first hardened layer and the second hardened layer are both urethane acrylic resin layers;
  • the substrate layer is a PET substrate, a PMMA substrate, a PC substrate, or the substrate layer is PMMA And a composite substrate of PC;
  • the first adhesive layer is acrylic glue.
  • the first PET release film has a thickness of 40-60 ⁇ m; the first hardened layer and the second hardened layer each have a thickness of 15-20 ⁇ m; the substrate layer has a thickness of 125-300 ⁇ m; The thickness of the silica gel layer is 50-70 ⁇ m; the thickness of the fluorinated silicone release layer is 40-60 ⁇ m.
  • the substrate layer is a PET substrate having a thickness of 125-188 ⁇ m; and at a peeling speed of 300 mm/min, the silicone layer has a peel strength of more than 100 g/25 mm.
  • a coating and coating method for a curved surface protective film which comprises cascading from top to bottom a first PET release film, a first hardened layer, a substrate layer, a second hardened layer, a silica gel layer and a fluorinated silicone release layer; the coating and coating method comprises:
  • a first coating step taking a substrate layer, respectively coating a first resin and a second resin on a top surface and a bottom surface of the substrate layer, wherein the first resin and the second resin are cured to form a first a hardened layer and a second hardened layer;
  • a first lamination step taking a first PET release film, the first PET release film comprising a PET release film body, and a first adhesive layer disposed under the PET release film body;
  • the release film body is a top surface, and the first adhesive layer is adhered to the top surface of the first hardened layer;
  • a second coating step coating a layer of silica gel on the bottom surface of the second hardened layer, and curing the silica gel to form a silica gel layer;
  • a second coating step attaching a fluorinated silicone release layer to the bottom surface of the silica gel layer; thereby finally obtaining the curved protective film.
  • the first resin and the second resin are both urethane acrylic resin; coating is performed by a roll coating method, and the rotation speed of the coating roller is 20-40 m/min.
  • the feed rate of the substrate layer is 3-30 m/min; after the coating is finished, curing treatment is performed in combination with oven drying and ultraviolet light irradiation, thereby obtaining the first hardened layer and the second hardened layer.
  • coating is performed by roll coating
  • the aging treatment is performed.
  • the coating roller is a ceramic oblique toothed anilox roller; in the curing process, first drying in an oven, followed by ultraviolet light irradiation; the temperature of the oven is 50-100 ° C , drying time is 2-4min; the power of the ultraviolet lamp is 80-100W/cm, and the irradiation time is 3-5s;
  • the coating roller is an anilox roller; curing treatment is carried out at 120 ° C, the time is 120-150 s;
  • the ripening treatment was carried out as follows: standing at room temperature for 72 h or at 50 ° C for 24 h.
  • a method for forming a curved protective film comprising: a first PET release film, a first hardened layer, a substrate layer, a second hardened layer, a silica gel layer, and a fluorinated silicone laminated in this order from top to bottom a release layer; the molding method comprises the following steps:
  • Laminating a second PET release film taking two second PET release films, respectively coating two of the second PET release films on the top surface of the first PET release film and the fluorination a semi-finished product is obtained on the bottom surface of the silicone release layer;
  • the mold comprises an upper mold and a lower mold, and after inserting the semi-finished product of a preset size into the lower mold, covering the upper mold;
  • Heating the mold placing the mold into the first temperature increasing tank, the second temperature increasing tank and the third temperature increasing tank, wherein the temperature of the first temperature increasing tank is 140-180 ° C, and the temperature of the second temperature increasing tank 170-220 ° C, the temperature of the third temperature increasing tank is 170-220 ° C; the storage time of the mold in the first temperature increasing tank, the second temperature increasing tank and the third temperature increasing tank are both 5-15min;
  • Pressing the mold pressing the upper mold downwardly using a pressing device, the pressing speed is 50-500 cm/min, and the pressing time is 2-10 min;
  • Cooling the mold maintaining the mold at -30-0 ° C for 2-10 min;
  • Molding opening the mold, taking out the material, tearing off the two second PET release films; thereby finally obtaining the curved protective film.
  • the second PET release film has a melting point of greater than 180 ° C and a thickness of 40-60 ⁇ m; and at 150 ° C for 30 min of heat shrinkage test conditions, the transverse shrinkage of the second PET release film is ⁇ 2 , longitudinal shrinkage ⁇ 0.2;
  • the upper mold and the lower mold are both graphite molds; and the heat transfer tubes are disposed in the wall surfaces of the upper mold and the lower mold.
  • the forming method is performed in a tunnel furnace, the tunnel furnace includes a running rail, the initial end of the running rail is provided with a mold inlet, and the end end thereof is provided with a mold outlet; in the running direction of the rail, in the running a first temperature increasing tank, a second temperature increasing tank, a third temperature increasing tank, a press forming box and a freezing box are arranged in sequence on the track; the first temperature increasing tank, the second temperature increasing tank and the third temperature increasing tank are both A heater is disposed; the lower pressure molding box is provided with a lower pressure cylinder; and the first temperature increasing tank, the second temperature increasing tank, the third temperature increasing tank, the lower pressure molding box and the freezer are all wrapped with heat insulating cotton.
  • the curved protective film provided by the present invention has a hardened layer provided on both upper and lower sides of the substrate layer. If only one hardened layer is provided, the internal stress is excessive during the hardening process, resulting in curling of the protective film;
  • the double-sided hardening method can double-face the internal stress during the hardening process and keep the protective film as straight as possible. Also, double-sided hardening can increase the hardness of the protective film. After double-sided hardening treatment, the surface of the material can reach 6H-9HS hardness under the pressure of 750g (test according to JIS 5600-5-4:1999), and tested at a rate of 60 times/min with #0000 steel wool under the pressure of 1kg. , anti-friction can reach more than 2000 times, scratch-resistant and wear-resistant, long life.
  • the curved protective film provided by the present invention has a PET release layer disposed on the first hardened layer, the surface is smooth, and does not affect the touch screen experience; and the silicone layer is disposed on the second hardened layer to improve the final sticker of the product. Stability; and silica gel has good fluidity and is easy to vent.
  • the coating and coating method of the curved surface protective film provided by the invention has the advantages of simple process, few steps and safe operation.
  • the method for forming the curved surface protective film provided by the invention is simple in process, safe in operation, and low in cost.
  • FIG. 1 is a schematic structural view of a curved protective film provided by the present invention.
  • FIG. 2 is a schematic structural view of a curved protective film provided by the present invention when placed in a mold during molding;
  • FIG 3 is a schematic structural view of a tunnel furnace used in forming a curved protective film according to the present invention.
  • a curved protective film comprising a first PET release film 40, a first hardened layer 20, a substrate layer 10, a second hardened layer 30, a silica gel layer 50, and fluorine laminated in this order from top to bottom.
  • the curved protective film provided by the invention has a hardened layer on both upper and lower sides of the substrate layer. If only one hardened layer is provided, the internal stress is too large during the hardening process, resulting in curling of the protective film;
  • the method can double-face the internal stress during the hardening process and keep the protective film as straight as possible.
  • double-sided hardening can increase the hardness of the protective film. After double-sided hardening treatment, the surface of the material can reach 6H-9HS hardness under the pressure of 750g (test according to JIS 5600-5-4:1999), and tested at a rate of 60 times/min with #0000 steel wool under the pressure of 1kg. , anti-friction can reach more than 2000 times, scratch-resistant and wear-resistant, long life.
  • the curved protective film provided by the invention solves the problem of poor stability and experience of the traditional protective film-fitting curved mobile phone, and at the same time improves the durability and functionality of the laminated curved protective film, etc.
  • the trend of adapting to curved mobile phones provides more stable, effective and comprehensive protection for curved mobile phone screens.
  • this product provides a good solution for the further development of the mobile phone protective film industry.
  • the applied materials, equipment utilization, processing methods, product concepts, etc. are all a new research and development direction, and provide solutions to existing problems in the industry. .
  • the first hardened layer and the second hardened layer are both urethane acrylic resin layers.
  • the urethane acrylate resin further contains a small amount of other components such as urethane or siloxane, that is, components corresponding to the additive auxiliary, and these components do not have a major hardness effect in the hardened layer.
  • the substrate layer is a PET substrate, a PMMA substrate, a PC substrate, or the substrate layer is a composite substrate of PMMA and PC.
  • a thermoplastic material has properties of heat softening and cooling hardening, is easily formed by hot bending in a range of thickness of 125 to 300 ⁇ m, and has low resilience.
  • the coating step on the substrate can be replaced with a method of coating the AB glue.
  • the first adhesive layer is an acrylic adhesive. After the hardened layer is formed, the surface of the material is smooth, and in order to prevent the occurrence of bubbles and silica gel transfer phenomenon, an acrylic adhesive type PET release film is used.
  • the first PET release film has a thickness of 40-60 ⁇ m; the first hardened layer and the second hardened layer each have a thickness of 15-20 ⁇ m; the substrate layer has a thickness of 125-300 ⁇ m; and the thickness of the silica gel layer is 50-70 ⁇ m; the thickness of the fluorinated silicone release layer is 40-60 ⁇ m.
  • the substrate layer is a PET substrate having a thickness of 125-188 ⁇ m.
  • the substrate of the thickness is less resilience during the test, and is easier to control, and can be better coated with the high-viscosity aid. Curved screen.
  • the gel peel strength of the silica gel layer is greater than 100 g/25 mm under the conditions of a peeling speed of 300 mm/min. That is to use high-viscosity silica gel to form a silica gel layer, high-viscosity silica gel can improve production The final fit stability of the product; and the silica gel has good fluidity and is easier to vent.
  • the hot-bent-formed protective film is mainly a lower buckle that can be pressed according to the shape of the cover of the mobile phone, but it still needs high adhesiveness to assist the arc position, one is to stick to the screen, and the other is to use high viscosity.
  • the gel property improves the overall stability and effectively prevents the shape of the product from rebounding.
  • a coating and coating method for a curved protective film comprising: a first PET release film, a first hardened layer, a substrate layer, a second hardened layer, a silica gel layer and a fluorinated organic layer laminated in this order from top to bottom Silicon release layer; coating and coating method includes:
  • a first coating step taking a substrate layer, respectively coating a first resin and a second resin on a top surface and a bottom surface of the substrate layer, wherein the first resin and the second resin are cured to form a first hardened layer and a second hardened layer Floor;
  • the first laminating step taking the first PET release film, the first PET release film comprises a PET release film body, and the first adhesive layer disposed under the PET release film body; the top of the PET release film body a surface, the first adhesive layer is adhered to the top surface of the first hardened layer;
  • a second coating step coating a layer of silica gel on the bottom surface of the second hardened layer, and curing the silica gel to form a silica gel layer;
  • the second laminating step attaching the fluorinated silicone release layer to the bottom surface of the silica gel layer; after the aging treatment, the curved protective film is finally obtained.
  • the first resin and the second resin are both urethane acrylic resin; coating by roll coating, the rotation speed of the coating roller is 20-40 m/min, the substrate layer The feeding speed is 3-30m/min, under which the coating with good hardness and light transmittance can be obtained; after the coating is finished, the curing process is combined with oven drying and ultraviolet light irradiation, thereby Obtaining a first hardened layer and a second hardened layer;
  • coating is performed by roll coating
  • the aging treatment is performed.
  • the coating roller in the first coating step, is a ceramic helical toothed anilox roller; in the curing process, first drying in an oven, followed by ultraviolet light irradiation; the temperature of the oven is 50-100 ° C, The drying time is 2-4 min; the power of the ultraviolet lamp is 80-100 W/cm, and the irradiation time is 3-5 s; in the second coating step, the coating roller is an anilox roller; the curing treatment is performed at 120 ° C for a time of 120-150s;
  • the ripening treatment was carried out as follows: standing at room temperature for 72 h or at 50 ° C for 24 h.
  • a method of forming a curved protective film comprising a first PET release film 40, a first hardened layer 20, a substrate layer 10, a second hardened layer 30, a silica gel layer 50, and fluorine laminated in this order from top to bottom.
  • the silicone release layer 60; the molding method comprises the following steps:
  • the second PET release film 70 is covered (as shown in FIG. 2): two second PET release films 70 are taken, and two second PET release films 70 are respectively attached to the first PET release film 40.
  • a semi-finished product is obtained;
  • the mold includes an upper mold and a lower mold, and according to the required model, the semi-finished product is cut into corresponding sizes by a laser device, and the cut semi-finished product is placed in the lower mold, and then the upper mold is according to the groove and the lower mold. Covering; at this time, since the material has not softened, the upper mold and the lower mold cannot be pressed;
  • Heating the mold placing the mold into the first heating chamber, the second heating chamber and the third heating chamber in sequence, the temperature of the first heating chamber is 140-180 ° C, and the temperature of the second heating chamber is 170-220 ° C, The temperature of the third temperature increasing tank is 170-220 ° C; the storage time of the mold in the first heating chamber, the second heating chamber and the third heating chamber is 5-15 min; at this time, in the three heating chambers, the material starts. Softening, affected by the gravity of the upper mold, the gap between the molds will become smaller and smaller;
  • Pressing the mold press the mold down with the pressing device, the pressing speed is 50-500cm/min, and the pressing time is 2-10min; that is, the pressing speed is slowed down to avoid damage to the mold and material.
  • the lower mold is completely coincident;
  • the pressing device is kept under the pressure state and enters the -30-0 ° C condition with the mold, and is kept for 2-10 min;
  • Molding Open the mold, take out the material, and tear off the two second PET release films; thus finally obtaining a curved protective film.
  • the second PET release film has a melting point greater than 180 ° C and a thickness of 40-60 ⁇ m; and at 150 ° C for 30 min under heat shrinkage test conditions, the transverse shrinkage of the second PET release film is ⁇ 2, The longitudinal shrinkage is ⁇ 0.2. That is, the second PET release film is a high temperature resistant PET release film. After the product is formed by hot bending, it needs to be torn off. When the product is officially shipped, there is no second PET release film with high temperature resistance.
  • the second PET release film is mainly for preventing excessive deformation of the material during the hot bending process, reducing the hot pressing mold/external foreign matter pressing out the indentation or pressing point of the material, and maintaining the cleanness and flatness of the material.
  • a release agent is sprayed on the surfaces of the upper mold and the lower mold, and after the release agent is dried, it is wiped with a dust-free cloth, and then the semi-finished product is placed in the lower mold.
  • the upper mold and the lower mold are both graphite molds, and a graphite mold with a pressure resistance of 135 (Mpa), a bending resistance of 65 (Mpa), a bulk density of 1.92, and a hardness of 67 (HSD);
  • the graphite mold is light in weight and has a specific gravity. It is 1/5 of copper; it has good processing performance, no burr after machining, and is easy to be used for manual mold repair; graphite has a melting point of 3850 ⁇ 50°C, a boiling point of 4250°C, and a small thermal expansion coefficient.
  • a heat pipe is disposed in the wall surfaces of the upper mold and the lower mold, so that the material in the mold is better heated and the molding is better.
  • the mold is made for different types of curved mobile phones, and the average value of the rebound bias is calculated through multiple hot bending/cooling tests.
  • the rebound value is 15-35°; the mold rest is performed according to the above parameters, so that the curved portion of the mold is recessed by 20-40°; thereby the mold tolerance is maximized to offset the rebound coefficient of the material.
  • the die gap between the upper mold and the lower mold is set according to the thickness of the pre-formed material, for example, the mold gap between the upper mold and the lower mold can be set to 200-550 ⁇ m.
  • the forming method is carried out in a tunnel furnace.
  • the tunnel furnace includes a running rail 80.
  • the initial end of the running rail 80 is provided with a mold inlet 81, and the end end thereof is provided with a mold outlet 82.
  • a mold taking portion 88 is disposed; in the running direction of the rail 80, a first temperature increasing tank 83, a second temperature increasing tank 84, a third temperature increasing tank 85, a press forming box 86, and a freezing box 87 are sequentially disposed on the rail 80 ( a rapid cooling zone); a heater is provided in each of the first temperature increasing tank 83, the second temperature increasing tank 84, and the third temperature increasing tank 85, and has a separate temperature control; a lower pressure cylinder is disposed in the lower pressure forming box 86; 83.
  • the second temperature increasing tank 84, the third temperature increasing tank 85, the lower pressing forming box 86 and the freezing box 87 are all wrapped with heat insulating cotton to maximize the stability of the temperature.
  • the first coating step taking a PET substrate layer having a thickness of 125 ⁇ m, and applying a urethane acrylic resin having a thickness of 18 ⁇ m on the top surface and the bottom surface of the PET substrate by a roll coating method, and the coating roller is a ceramic oblique toothed mesh.
  • the speed of the roller and the coating roller is 40 m/min, and the feeding speed of the PET substrate is 30 m/min; after the urethane acrylic resin is cured, the first hardened layer and the second hardened layer are formed; and this is combined with oven drying and ultraviolet light irradiation. Curing in two ways, the oven temperature is 50-100 ° C, the drying time is 2-4min; the power of the ultraviolet lamp is 80-100W/cm, and the irradiation time is 3-5s;
  • a first covering step taking a first PET release film of a thickness of 50 ⁇ m and attaching it to the top surface of the first hardened layer;
  • the second coating step coating a 50 ⁇ m silica gel on the bottom surface of the second hardened layer by a roll coating method, and the coating roller is an anilox roller;
  • the silica gel used is a high-viscosity silica gel at a peeling speed of 300 mm/min.
  • the peeling strength of the silica gel layer is greater than 100 g / 25 mm; then curing treatment is carried out at 120 ° C for 120 s to form a silica gel layer;
  • a second laminating step laminating a fluorinated silicone release layer having a thickness of 50 ⁇ m on the bottom surface of the silica gel layer; and then aging at room temperature for 72 hours to obtain a first semi-finished product;
  • Laminating the second PET release film taking two second PET release films having a thickness of 50 ⁇ m, respectively, on the top surface of the first PET release film and the bottom surface of the fluorinated silicone release layer to obtain a second semi-finished product;
  • the second PET release film is resistant to temperature of 180 ° C;
  • the second semi-finished product is cut into corresponding dimensions by laser equipment to obtain the third semi-finished product;
  • the forming equipment comprises a tunnel furnace, the tunnel furnace comprises a running track, the initial end of the running track is provided with a mold inlet, and the ending end is provided with a die outlet; in the track running direction, a first heating box is sequentially arranged on the running track a second temperature increasing tank, a third temperature increasing tank, a lower pressure forming box and a freezing box; a lower pressing cylinder is arranged in the lower forming forming box, and the lower pressing cylinder can enter the freezing box along the running track;
  • the mold is a graphite mold, including the upper mold and the lower mold; first, spray the release agent on the surface of the upper mold and the lower mold, after the release agent is dried, wipe with a dust-free cloth, and then put the third semi-finished product Putting into the lower mold, covering the upper mold;
  • the mold enters the running track from the mold inlet, and then passes through the first heating tank,
  • the second heating chamber and the third heating chamber the temperature of the first heating chamber is 180 ° C, the temperature of the second heating chamber is 220 ° C, the temperature of the third heating chamber is 170 ° C;
  • the graphite mold is in the first heating chamber, the second heating
  • the storage time in the tank and the third heating tank are both 15 min;
  • Pressing the mold When the mold completely passes through all the heating boxes, it enters the lower pressing forming box, and the lower pressing cylinder is pressed down the mold, the pressing speed is 50cm/min, and the pressing time is 10min;
  • Cooling mold the lower pressing cylinder is kept under pressure and enters the freezer together with the mold, and the temperature of the freezer is -30 ° C for 2 min;
  • Mold out the mold comes out of the freezer and goes to the die exit with the running track.
  • the mold is warmed up, the material in the mold is taken out, and the two second PET release films are torn off; A curved protective film is obtained.
  • Embodiment 2 is different from Embodiment 1 in that: the thickness of the first PET release film is 40 ⁇ m; the thickness of the PET substrate is 188 ⁇ m; the thickness of the first hardened layer is 15 ⁇ m, and the thickness of the second hardened layer is 20 ⁇ m; The thickness of the fluorinated silicone release layer is 60 ⁇ m;
  • the ripening treatment was carried out as follows: it was allowed to stand at 50 ° C for 24 h.
  • Embodiment 3 is different from Embodiment 1 in that, in the first coating step, the rotation speed of the coating roller is 20 m/min, and the feed rate of the PET substrate is 3 m/min;
  • the high-viscosity silica gel is cured at 120 ° C for 150 s to form a silica gel layer;
  • the temperature of the first temperature increasing tank is 140 ° C, and the temperature of the second temperature increasing tank is 170 ° C, the temperature of the third heating chamber is 220 ° C; the storage time of the graphite mold in the first heating chamber is 15 min, and the storage time in the second heating chamber and the third heating chamber is 5 min;
  • the pressing speed is 500 cm/min, and the pressing time is 2 min;
  • the lower pressing cylinder In the step of cooling the mold, the lower pressing cylinder is kept under the pressed state and enters the freezer together with the mold, and the temperature of the freezer is 0 ° C for 10 min.
  • Comparative Example 1 differs from Example 1 in that the mold is a steel mold.
  • Comparative Example 2 is different from Example 1 in that the silica gel layer is not formed by curing of high-viscosity silica gel, and the silica gel of Comparative Example 2 has a peeling strength of less than 100 g/25 mm at a peeling speed of 300 mm/min, and silica gel.
  • the coating thickness was 30 ⁇ m.
  • the curved surface protective films obtained in the examples 1-3 can well match the curved screen, the fitting degree is good, and the scratch-resistant and wear-resistant, no rebound and lift-up phenomenon, the first embodiment is the best implementation. example.
  • the curved protective film of Comparative Example 1 is prepared by using a steel mold.
  • the steel mold has high manufacturing cost and large mold weight, which makes the upper mold easy to compress the material; the steel mold has high expansion property, which causes the material to be hot-bent. Insufficient precision affects fit.
  • the finished product after molding the adhesiveness of the silicone layer is insufficient, and it is impossible to fit the screen of the mobile phone, and a serious material lifting phenomenon occurs in the arc position.

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Abstract

一种曲面保护膜，包括从上往下依次层叠的第一PET离型膜(40)、第一硬化层(20)、基材层(10)、第二硬化层(30)、硅胶层(50)和氟化有机硅离型层(60)；其中，第一PET离型膜(40)包括PET离型膜本体，以及设置在PET离型膜本体下方的第一胶层。该曲面保护膜硬度大，贴合曲面手机后稳定性好，能够与曲面屏幕完美贴合，耐用耐刮，为曲面手机屏幕提供更稳定、有效以及全面的保护；并且容易贴膜，体验性好。还公开了一种曲面保护膜的涂布覆合方法，工艺简单，步骤少，操作安全。又公开了一种曲面保护膜的成型方法，工艺简单，操作安全简单，成本低。

Description

一种曲面保护膜及其涂布覆合方法和成型方法 技术领域
本发明涉及一种保护膜技术领域，尤其涉及一种曲面保护膜及其涂布覆合方法和成型方法。
背景技术
2.5D曲面手机和3D曲面手机的普遍性越来越高，从2015年—2016年发布的旗舰机中可知，弧面手机占有率接近90％。而且从增涨的数据以及一些统计信息中可判断，曲面手机的是大潮流的发展趋势，市场占有率依然会持续增加。随着手机日新月异的发展，现有的手机保护膜已越来越难以满足消费者的需求了。为了迎合曲面手机的发展，曲面手机保护膜相继出现。现有的曲面保护膜主要包括三大类：TPU+亚克力胶贴膜、热弯PET贴膜、热弯钢化玻璃贴膜。
但是，上述的曲面保护膜存在以下缺陷：
(1)TPU+亚克力胶贴膜：TPU材料属于软膜系列，整体柔软，不够挺直，导致贴膜期间对位不准确，对贴膜手法要求高；并且，亚克力胶粘度高，流动性差，贴膜时需要借助相应的刮卡辅助排气，影响了整体的贴膜体验性；
(2)热弯PET贴膜：采用PET为基材，缺乏其他硬化层设计，产品表面硬度低，整体小于3H(测试依据JIS 5600-5-4：1999)，产品耐用性差；
(3)热弯钢化玻璃贴膜：成本高，边缘易破碎，由于玻璃整体刚硬，导致热弯过程中存在的公差值无法用相应的胶层来弥补，产品中部会出现无胶现象，影响操控灵敏度。
发明内容
为了克服现有技术的不足，本发明的目的之一在于提供一种曲面保护膜，该曲面保护膜硬度大，贴合曲面手机后稳定性好，能够与曲面屏幕完美贴合，耐用耐刮，为曲面手机屏幕提供更稳定、有效以及全面的保护；并且容易贴膜，体验性好。
本发明的目的之二在于提供一种曲面保护膜的涂布覆合方法，工艺简单，步骤少，操作安全。
本发明的目的之三在于提供一种曲面保护膜的成型方法，工艺简单，操作安全简单，成本低。
本发明的目的之一采用如下技术方案实现：
一种曲面保护膜，包括从上往下依次层叠的第一PET离型膜、第一硬化层、基材层、第二硬化层、硅胶层和氟化有机硅离型层；其中，所述第一PET离型膜包括PET离型膜本体，以及设置在所述PET离型膜本体下方的第一胶层。
进一步地，所述第一硬化层和所述第二硬化层均为聚氨酯丙烯酸树脂层；所述基材层为PET基材、PMMA基材、PC基材，或者，所述基材层为PMMA和PC的复合基材；所述第一胶层为亚克力胶。
进一步地，所述第一PET离型膜的厚度为40-60μm；所述第一硬化层和所述第二硬化层的厚度均15-20μm；所述基材层的厚度为125-300μm；所述硅胶层的厚度为50-70μm；所述氟化有机硅离型层的厚度为40-60μm。
进一步地，所述基材层为PET基材，其厚度为125-188μm；在剥离速度为300mm/min的条件下，所述硅胶层的剥离强度大于100g/25mm。
本发明的目的之二采用如下技术方案实现：
一种曲面保护膜的涂布覆合方法，所述曲面保护膜包括从上往下依次层叠 的第一PET离型膜、第一硬化层、基材层、第二硬化层、硅胶层和氟化有机硅离型层；所述涂布覆合方法包括：
第一涂布步骤：取基材层，在所述基材层的顶面和底面分别涂布第一树脂和第二树脂，所述第一树脂和所述第二树脂固化后，形成第一硬化层和第二硬化层；
第一覆合步骤：取第一PET离型膜，所述第一PET离型膜包括PET离型膜本体，以及设置在所述PET离型膜本体下方的第一胶层；以所述PET离型膜本体为顶面，所述第一胶层与所述第一硬化层的顶面贴合；
第二涂布步骤：在所述第二硬化层的底面涂布一层硅胶，硅胶固化后，形成硅胶层；
第二覆合步骤：在所述硅胶层的底面贴覆氟化有机硅离型层；从而最终得到所述曲面保护膜。
进一步地，在所述第一涂布步骤中，所述第一树脂和所述第二树脂均为聚氨酯丙烯酸树脂；采用辊涂方式进行涂布，涂布辊的转速为20-40m/min，所述基材层的进料速度为3-30m/min；涂布结束后，结合烘箱干燥和紫外光照射这两种方式进行固化处理，从而获取所述第一硬化层和所述第二硬化层；
在所述第二涂布步骤中，采用辊涂方式进行涂布；
在所述第二覆合步骤中：贴覆所述氟化有机硅离型层后，进行熟成处理。
进一步地，在所述第一涂布步骤中，所述涂布辊为陶瓷斜齿形网纹辊；固化处理时，首先进行烘箱干燥，然后进行紫外光照射；烘箱的温度为50-100℃，干燥时间为2-4min；紫外灯的功率为80-100W/cm，照射时间3-5s；
在所述第二涂布步骤中，所述涂布辊为网纹辊；在120℃下进行固化处理，时间为120-150s；
在所述第二覆合步骤中，熟成处理的操作如下：在常温下放置72h，或在50℃的条件下放置24h。
本发明的目的之三采用如下技术方案实现：
一种曲面保护膜的成型方法，所述曲面保护膜包括从上往下依次层叠的第一PET离型膜、第一硬化层、基材层、第二硬化层、硅胶层和氟化有机硅离型层；所述成型方法包括以下步骤：
覆合第二PET离型膜：取两张第二PET离型膜，分别把两张所述第二PET离型膜贴覆在所述第一PET离型膜的顶面和所述氟化有机硅离型层的底面上，得到半成品；
放入模具：所述模具包括上模具和下模具，把预设尺寸的所述半成品放入所述下模具内后，盖合所述上模具；
加热模具：把所述模具放入依次放入第一升温箱、第二升温箱和第三升温箱内，所述第一升温箱的温度为140-180℃，所述第二升温箱的温度为170-220℃，所述第三升温箱的温度为170-220℃；所述模具在所述第一升温箱、所述第二升温箱和所述第三升温箱内的保存时间均为5-15min；
下压模具：使用下压设备往下压所述上模具，下压速度为50-500cm/min，下压时间为2-10min；
冷却模具：把所述模具至于-30-0℃的条件下，保持2-10min；
出模：打开所述模具，取出材料，撕掉两张所述第二PET离型膜；从而最终得到所述曲面保护膜。
进一步地，所述第二PET离型膜的熔点大于180℃，其厚度为40-60μm；在150℃，30min的热收缩测试条件下，所述第二PET离型膜的横向收缩率≤2，纵向收缩率≤0.2；
所述上模具和所述下模具均为石墨模具；所述上模具和所述下模具的壁面内均设置有导热管。
进一步地，所述成型方法在隧道炉中进行，所述隧道炉包括运行轨道，所述运行轨道的初始端设置有模具入口，其终止端设置有模具出口；沿轨道运行方向，在所述运行轨道上依次设置有第一升温箱、第二升温箱、第三升温箱、下压成型箱和冷冻箱；所述第一升温箱、所述第二升温箱和所述第三升温箱内均设置有加热器；所述下压成型箱内设置有下压气缸；所述第一升温箱、第二升温箱、第三升温箱、下压成型箱和冷冻箱外均包裹有保温棉。
相比现有技术，本发明的有益效果在于：
(1)本发明所提供的曲面保护膜，在基材层的上下两侧均设置有硬化层，如果只设一层硬化层，会导致硬化过程中内应力过大，导致保护膜卷曲；而双面硬化的方式能够双面抵消硬化过程中的内应力，保持保护膜整体平直。并且，双面硬化能够提升保护膜的硬度。双面硬化处理后，材料表面在750g的压力下可达6H-9HS硬度(测试依据JIS 5600-5-4：1999)，在1kg的压力下用#0000钢丝绒在60次/min的速率测试，耐摩擦可达2000次以上，耐刮耐磨，寿命长。
(2)本发明所提供的曲面保护膜，在第一硬化层上设置PET离型层，表面光滑，不会影响触屏体验；在第二硬化层上设置硅胶层，可提高产品最终的贴合稳定性；且硅胶流动性较好，易于排气。
(3)本发明所提供的曲面保护膜的涂布覆合方法，工艺简单，步骤少，操作安全。
(4)本发明所提供的曲面保护膜的成型方法工艺简单，操作安全简单，成本低。
附图说明
图1为本发明所提供的曲面保护膜的结构示意图；
图2为本发明所提供的曲面保护膜在成型时放入模具时的结构示意图；
图3为本发明所提供的曲面保护膜成型时使用的隧道炉的结构示意图。
图中：10、基材层；20、第一硬化层；30、第二硬化层；40、第一PET离型膜；50、硅胶层；60、氟化有机硅离型层；70、第二PET离型膜；80、轨道；81、模具入口；82、模具出口；83、第一升温箱；84、第二升温箱；85、第三升温箱；86、下压成型箱；87、冷冻箱；88、取模处。
具体实施方式
下面，结合附图以及具体实施方式，对本发明做进一步描述，需要说明的是，在不相冲突的前提下，以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。
如图1所示，一种曲面保护膜，包括从上往下依次层叠的第一PET离型膜40、第一硬化层20、基材层10、第二硬化层30、硅胶层50和氟化有机硅离型层60；其中，第一PET离型膜40包括PET离型膜本体，以及设置在PET离型膜本体下方的第一胶层。
本发明所提供的曲面保护膜，在基材层的上下两侧均设置有硬化层，如果只设一层硬化层，会导致硬化过程中内应力过大，导致保护膜卷曲；而双面硬化的方式能够双面抵消硬化过程中的内应力，保持保护膜整体平直。并且，双面硬化能够提升保护膜的硬度。双面硬化处理后，材料表面在750g的压力下可达6H-9HS硬度(测试依据JIS 5600-5-4：1999)，在1kg的压力下用#0000钢丝绒在60次/min的速率测试，耐摩擦可达2000次以上，耐刮耐磨，寿命长。
本发明所提供的曲面保护膜，解决了传统保护膜贴合曲面手机的稳定性差、体验性的问题，同时提升贴合曲面保护膜的耐用性、功能性等问题，以更 好的适应曲面手机的发展趋势，为曲面手机屏幕提供更加稳定、有效以及全面的保护。同时，该产品为手机保护膜行业的进一步发展提供良好的方案，所应用的材料、设备利用、加工方式、产品理念等都是一个全新的研发方向，同时为行业内的现有问题提供解决方向。
作为进一步的实施方式，第一硬化层和第二硬化层均为聚氨酯丙烯酸树脂层。其中聚氨酯丙烯酸树脂内还含有氨基甲酸乙酯、硅氧烷等少量其他成分，即相当于添加剂辅助类的成分，这些成分在硬化层中不起主要的硬度作用的。
作为进一步的实施方式，基材层为PET基材、PMMA基材、PC基材，或者，基材层为PMMA和PC的复合基材。此类热塑性材料，具有受热软化、冷却硬化的性能，在125-300μm厚度的范围内容易热弯成型，且反弹性小。但是，如果采用PMMA基材、PC基材，或者，采用PMMA和PC的复合基材时，在基材上的涂布步骤可以换成贴覆AB胶的方式。
作为进一步的实施方式，第一胶层为亚克力胶。形成硬化层后，材料的表面较光滑，为防止存在气泡和硅胶转移现象发生，采用亚克力胶型PET离型膜。
作为进一步的实施方式，第一PET离型膜的厚度为40-60μm；第一硬化层和第二硬化层的厚度均15-20μm；基材层的厚度为125-300μm；硅胶层的厚度为50-70μm；氟化有机硅离型层的厚度为40-60μm。
作为进一步的实施方式，基材层为PET基材，其厚度为125-188μm，此厚度的基材在测试过程中发现反弹性较小，较易控制，同时配合高粘胶辅助可较好覆合弧面屏幕。
作为进一步的实施方式，在剥离速度为300mm/min的条件下，硅胶层的胶剥离强度大于100g/25mm。即采用高粘硅胶形成硅胶层，高粘硅胶可提高产 品最终的贴合稳定性；且硅胶流动性较好，更易于排气。热弯成型的保护膜主要是成型后可按手机盖板的形状对应的下扣，但是依然需要高粘胶性对弧度位置进行辅助性贴合，一是贴住屏幕，二则是利用高粘胶性提高整体稳定性，有效防止产品的形状反弹现象。
一种曲面保护膜的涂布覆合方法，曲面保护膜包括从上往下依次层叠的第一PET离型膜、第一硬化层、基材层、第二硬化层、硅胶层和氟化有机硅离型层；涂布覆合方法包括：
第一涂布步骤：取基材层，在基材层的顶面和底面分别涂布第一树脂和第二树脂，第一树脂和第二树脂固化后，形成第一硬化层和第二硬化层；
第一覆合步骤：取第一PET离型膜，第一PET离型膜包括PET离型膜本体，以及设置在PET离型膜本体下方的第一胶层；以PET离型膜本体为顶面，第一胶层与第一硬化层的顶面贴合；
第二涂布步骤：在第二硬化层的底面涂布一层硅胶，硅胶固化后，形成硅胶层；
第二覆合步骤：在硅胶层的底面贴覆氟化有机硅离型层；熟成处理后，从而最终得到曲面保护膜。
作为进一步的实施方式，在第一涂布步骤中，第一树脂和第二树脂均为聚氨酯丙烯酸树脂；采用辊涂方式进行涂布，涂布辊的转速为20-40m/min，基材层的进料速度为3-30m/min，在此条件下能获得硬度和透光性均较好的涂层；涂布结束后，结合烘箱干燥和紫外光照射这两种方式进行固化处理，从而获取第一硬化层和第二硬化层；
在第二涂布步骤中，采用辊涂方式进行涂布；
在第二覆合步骤中：贴覆氟化有机硅离型层后，进行熟成处理。
作为进一步的实施方式，在第一涂布步骤中，涂布辊为陶瓷斜齿形网纹辊；固化处理时，首先进行烘箱干燥，然后进行紫外光照射；烘箱的温度为50-100℃，干燥时间为2-4min；紫外灯的功率为80-100W/cm，照射时间3-5s；在第二涂布步骤中，涂布辊为网纹辊；在120℃下进行固化处理，时间为120-150s；
在第二覆合步骤中，熟成处理的操作如下：在常温下放置72h，或在50℃的条件下放置24h。
一种曲面保护膜的成型方法，曲面保护膜包括从上往下依次层叠的第一PET离型膜40、第一硬化层20、基材层10、第二硬化层30、硅胶层50和氟化有机硅离型层60；成型方法包括以下步骤：
覆合第二PET离型膜70(如图2所示)：取两张第二PET离型膜70，分别把两张第二PET离型膜70贴覆在第一PET离型膜40的顶面和氟化有机硅离型层60的底面上，得到半成品；
放入模具：模具包括上模具和下模具，根据需要的型号，将半成品用激光设备切割成相应的尺寸，把切割好的半成品放入下模具内后，然后将上模具根据槽位与下模具盖合；此时由于材料还没软化，故上模具与下模具无法压紧；
加热模具：把模具放入依次放入第一升温箱、第二升温箱和第三升温箱内，第一升温箱的温度为140-180℃，第二升温箱的温度为170-220℃，第三升温箱的温度为170-220℃；模具在第一升温箱、第二升温箱和第三升温箱内的保存时间均为5-15min；此时这3个升温箱体中，材料开始软化，受上模具的重力影响，模具重合的间隙会越来越小；
下压模具：使用下压设备往下压上模具，下压速度为50-500cm/min，下压时间为2-10min；即缓速下压，避免造成模具和材料损坏，此时上模具与下模具完全重合；
冷却模具：下压设备保持下压状态与模具一起进入-30-0℃的条件下，保持2-10min；
出模：打开模具，取出材料，撕掉两张第二PET离型膜；从而最终得到曲面保护膜。
作为进一步的实施方式，第二PET离型膜的熔点大于180℃，其厚度为40-60μm；在150℃，30min的热收缩测试条件下，第二PET离型膜的横向收缩率≤2，纵向收缩率≤0.2。即第二PET离型膜为耐高温PET离型膜，产品热弯成型完成后，需要撕掉，产品正式出货时是没有耐高温的第二PET离型膜。第二PET离型膜主要是为了防止热弯过程中材料过度变形，减少热压模具/外部异物对材料压出压痕或压点，保持材料的洁净和平整度。
作为进一步的实施方式，在放入模具步骤中，首先在上模具和下模具的表面喷上脱模剂，待脱模剂干燥后，用无尘布擦拭，然后把半成品放入下模具内。
作为进一步的实施方式，上模具和下模具均为石墨模具，采用抗压135(Mpa)，抗折65(Mpa)，体积密度1.92，硬度67(HSD)的石墨模具；石墨模具重量轻，比重是铜的1/5；加工性能好，机加工后无毛刺，易用于后期手工修模；石墨的熔点为3850±50℃，沸点为4250℃，热膨胀系数也很小，在高温环境下报损率低，降低生产成本；导热性能好，对材料传热处理佳；抗热震性好，石墨在常温下使用时能经受住温度的剧烈变化而不致破坏，温度突变时，体积变化不大，不会产生裂纹。上模具和下模具的壁面内均设置有导热管，使得模具内的材料更好地受热，成型更好。
在具体的应用中，针对不同型号的曲面手机，制作模具，通过多次热弯/冷却测试，计算出反弹偏距的平均值。根据本发明的曲面保护膜来计算，反弹值在15-35°；根据以上参数进行模具休整，使模具的曲面部分内凹20-40°；由此模具公差来最大化抵消材料的反弹系数。并且，在实际操作中，上模具和下模具之间的模具间隙根据预制材料的厚度进行设定，例如，可以把上模具和下模具之间的模具间隙设置为200-550μm。
作为进一步的实施方式，成型方法在隧道炉中进行，如图3所示，隧道炉包括运行轨道80，运行轨道80的初始端设置有模具入口81，其终止端设置有模具出口82，轨道的末尾处设置有取模处88；沿轨道80运行方向，在轨道80上依次设置有第一升温箱83、第二升温箱84、第三升温箱85、下压成型箱86和冷冻箱87(急速降温区域)；第一升温箱83、第二升温箱84和第三升温箱85内均设置有加热器，有单独温控；下压成型箱86内设置有下压气缸；第一升温箱83、第二升温箱84、第三升温箱85、下压成型箱86和冷冻箱87外均包裹有保温棉，最大化保证温度的稳定性。
实施例1
一种曲面保护膜，其依据下述方法制备而成：
一、涂布覆合
第一涂布步骤：取厚度为125μm的PET基材层，采用辊涂方式在PET基材的顶面和底面分别涂布厚度为18μm的聚氨酯丙烯酸树脂，涂布辊为陶瓷斜齿形网纹辊，涂布辊的转速为40m/min，PET基材的进料速度为30m/min；聚氨酯丙烯酸树脂固化后，形成第一硬化层和第二硬化层；先后结合烘箱干燥和紫外光照射这两种方式进行固化处理，烘箱的温度为50-100℃，干燥时间为 2-4min；紫外灯的功率为80-100W/cm，照射时间3-5s；
第一覆合步骤：取厚度为50μm的亚克力胶型第一PET离型膜，并贴覆在第一硬化层的顶面上；
第二涂布步骤：采用辊涂方式在第二硬化层的底面涂布一层50μm的硅胶，涂布辊为网纹辊；所用硅胶为高粘硅胶，在剥离速度为300mm/min的条件下，所述硅胶层的剥离强度大于100g/25mm；然后在120℃下进行固化处理120s，形成硅胶层；
第二覆合步骤：在硅胶层的底面贴覆厚度为50μm的氟化有机硅离型层；然后在在常温下放置72h熟成，得到第一半成品；
二、成型
覆合第二PET离型膜：取两张厚度50μm的第二PET离型膜，分别在第一PET离型膜的顶面和氟化有机硅离型层的底面上，得到第二半成品；第二PET离型膜耐温180℃；
裁剪：根据需要的型号，将第二半成品用激光设备切割成相应的尺寸，得到第三半成品；
设置成型设备：成型设备包括隧道炉，隧道炉包括运行轨道，运行轨道的初始端设置有模具入口，其终止端设置有模具出口；沿轨道运行方向，在运行轨道上依次设置有第一升温箱、第二升温箱、第三升温箱、下压成型箱和冷冻箱；下压成型箱内设置有下压气缸，下压气缸能够随运行轨道进入冷冻箱；
放入模具：模具为石墨模具，包括上模具和下模具；首先在上模具和下模具的表面喷上脱模剂，待脱模剂干燥后，用无尘布擦拭，然后把第三半成品放入下模具内，盖合所述上模具；
加热模具：模具从模具进口进入运行轨道，然后依次通过第一升温箱、第 二升温箱和第三升温箱，第一升温箱的温度为180℃，第二升温箱的温度为220℃，第三升温箱的温度为170℃；石墨模具在第一升温箱、第二升温箱和第三升温箱内的保存时间均为15min；
下压模具：当模具完全通过所有升温箱后进入下压成型箱，下压气缸往下压上模具，下压速度为50cm/min，下压时间为10min；
冷却模具：下压气缸保持下压状态与模具一起进入冷冻箱，冷冻箱的温度为-30℃，保持2min；
出模：模具从冷冻箱中出来，随运行轨道到达模具出口，从模具出口运行至取模处时，模具回温，取出模具中的材料，撕掉两张第二PET离型膜；从而最终得到曲面保护膜。
实施例2
实施例2与实施例1的不同之处在于：第一PET离型膜的厚度为40μm；PET基材的厚度为188μm；第一硬化层的厚度为15μm，第二硬化层的厚度为20μm；氟化有机硅离型层的厚度为60μm；
在第二覆合步骤中，熟成处理的操作如下：在50℃的条件下放置24h。
其他与具体实施例1相同。
实施例3
实施例3与实施例1的不同之处在于：在第一涂布步骤中，涂布辊的转速为20m/min，PET基材的进料速度为3m/min；
在第二涂布步骤中，高粘硅胶在120℃下进行固化处理150s，形成硅胶层；
在加热模具步骤中，第一升温箱的温度为140℃，第二升温箱的温度为 170℃，第三升温箱的温度为220℃；石墨模具在第一升温箱的保存时间为15min，在第二升温箱和第三升温箱内的保存时间均为5min；
在下压模具步骤中，下压速度为500cm/min，下压时间为2min；
在冷却模具步骤中，下压气缸保持下压状态与模具一起进入冷冻箱，冷冻箱的温度为0℃，保持10min。
其他与具体实施例1相同。
对比例1
对比例1与实施例1的不同之处在于：所述模具为钢制模具。
其他与具体实施例1相同。
对比例2
对比例2与实施例1的不同之处在于：硅胶层并不是由高粘硅胶固化形成的，对比例2的硅胶在剥离速度为300mm/min的条件下，剥离强度小于100g/25mm，且硅胶的涂布厚度为30μm。
其他与具体实施例1相同。
效果评价及性能检测
对实施例1-3和对比例1-2的曲面保护膜的性能进行检测，检测项目及结果参见表1。
表1：性能检测结果记录表
Figure PCTCN2017092080-appb-000001
Figure PCTCN2017092080-appb-000002
由上表1可得，实施例1-3获取的曲面保护膜均能够很好地吻合曲面屏幕，贴合度好，且耐刮耐磨，无反弹翘起现象，实施例1为最佳实施例。而对比例1的曲面保护膜是用钢制模具制备而成的，钢制模具制作成本高，模具重量大，导致上模具容易把材料压损；钢模具膨胀性较高，导致材料热弯的精准度不足，影响贴合。而对比例2的曲面保护膜，成型后的成品，硅胶层的粘性不足，无法贴合手机屏幕，弧度位置出现严重的材料起翘现象。
上述实施方式仅为本发明的优选实施方式，不能以此来限定本发明保护的范围，本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。

Claims (10)

  1. 一种曲面保护膜，其特征在于：包括从上往下依次层叠的第一PET离型膜、第一硬化层、基材层、第二硬化层、硅胶层和氟化有机硅离型层；其中，所述第一PET离型膜包括PET离型膜本体，以及设置在所述PET离型膜本体下方的第一胶层。
  2. 如权利要求1所述的曲面保护膜，其特征在于：所述第一硬化层和所述第二硬化层均为聚氨酯丙烯酸树脂层；所述基材层为PET基材、PMMA基材、PC基材，或者，所述基材层为PMMA和PC的复合基材；所述第一胶层为亚克力胶。
  3. 如权利要求2所述的曲面保护膜，其特征在于：所述第一PET离型膜的厚度为40-60μm；所述第一硬化层和所述第二硬化层的厚度均15-20μm；所述基材层的厚度为125-300μm；所述硅胶层的厚度为50-70μm；所述氟化有机硅离型层的厚度为40-60μm。
  4. 如权利要求1-3任一项所述的曲面保护膜，其特征在于：所述基材层为PET基材，其厚度为125-188μm；在剥离速度为300mm/min的条件下，所述硅胶层的剥离强度大于100g/25mm。
  5. 一种曲面保护膜的涂布覆合方法，所述曲面保护膜包括从上往下依次层叠的第一PET离型膜、第一硬化层、基材层、第二硬化层、硅胶层和氟化有机硅离型层；其特征在于所述涂布覆合方法包括：
    第一涂布步骤：取基材层，在所述基材层的顶面和底面分别涂布第一树脂和第二树脂，所述第一树脂和所述第二树脂固化后，形成第一硬化层和第二硬化层；
    第一覆合步骤：取第一PET离型膜，所述第一PET离型膜包括PET离型 膜本体，以及设置在所述PET离型膜本体下方的第一胶层；以所述PET离型膜本体为顶面，所述第一胶层与所述第一硬化层的顶面贴合；
    第二涂布步骤：在所述第二硬化层的底面涂布一层硅胶，硅胶固化后，形成硅胶层；
    第二覆合步骤：在所述硅胶层的底面贴覆氟化有机硅离型层，从而最终得到所述曲面保护膜。
  6. 如权利要求5所述的曲面保护膜的涂布覆合方法，其特征在于：
    在所述第一涂布步骤中，所述第一树脂和所述第二树脂均为聚氨酯丙烯酸树脂；采用辊涂方式进行涂布，涂布辊的转速为20-40m/min，所述基材层的进料速度为3-30m/min；涂布结束后，结合烘箱干燥和紫外光照射这两种方式进行固化处理，从而获取所述第一硬化层和所述第二硬化层；
    在所述第二涂布步骤中，采用辊涂方式进行涂布；
    在所述第二覆合步骤中：贴覆所述氟化有机硅离型层后，进行熟成处理。
  7. 如权利要求6所述的曲面保护膜的涂布覆合方法，其特征在于：在所述第一涂布步骤中，所述涂布辊为陶瓷斜齿形网纹辊；固化处理时，首先进行烘箱干燥，然后进行紫外光照射；烘箱的温度为50-100℃，干燥时间为2-4min；紫外灯的功率为80-100W/cm，照射时间3-5s；
    在所述第二涂布步骤中，所述涂布辊为网纹辊；在120℃下进行固化处理，时间为120-150s；
    在所述第二覆合步骤中，熟成处理的操作如下：在常温下放置72h，或在50℃的条件下放置24h。
  8. 一种曲面保护膜的成型方法，所述曲面保护膜包括从上往下依次层叠的 第一PET离型膜、第一硬化层、基材层、第二硬化层、硅胶层和氟化有机硅离型层；其特征在于所述成型方法包括以下步骤：
    覆合第二PET离型膜：取两张第二PET离型膜，分别把两张所述第二PET离型膜贴覆在所述第一PET离型膜的顶面和所述氟化有机硅离型层的底面上，得到半成品；
    放入模具：所述模具包括上模具和下模具，把预设尺寸的所述半成品放入所述下模具内后，盖合所述上模具；
    加热模具：把所述模具放入依次放入第一升温箱、第二升温箱和第三升温箱内，所述第一升温箱的温度为140-180℃，所述第二升温箱的温度为170-220℃，所述第三升温箱的温度为170-220℃；所述模具在所述第一升温箱、所述第二升温箱和所述第三升温箱内的保存时间均为5-15min；
    下压模具：使用下压设备往下压所述上模具，下压速度为50-500cm/min，下压时间为2-10min；
    冷却模具：把所述模具至于-30-0℃的条件下，保持2-10min；
    出模：打开所述模具，取出材料，撕掉两张所述第二PET离型膜；从而最终得到所述曲面保护膜。
  9. 如权利要求8所述的曲面保护膜的成型方法，其特征在于：所述第二PET离型膜的熔点大于180℃，其厚度为40-60μm；在150℃，30min的热收缩测试条件下，所述第二PET离型膜的横向收缩率≤2，纵向收缩率≤0.2；
    所述上模具和所述下模具均为石墨模具；所述上模具和所述下模具的壁面内均设置有导热管。
  10. 如权利要求8或9所述的曲面保护膜的成型方法，其特征在于：所述成型方法在隧道炉中进行，所述隧道炉包括运行轨道，所述运行轨道的初始端 设置有模具入口，其终止端设置有模具出口；沿轨道运行方向，在所述运行轨道上依次设置有第一升温箱、第二升温箱、第三升温箱、下压成型箱和冷冻箱；所述第一升温箱、所述第二升温箱和所述第三升温箱内均设置有加热器；所述下压成型箱内设置有下压气缸；所述第一升温箱、第二升温箱、第三升温箱、下压成型箱和冷冻箱外均包裹有保温棉。
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