CN110920196A - Ultraviolet-resistant high-haze high-transmittance polyester film and preparation method thereof - Google Patents
Ultraviolet-resistant high-haze high-transmittance polyester film and preparation method thereof Download PDFInfo
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- CN110920196A CN110920196A CN201911119409.4A CN201911119409A CN110920196A CN 110920196 A CN110920196 A CN 110920196A CN 201911119409 A CN201911119409 A CN 201911119409A CN 110920196 A CN110920196 A CN 110920196A
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- 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
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08K2003/2241—Titanium dioxide
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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Abstract
The invention discloses an anti-ultraviolet high-haze high-transmittance polyester film and a preparation method thereof, wherein the film consists of an upper surface layer, a core layer and a lower surface layer, and the core layer is prepared from the following raw materials in percentage by weight: 5-10% of uvioresistant polyester slices and 90-95% of polyethylene terephthalate slices; the upper surface layer is prepared from the following raw materials in percentage by weight: 3-9% of uvioresistant polyester slice, 1-3% of anti-blocking agent and 90-96% of polyethylene terephthalate slice; the lower surface layer is prepared from the following raw materials in percentage by weight: 10-30% of high-haze high-light-transmittance diffusion master batch and 70-90% of polyethylene terephthalate chips. The polyester film obtained by the invention has the characteristics of ultraviolet resistance, high haze, high light transmittance and the like, the haze can reach more than 70%, the light transmittance is kept more than 80%, the polyester film can be widely applied to the fields of automobile window films and architectural glass films, the performance is outstanding, the process is simple and convenient, and the polyester film has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of plastic film manufacturing, in particular to an anti-ultraviolet high-haze high-transmittance polyester film and a preparation method thereof.
Background
Polyethylene terephthalate (PET) has good fiber forming property, mechanical property, wear resistance, creep resistance and electrical insulation property, and is widely applied to the fields of fibers, films, polyester bottles, engineering plastics and the like. However, the outdoor polyester product is inevitably affected by external environmental factors (such as light, heat, water and the like) in the use process and is aged, the varieties of common PET films in the market at present are numerous, the product performance is emphasized, and in the ultraviolet-resistant field, although various film production enterprises and universities are researched, the current PET film still does not meet the expected requirements of customers in terms of aging resistance time and aging resistance effect.
In recent years, with the development of automobiles and the construction industry, the variety and the construction structure of the automobiles and the construction industry are changing, and the development of window films and glass attachment films is also rapidly progressing. Because automobiles are often exposed to the sun and exposed to the sun, the glass film needs to have certain shielding property and good light transmission property and also needs to effectively prevent ultraviolet rays from radiating passengers; architectural glazing films need to be able to effectively reduce the penetration rate of ultraviolet light in glass, and to have both high haze and high light transmission, while ensuring privacy, good light transmission in space. In order to meet the use requirements, the development of a film with ultraviolet resistance, high haze and high light transmittance is required.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides an anti-ultraviolet high-haze high-transmittance polyester film and a preparation method thereof, the preparation method is simple and easy to operate, and the prepared anti-ultraviolet high-haze high-transmittance film has the characteristics of excellent anti-ultraviolet property, high haze property, high transmittance and the like, and is particularly suitable for environments needing ultraviolet resistance, low visibility and high transmittance, such as automobile window films, architectural glass films and the like.
The invention provides an anti-ultraviolet high-haze high-transmittance polyester film which comprises an upper surface layer, a core layer and a lower surface layer, wherein the core layer is prepared from the following raw materials in percentage by weight: 5-10% of uvioresistant polyester slices and 90-95% of polyethylene terephthalate slices; the upper surface layer is prepared from the following raw materials in percentage by weight: 3-7% of uvioresistant polyester slice, 1-3% of anti-blocking agent and 90-96% of polyethylene terephthalate slice; the lower surface layer is prepared from the following raw materials in percentage by weight: 30-35% of high-haze high-light-transmittance diffusion master batch and 65-70% of polyethylene terephthalate slices;
the high-haze high-light-transmittance diffusion master batch is prepared from the following raw materials in percentage by weight: 85-90% of polyethylene glycol terephthalate and 10-15% of PMMA/organic silicon composite microspheres;
the uvioresistant polyester slice is prepared from the following raw materials in percentage by weight: 92-95% of polyethylene glycol terephthalate and 5-8% of inorganic nano anti-ultraviolet absorbent.
Preferably, the PMMA/organosilicon composite microspheres are prepared from the following raw materials: the organic silicon monomer blend, methyl methacrylate, vinyl trichlorosilane, an initiator I, an initiator II, a catalyst and a blocking agent; preferably, the silicone monomer blend is represented by the formula CnH2n+1-SiCH3(OCH3)2、CN-SiCH3(OCH3)2、NH2-SiCH3(OCH3)2The organosilicon monomer is obtained by blending according to the molar ratio of (0.8-1) to (0.85-1) to (0.9-1), wherein n is 15-20; preferably, the initiator I is cyclotetrasiloxane, the initiator II is dibenzoyl peroxide, the catalyst is ethylene titanate, and the end-capping agent is trimethylsilane.
Preferably, the molar ratio of the organosilicon monomer blend to the methyl methacrylate to the vinyltrichlorosilane is (3-3.5): (5-6): (0.5 to 2); preferably, the sum of the weight of the initiator I, the initiator II, the catalyst and the end-capping reagent is 0.1 to 0.5 percent of the weight of the organosilicon monomer blend.
Preferably, the preparation method of the PMMA/organosilicon composite microsphere is as follows: under the protection of inert atmosphere and the vacuum degree of-0.12 to-0.10 Mpa, adding an organic silicon monomer blend and initiator I cyclotetrasiloxane into a solvent, hydrolyzing to be transparent, then adding methyl methacrylate, vinyl trichlorosilane, initiator II dibenzoyl peroxide, catalyst ethylene titanate and end capping agent trimethylsilane, and reacting for 3 to 5 hours under the conditions that the temperature is 100 to 110 ℃ and the stirring speed is 1000 to 1500r/min to obtain the product.
Preferably, the preparation method of the high-haze high-transmittance diffusion master batch comprises the following steps: the polyethylene terephthalate and PMMA/organic silicon composite microspheres are subjected to melt blending extrusion, cooling, grain cutting and drying to obtain the composite material.
Preferably, the inorganic nano ultraviolet-resistant absorbent is at least one of nano titanium dioxide and zinc oxide.
The preparation method of the anti-ultraviolet high-haze high-transmittance polyester film comprises the following steps:
s1, heating and melting the raw materials of the core layer, the upper surface layer and the lower surface layer at 270-290 ℃ respectively to obtain a core layer melt, an upper surface layer melt and a lower surface layer melt;
s2, converging and extruding the core layer melt, the upper surface layer melt and the lower surface layer melt in a three-layer co-extrusion die head to obtain a mixed melt, wherein the temperature of the three-layer co-extrusion die head is 265-295 ℃;
s3, attaching the mixed melt to form a casting sheet;
s4, preheating the cast sheet, and then longitudinally stretching the cast sheet in a double-point stretching mode, wherein the stretching multiple is 4.0-4.5 times, and then cooling to 20-40 ℃;
s5, preheating the sheet obtained by longitudinal stretching in the step S4, and then transversely stretching the sheet, wherein the stretching multiple of the transverse stretching is 4.0-4.5 times;
s6, heat setting the sheet obtained by transversely stretching in the step S5 at 200-250 ℃ to form a film;
s7, performing corona treatment on the upper surface and the lower surface of the film to enable the surface tension of the film to reach 52-60 mN/m, and obtaining the anti-ultraviolet high-haze high-transmittance polyester film.
Preferably, the core layer melt obtained in the step S1 is filtered by a disc filter with a pore size of 15-25 μm.
Preferably, in step S3, the attaching specifically includes: after passing through the electrostatic attaching wire or the electrostatic attaching band, the mixed melt is attached to the surface of a cold roll to form a cast sheet; preferably, the voltage of the electrostatic attaching wire or the electrostatic attaching belt is 6-20 kV, the current is 6-20 mA, and the running speed is 10-20 mm/min; preferably, the distance between the electrostatic sticking wire or the electrostatic sticking belt and the lip of the cold roll is 30-120 mm.
The invention has the following beneficial effects:
compared with the traditional BOPET film, the uvioresistant high-haze high-transmittance biaxially oriented polyester film has excellent uvioresistant performance and high-haze high-transmittance property, the haze can reach more than 70%, the transmittance is kept more than 80%, the ultraviolet can be absorbed more effectively, and the harm to people and the like is reduced; and the effect of shielding without shading is achieved. The preparation method has more advantages in the aspects of production cost, environmental protection, energy consumption and the like, can be widely applied to the fields of automobile window films and architectural glass films, has outstanding performance and simple and convenient process, and has wide application prospect.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The anti-ultraviolet high-haze high-transmittance polyester film comprises an upper surface layer, a core layer and a lower surface layer, wherein the core layer is prepared from the following raw materials in percentage by weight: 5% of uvioresistant polyester slice and 95% of polyethylene terephthalate slice; the upper surface layer is prepared from the following raw materials in percentage by weight: 5% of uvioresistant polyester slice, 1% of anti-blocking agent and 94% of polyethylene terephthalate slice; the lower surface layer is prepared from the following raw materials in percentage by weight: 10% of high-haze high-light-transmittance diffusion master batch and 90% of polyethylene terephthalate slices;
the high-haze high-transmittance diffusion master batch is prepared from the following raw materials in percentage by weight: 90% of polyethylene terephthalate and 10% of PMMA/organic silicon composite microspheres.
The uvioresistant polyester slice is prepared from the following raw materials in percentage by weight: 95 percent of polyethylene glycol terephthalate and 5 percent of inorganic nano anti-ultraviolet absorbent. Wherein, the inorganic nano anti-ultraviolet absorbent is nano titanium dioxide.
The preparation method of the PMMA/organosilicon composite microsphere comprises the following steps: under the protection of inert atmosphere and the vacuum degree of-0.12 Mpa, adding an organic silicon monomer blend and initiator I cyclotetrasiloxane into a solvent, hydrolyzing to be transparent, then adding methyl methacrylate, vinyl trichlorosilane, initiator II dibenzoyl peroxide, catalyst ethylene titanate and end-capping agent trimethylsilane, and reacting for 3 hours under the conditions that the temperature is 100 ℃ and the stirring speed is 1000 r/min.
Wherein the solvent is obtained by mixing water and ethanol according to the volume ratio of 10: 1.
The organosilicon monomer blend has a chemical formula of CnH2n+1-SiCH3(OCH3)2、CN-SiCH3(OCH3)2、NH2-SiCH3(OCH3)2Was blended at a molar ratio of 0.8:0.85:0.9, where n is 15.
The mol ratio of the organic silicon monomer blend, the methyl methacrylate and the vinyl trichlorosilane is 3: 5: 0.5, wherein the total weight of the initiator I, the initiator II, the catalyst and the end-capping reagent is 0.1 percent of the weight of the organic silicon monomer blend.
The preparation method of the high-haze high-transmittance diffusion master batch comprises the following steps: the polyethylene terephthalate and PMMA/organic silicon composite microspheres are melted, blended and extruded by a double-screw extruder, and then are cooled, granulated and dried to obtain the PMMA/organic silicon composite microspheres.
The preparation method of the anti-ultraviolet high-haze high-transmittance polyester film comprises the following steps:
s1, mixing the raw materials of the core layer to obtain a mixed slice, drying the mixed slice in a vulcanization bed for 60min at 140 ℃, drying the mixed slice in a drying tower at 140 ℃ for 3h until the water content is 50ppm, adding the dried mixed slice into a main extruder, heating and melting the dried mixed slice in the main extruder to obtain a core layer melt, and filtering the core layer melt by a 15 mu pore disc type filter, wherein the temperature of the main extruder is 270 ℃; respectively adding the raw materials of the upper surface layer and the lower surface layer into two auxiliary extruders, and carrying out melting and vacuumizing treatment to obtain an upper surface layer melt and a lower surface layer melt, wherein the temperature of the auxiliary extruders is 270 ℃;
s2, converging and extruding the core layer melt, the upper surface layer melt and the lower surface layer melt in a three-layer co-extrusion die head respectively to obtain a mixed melt, wherein the temperature of the three-layer co-extrusion die head is 265 ℃;
s3, enabling the mixed melt to pass through an electrostatic adhesion wire or an electrostatic adhesion belt, and then closely adhering the mixed melt to the surface of a grounded cold roll to form a cast sheet, wherein the voltage of the electrostatic adhesion wire or the electrostatic adhesion belt is 6kV, the current of the electrostatic adhesion wire or the electrostatic adhesion belt is 6mA, the running speed of the electrostatic adhesion wire or the electrostatic adhesion belt is 10mm/min, and the distance between the electrostatic adhesion wire or the electrostatic adhesion belt and the lip of the cold roll is 30 mm;
s4, peeling the cast sheet from the cold roll to form a sheet, preheating the sheet, then entering a longitudinal stretching area, completing 4.0 times of stretching in a double-point stretching mode, and then cooling to 20 ℃;
s5, preheating the longitudinally stretched sheet, and transversely stretching the sheet, wherein the stretching ratio of the transverse stretching is 4.0 times;
s6, heat-setting the transversely stretched sheet into a film at 200 ℃, simultaneously adding a catalyst with platinum as an effective component at the front part of an air exchange box in a heat-setting area, catalytically decomposing oligomer in the transversely stretched sheet into water and carbon dioxide, and cooling the film to enter a traction area;
s7, conveying the film to a thickness gauge through a traction device in the traction area, feeding the detection result back to a three-layer co-extrusion die head by the thickness gauge, and automatically adjusting the thickness of the extruded mixed melt by the three-layer co-extrusion die head; and then, performing corona treatment on the upper surface and the lower surface of the film to ensure that the surface tension of the film reaches 52mN/m, thus obtaining the anti-ultraviolet high-haze high-transmittance polyester film.
Example 2
The anti-ultraviolet high-haze high-transmittance polyester film comprises an upper surface layer, a core layer and a lower surface layer, wherein the core layer is prepared from the following raw materials in percentage by weight: 7% of uvioresistant polyester slice and 93% of polyethylene terephthalate slice; the upper surface layer is prepared from the following raw materials in percentage by weight: 7% of uvioresistant polyester slice, 1% of anti-blocking agent and 92% of polyethylene terephthalate slice; the lower surface layer is prepared from the following raw materials in percentage by weight: 20% of high-haze high-light-transmittance diffusion master batch and 80% of polyethylene terephthalate slice;
the high-haze high-transmittance diffusion master batch is prepared from the following raw materials in percentage by weight: 88% of polyethylene terephthalate and 12% of PMMA/organic silicon composite microspheres.
The uvioresistant polyester slice is prepared from the following raw materials in percentage by weight: 94 percent of polyethylene glycol terephthalate and 6 percent of inorganic nano anti-ultraviolet absorbent. Wherein, the inorganic nano anti-ultraviolet absorbent is nano titanium dioxide.
The preparation method of the PMMA/organosilicon composite microsphere comprises the following steps: under the protection of inert atmosphere and the vacuum degree of-0.11 Mpa, adding an organic silicon monomer blend and initiator I cyclotetrasiloxane into a solvent, hydrolyzing to be transparent, then adding methyl methacrylate, vinyl trichlorosilane, initiator II dibenzoyl peroxide, catalyst ethylene titanate and end capping agent trimethylsilane, and reacting for 4 hours at the temperature of 105 ℃ and the stirring speed of 1200r/min to obtain the catalyst.
Wherein the solvent is obtained by mixing water and ethanol according to the volume ratio of 10: 1.
The organosilicon monomer blend has a chemical formula of CnH2n+1-SiCH3(OCH3)2、CN-SiCH3(OCH3)2、NH2-SiCH3(OCH3)2Was blended at a molar ratio of 0.9:0.9:0.95, wherein n is 18.
The mol ratio of the organic silicon monomer blend, the methyl methacrylate and the vinyl trichlorosilane is 3.2: 5.5: 1; the sum of the weight of the initiator I, the initiator II, the catalyst and the end-capping reagent is 0.3 percent of the weight of the organic silicon monomer blend.
The preparation method of the high-haze high-transmittance diffusion master batch comprises the following steps: the polyethylene terephthalate and PMMA/organic silicon composite microspheres are melted, blended and extruded by a double-screw extruder, and then are cooled, granulated and dried to obtain the PMMA/organic silicon composite microspheres.
The preparation method of the anti-ultraviolet high-haze high-transmittance polyester film comprises the following steps:
s1, mixing the raw materials of the core layer to obtain a mixed slice, drying the mixed slice in a vulcanization bed for 60min at 150 ℃, drying the mixed slice in a drying tower at 150 ℃ for 5h until the water content reaches 45ppm, adding the dried mixed slice into a main extruder, heating and melting the dried mixed slice in the main extruder to obtain a core layer melt, and filtering the core layer melt by a disc filter with the aperture of 20 mu, wherein the temperature of the main extruder is 280 ℃; respectively adding the raw materials of the upper surface layer and the lower surface layer into two auxiliary extruders, and carrying out melting and vacuumizing treatment to obtain an upper surface layer melt and a lower surface layer melt, wherein the temperature of the auxiliary extruders is 280 ℃;
s2, converging and extruding the core layer melt, the upper surface layer melt and the lower surface layer melt in a three-layer co-extrusion die head respectively to obtain a mixed melt, wherein the temperature of the three-layer co-extrusion die head is 285 ℃;
s3, enabling the mixed melt to pass through an electrostatic adhesion wire or an electrostatic adhesion belt, and then closely adhering the mixed melt to the surface of a grounded cold roll to form a cast sheet, wherein the voltage of the electrostatic adhesion wire or the electrostatic adhesion belt is 12kV, the current of the electrostatic adhesion wire or the electrostatic adhesion belt is 12mA, the running speed of the electrostatic adhesion wire or the electrostatic adhesion belt is 15mm/min, and the distance between the electrostatic adhesion wire or the electrostatic adhesion belt and the lip of the cold roll is 70 mm;
s4, peeling the cast sheet from the cold roll to form a sheet, preheating the sheet, then entering a longitudinal stretching area, completing 4.3 times of stretching in a double-point stretching mode, and then cooling to 30 ℃;
s5, preheating the longitudinally stretched sheet, and transversely stretching the sheet, wherein the stretching ratio of the transverse stretching is 4.3 times;
s6, performing heat setting on the transversely stretched sheet at 230 ℃ to form a film, adding a catalyst with platinum as an effective component at the front part of the air exchange box in the heat setting area, performing catalytic decomposition on an oligomer in the transversely stretched sheet to form water and carbon dioxide, and cooling the film to enter a traction area;
s7, conveying the film to a thickness gauge through a traction device in the traction area, feeding the detection result back to a three-layer co-extrusion die head by the thickness gauge, and automatically adjusting the thickness of the extruded mixed melt by the three-layer co-extrusion die head; and then, performing corona treatment on the upper surface and the lower surface of the film to ensure that the surface tension of the film reaches 52mN/m, thus obtaining the anti-ultraviolet high-haze high-transmittance polyester film.
Example 3
The anti-ultraviolet high-haze high-transmittance polyester film comprises an upper surface layer, a core layer and a lower surface layer, wherein the core layer is prepared from the following raw materials in percentage by weight: 9% of uvioresistant polyester slice and 91% of polyethylene terephthalate slice; the upper surface layer is prepared from the following raw materials in percentage by weight: 9% of uvioresistant polyester slice, 1% of anti-blocking agent and 90% of polyethylene terephthalate slice; the lower surface layer is prepared from the following raw materials in percentage by weight: 30% of high-haze high-light-transmittance diffusion master batch and 70% of polyethylene terephthalate slice;
the high-haze high-transmittance diffusion master batch is prepared from the following raw materials in percentage by weight: 85% of polyethylene terephthalate and 15% of PMMA/organic silicon composite microspheres.
The uvioresistant polyester slice is prepared from the following raw materials in percentage by weight: 92% of polyethylene glycol terephthalate and 8% of inorganic nano anti-ultraviolet absorbent. Wherein, the inorganic nano anti-ultraviolet absorbent is nano titanium dioxide.
The preparation method of the PMMA/organosilicon composite microsphere comprises the following steps: under the protection of inert atmosphere and the vacuum degree of-0.12 Mpa, adding an organic silicon monomer blend and initiator I cyclotetrasiloxane into a solvent, hydrolyzing to be transparent, then adding methyl methacrylate, vinyl trichlorosilane, initiator II dibenzoyl peroxide, catalyst ethylene titanate and end capping agent trimethylsilane, and reacting for 5 hours at the temperature of 110 ℃ and the stirring speed of 1500r/min to obtain the catalyst.
Wherein the solvent is obtained by mixing water and ethanol according to the volume ratio of 10: 1.
The organosilicon monomer blend has a chemical formula of CnH2n+1-SiCH3(OCH3)2、CN-SiCH3(OCH3)2、NH2-SiCH3(OCH3)2According to a molar ratio of 1: 1: 1, wherein n is 20.
The mol ratio of the organic silicon monomer blend, the methyl methacrylate and the vinyl trichlorosilane is 3: 6: 1; the sum of the weight of the initiator I, the initiator II, the catalyst and the end-capping reagent is 0.5 percent of the weight of the organic silicon monomer blend.
The preparation method of the high-haze high-transmittance diffusion master batch comprises the following steps: the polyethylene terephthalate and PMMA/organic silicon composite microspheres are melted, blended and extruded by a double-screw extruder, and then are cooled, granulated and dried to obtain the PMMA/organic silicon composite microspheres.
The preparation method of the anti-ultraviolet high-haze high-transmittance polyester film comprises the following steps:
s1, mixing the raw materials of the core layer to obtain a mixed slice, drying the mixed slice in a vulcanization bed for 60min at 170 ℃, drying the mixed slice in a drying tower at 170 ℃ for 6h until the water content is 40ppm, adding the dried mixed slice into a main extruder, heating and melting the dried mixed slice in the main extruder to obtain a core layer melt, and filtering the core layer melt by a disc filter with the pore size of 25 mu, wherein the temperature of the main extruder is 290 ℃; respectively adding the raw materials of the upper surface layer and the lower surface layer into two auxiliary extruders, and carrying out melting and vacuumizing treatment to obtain an upper surface layer melt and a lower surface layer melt, wherein the temperature of the auxiliary extruders is 290 ℃;
s2, converging and extruding the core layer melt, the upper surface layer melt and the lower surface layer melt in a three-layer co-extrusion die head respectively to obtain a mixed melt, wherein the temperature of the three-layer co-extrusion die head is 305 ℃;
s3, after passing through the electrostatic adhesion wire or electrostatic adhesion belt, the mixed melt is tightly adhered to the surface of the grounded cold roll to form a cast sheet, wherein the voltage of the electrostatic adhesion wire or electrostatic adhesion belt is 20kV, the current of the electrostatic adhesion wire or electrostatic adhesion belt is 20mA, the running speed of the electrostatic adhesion wire or electrostatic adhesion belt is 20mm/min, and the distance between the electrostatic adhesion wire or electrostatic adhesion belt and the lip of the cold roll is 120 mm;
s4, peeling the cast sheet from the cold roll to form a sheet, preheating the sheet, then entering a longitudinal stretching area, completing 4.5 times of stretching in a double-point stretching mode, and then cooling to 40 ℃;
s5, preheating the longitudinally stretched sheet, and transversely stretching the sheet, wherein the stretching ratio of the transverse stretching is 4.5 times;
s6, heat-setting the transversely stretched sheet into a film at 250 ℃, simultaneously adding a catalyst with platinum as an effective component at the front part of the air exchange box in the heat-setting area, catalytically decomposing oligomer in the transversely stretched sheet into water and carbon dioxide, and cooling the film to enter a traction area;
s7, conveying the film to a thickness gauge through a traction device in the traction area, feeding the detection result back to a three-layer co-extrusion die head by the thickness gauge, and automatically adjusting the thickness of the extruded mixed melt by the three-layer co-extrusion die head; and then, performing corona treatment on the upper surface and the lower surface of the film to ensure that the surface tension of the film reaches 52mN/m, thus obtaining the anti-ultraviolet high-haze high-transmittance polyester film.
Comparative example
The polyester film of the comparative example consisted of an upper skin layer, a core layer and a lower skin layer, the core layer being made from the following raw materials: 100% of PET polyester chips; the upper surface layer is prepared from the following raw materials: 1% of PET polyester anti-sticking master batch and 99% of PET polyester chips; the lower surface layer is prepared from the following raw materials: 10% of PET polyester anti-sticking master batch and 90% of PET polyester chips;
the comparative example was prepared in the same manner as in example 1.
The main physical property indexes of the polyester film prepared above are shown in tables 1 to 5.
Table 1: haze comparison of examples 1-3 and comparative examples in accelerated aging test
Table 2: comparative table of light transmittance under accelerated aging test for examples 1-3 and comparative example
Table 3: gloss comparison of examples 1-3 with comparative examples in accelerated aging test
Table 4: comparative tables of longitudinal elongation in accelerated aging test between examples 1 to 3 and comparative example
Table 5: comparative tables of nominal strains at break under accelerated aging test for examples 1-3 and comparative examples
In summary, the following conclusions can be drawn:
1. as can be seen from the test results of examples 1-3 and comparative example, the process parameters do not affect the uvioresistant performance of the film;
2. as can be seen from the test results of the comparative example and examples 1-3, under the conditions of simulated sunlight and accelerated aging test, the film without the added anti-UV absorber is aged firstly, and the haze, the light transmittance, the gloss, the tensile strength and the fracture nominal strain of the film are all changed dramatically during the process of 3000-5000 hours, and the mechanical and optical properties of the film are reduced obviously, namely the sample without the added anti-UV absorber is aged for 3000-5000 hours. The samples obtained in examples 1 to 3 can be maintained for a longer time without aging under the conditions of simulated sunlight and accelerated aging test, compared with the sample without the ultraviolet absorbent obtained in the comparative example, and the aging time of the film is longer with the increase of the addition amount.
3. As can be seen from the test results in tables 1 and 2, the samples obtained in examples 1 to 3 have high haze and transmittance at the beginning of the test, and the haze of the film can reach more than 70%, the transmittance can reach more than 80%, and the performance of high haze and high transmittance can be maintained for a longer time.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The anti-ultraviolet high-haze high-transmittance polyester film is characterized by comprising an upper surface layer, a core layer and a lower surface layer, wherein the core layer is prepared from the following raw materials in percentage by weight: 5-10% of uvioresistant polyester slices and 90-95% of polyethylene terephthalate slices; the upper surface layer is prepared from the following raw materials in percentage by weight: 3-9% of uvioresistant polyester slice, 1-3% of anti-blocking agent and 90-96% of polyethylene terephthalate slice; the lower surface layer is prepared from the following raw materials in percentage by weight: 10-30% of high-haze high-light-transmittance diffusion master batch and 70-90% of polyethylene terephthalate slices;
the high-haze high-light-transmittance diffusion master batch is prepared from the following raw materials in percentage by weight: 85-90% of polyethylene glycol terephthalate and 10-15% of PMMA/organic silicon composite microspheres;
the uvioresistant polyester slice is prepared from the following raw materials in percentage by weight: 92-95% of polyethylene glycol terephthalate and 5-8% of inorganic nano anti-ultraviolet absorbent.
2. The ultraviolet-resistant high-haze high-transmittance polyester film as claimed in claim 1, wherein the PMMA/organosilicon composite microspheres are prepared from the following raw materials: the organic silicon monomer blend, methyl methacrylate, vinyl trichlorosilane, an initiator I, an initiator II, a catalyst and a blocking agent; preferably, the silicone monomer blend is represented by the formula CnH2n+1-SiCH3(OCH3)2、CN-SiCH3(OCH3)2、NH2-SiCH3(OCH3)2The organosilicon monomer is obtained by blending according to the molar ratio of (0.8-1) to (0.85-1) to (0.9-1), wherein n is 15-20; preferably, the initiator I is cyclotetrasiloxane, the initiator II is dibenzoyl peroxide, the catalyst is ethylene titanate, and the end-capping agent is trimethylsilane.
3. The ultraviolet-resistant high-haze high-transmittance polyester film as claimed in claim 2, wherein the molar ratio of the organosilicon monomer blend to the methyl methacrylate to the vinyltrichlorosilane is (3-3.5): (5-6): (0.5 to 2); preferably, the sum of the weight of the initiator I, the initiator II, the catalyst and the end-capping reagent is 0.1 to 0.5 percent of the weight of the organosilicon monomer blend.
4. The ultraviolet-resistant high-haze high-transmittance polyester film as claimed in claim 2 or 3, wherein the preparation method of the PMMA/organosilicon composite microspheres is as follows: under the protection of inert atmosphere and the vacuum degree of-0.12 to-0.10 Mpa, adding an organic silicon monomer blend and initiator I cyclotetrasiloxane into a solvent, hydrolyzing to be transparent, then adding methyl methacrylate, vinyl trichlorosilane, initiator II dibenzoyl peroxide, catalyst ethylene titanate and end capping agent trimethylsilane, and reacting for 3 to 5 hours under the conditions that the temperature is 100 to 110 ℃ and the stirring speed is 1000 to 1500r/min to obtain the product.
5. The ultraviolet-resistant high-haze high-transmittance polyester film as claimed in any one of claims 1 to 4, wherein the preparation method of the high-haze high-transmittance diffusion master batch comprises the following steps: the polyethylene terephthalate and PMMA/organic silicon composite microspheres are subjected to melt blending extrusion, cooling, grain cutting and drying to obtain the composite material.
6. The anti-ultraviolet high-haze high-transmittance polyester film as claimed in any one of claims 1 to 5, wherein the inorganic nano anti-ultraviolet absorbent is at least one of nano titanium dioxide and zinc oxide.
7. The preparation method of the anti-ultraviolet high-haze high-transmittance polyester film as claimed in any one of claims 1 to 6, which comprises the following steps:
s1, heating and melting the raw materials of the core layer, the upper surface layer and the lower surface layer at 270-290 ℃ respectively to obtain a core layer melt, an upper surface layer melt and a lower surface layer melt;
s2, converging and extruding the core layer melt, the upper surface layer melt and the lower surface layer melt in a three-layer co-extrusion die head to obtain a mixed melt, wherein the temperature of the three-layer co-extrusion die head is 265-295 ℃;
s3, attaching the mixed melt to form a casting sheet;
s4, preheating the cast sheet, and then longitudinally stretching the cast sheet in a double-point stretching mode, wherein the stretching multiple is 4.0-4.5 times, and then cooling to 20-40 ℃;
s5, preheating the sheet obtained by longitudinal stretching in the step S4, and then transversely stretching the sheet, wherein the stretching multiple of the transverse stretching is 4.0-4.5 times;
s6, heat setting the sheet obtained by transversely stretching in the step S5 at 200-250 ℃ to form a film;
s7, performing corona treatment on the upper surface and the lower surface of the film to enable the surface tension of the film to reach 52-60 mN/m, and obtaining the anti-ultraviolet high-haze high-transmittance polyester film.
8. The preparation method of the anti-ultraviolet high-haze high-transmittance biaxially oriented polyester film according to claim 7, characterized in that: and filtering the core layer melt obtained in the step S1 through a disc filter with the pore size of 15-25 mu.
9. The preparation method of the anti-ultraviolet high-haze high-transmittance biaxially oriented polyester film according to claim 7 or 8, characterized in that: in step S3, the attaching specifically includes: after passing through the electrostatic attaching wire or the electrostatic attaching band, the mixed melt is attached to the surface of a cold roll to form a cast sheet; preferably, the voltage of the electrostatic attaching wire or the electrostatic attaching belt is 6-20 kV, the current is 6-20 mA, and the running speed is 10-20 mm/min; preferably, the distance between the electrostatic sticking wire or the electrostatic sticking belt and the lip of the cold roll is 30-120 mm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114425899A (en) * | 2022-02-22 | 2022-05-03 | 广东卓尔新材料有限公司 | High-light-transmittance high-definition polyester film and preparation method thereof |
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| CN1660568A (en) * | 2004-02-24 | 2005-08-31 | 上海紫东化工塑料有限公司 | Sub-smooth type polyester film at least in single side and fabricating method |
| CN107839323A (en) * | 2017-09-29 | 2018-03-27 | 安徽国风塑业股份有限公司 | A kind of uvioresistant biaxially oriented polyester film and preparation method thereof |
| CN109796732A (en) * | 2018-12-28 | 2019-05-24 | 汕头市贝斯特科技有限公司 | A kind of high transparency haze polyester diffusion masterbatch and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1660568A (en) * | 2004-02-24 | 2005-08-31 | 上海紫东化工塑料有限公司 | Sub-smooth type polyester film at least in single side and fabricating method |
| CN107839323A (en) * | 2017-09-29 | 2018-03-27 | 安徽国风塑业股份有限公司 | A kind of uvioresistant biaxially oriented polyester film and preparation method thereof |
| CN109796732A (en) * | 2018-12-28 | 2019-05-24 | 汕头市贝斯特科技有限公司 | A kind of high transparency haze polyester diffusion masterbatch and preparation method thereof |
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