CN111574769A - Photochromic ETFE resin film and method for producing same - Google Patents

Photochromic ETFE resin film and method for producing same Download PDF

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Publication number
CN111574769A
CN111574769A CN202010411913.8A CN202010411913A CN111574769A CN 111574769 A CN111574769 A CN 111574769A CN 202010411913 A CN202010411913 A CN 202010411913A CN 111574769 A CN111574769 A CN 111574769A
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Prior art keywords
photochromic
resin film
etfe
etfe resin
parts
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CN202010411913.8A
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Inventor
郭兴龙
冯威
于洋洋
张恒
张永明
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/404—Multi-coloured
    • 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
    • B32B2419/00—Buildings or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—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 at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2258—Oxides; Hydroxides of metals of tungsten
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a photochromic ETFE resin film and a preparation method thereof. The photochromic ETFE resin film comprises the following raw materials in parts by mass: 100 parts of ethylene-tetrafluoroethylene copolymer particles, 15-30 parts of photochromic color master batch, 2-10 parts of antioxidant, 0.5-5 parts of ultraviolet absorbent, 1-8 parts of toughening agent, 2-10 parts of antistatic agent and 2-5 parts of lubricant. The raw materials are jointed by a 3-layer co-extrusion extruder, then extruded by a T-shaped die head, and cooled to obtain a multilayer ETFE resin film product. The prepared ETFE resin film can effectively improve the defect of single color of the ETFE film by adding the photochromic master batch; the color of the ETFE resin film is enhanced, the harm of ultraviolet rays to the skin of people is reduced, and the living standard of people is improved.

Description

Photochromic ETFE resin film and method for producing same
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a photochromic ETFE resin film and a preparation method thereof.
Background
Photochromic refers to that under the action of light with certain wavelength and intensity, the molecular structure in the compound changes, so that the absorption peak value of the compound to the light changes, and the color of the material changes correspondingly, and the change is reversible under the general condition, namely, the color of the compound changes under the irradiation of the light, and when the light on the compound disappears, the compound returns to the original color. At present, photochromic materials are applied and recorded on memory storage elements, packaging films and transparent films of computers, organic photoconductive materials are successfully developed by means of scientific research of Tianjin university at home, series products of laser printers, laser fax machines, digital copiers and the like with different specifications and models are produced, and no use record is found on ETFE (ethylene-tetrafluoroethylene copolymer) building films.
The ETFE (ethylene-tetrafluoroethylene copolymer) film for the building at present is widely applied to characteristic landmark buildings such as airports, large gymnasiums and the like due to the characteristics of high strength, aging resistance, good transparency and the like, but the ETFE building film used at present does not have a dimming function and cannot completely meet the requirements of people on entertainment and health.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, and the photochromic ETFE resin film is provided, so that the color can be changed along with the light intensity, and the defect of single color of the ETFE film can be effectively overcome; the colorfulness of the ETFE resin film is enhanced, the harm of ultraviolet rays to the skin of people is reduced, and the living standard of people is improved; meanwhile, the invention also provides a preparation method of the ETFE resin film, and the comprehensive performance of the ETFE resin film is ensured to the maximum extent.
The photochromic ETFE resin film comprises the following raw materials in parts by mass:
Figure BDA0002493576210000011
the ethylene-tetrafluoroethylene copolymer particles have the melt index of 3-30g/10min, the melting point of 230-265 ℃, and are obtained by adopting a water ring granulation mode, the surfaces of the particles are uniform, the interior of the particles is free from impurities, and the bulk density of the particles is 0.8-1.2 g/mL.
The photochromic ETFE master batch is prepared by mixing, melting, extruding and granulating a plurality of photochromic pigments and ETFE powder, wherein the adopted photochromic pigments are one or more of organic photochromic materials or inorganic photochromic materials.
Further, the organic photochromic material is a spiropyran, diarylethene or azo compound; the inorganic photochromic material is a transition metal oxide, a metal halide or a rare earth complex compound.
The antioxidant is one or more of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine or 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; the antioxidant is added to prevent the ETFE resin from thermal oxidation degradation in the processing process, so that the forming processing of the ETFE resin film is smoothly carried out.
The ultraviolet absorbent is one or more than one of 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine-2-yl) -5-octyloxyphenol, 2- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) -5-hexyloxyphenol or 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester; the resin material is used for absorbing ultraviolet parts in light and ensuring that the resin material does not have performance change.
The toughening agent is one or more of carboxyl-terminated hyperbranched polyester, thermoplastic polyphenylene ether ketone, thermoplastic polyether sulfone or ethylene-vinyl acetate copolymer; the additive can improve the toughness of the material when added into the resin material, and can absorb certain energy when the material is impacted by an external object in the using process.
The antistatic agent is one or more than one of quaternary ammonium base acrylate copolymer, quaternary ammonium base maleimide copolymer or quaternary ammonium base methacrylamide copolymer; because the surface of the film material is difficult to clean in the external use process, the addition of the antistatic agent can reduce the dust deposition on the surface of the ETFE film material, so that the film can keep high light transmittance for a long time in the use process.
The lubricant is one or more of polytetrafluoroethylene micro powder, ethylene bis stearamide or low molecular weight polypropylene, and is mainly used for reducing the friction force between ETFE resin and a metal wall in the processing process, so that the processing flowability of the resin is improved, the possibility of carbonization of the ETFE resin at a dead angle of processing equipment is reduced, the probability of crystal points of the ETFE resin film is reduced, and the product quality of the film material is improved.
The preparation method of the photochromic ETFE resin film comprises the following steps:
(1) adding ethylene-tetrafluoroethylene copolymer particles, a toughening agent and a lubricating agent into an inner layer of a 3-layer co-extrusion extruder, adding the ethylene-tetrafluoroethylene copolymer particles and photochromic ETFE master batch into a middle layer of the 3-layer co-extrusion extruder, adding the ethylene-tetrafluoroethylene copolymer particles, an antioxidant, an ultraviolet absorbent and an antistatic agent into an outer layer of the 3-layer co-extrusion extruder, and heating to melt and extrude the materials;
(2) laminating the melt-extruded materials through a machine head, and extruding the materials through a T-shaped machine head to obtain a composite ETFE resin film;
(3) and (3) cooling the composite ETFE resin film in a cooling roller to obtain a photochromic ETFE resin film product.
The mass ratio of the addition amount of the ethylene-tetrafluoroethylene copolymer particles in the step (1) in the inner layer, the middle layer and the outer layer of the 3-layer co-extrusion extruder is 3:4: 3.
The melt extrusion temperature in the step (1) is 230-300 ℃, and the screw size of the extruder is
Figure BDA0002493576210000032
L/D is 20-50, and the rotating speed of the screw is 20-300 rpm.
In the step (2), in order to ensure the thickness precision of the film, the T-shaped machine head is provided with an automatic lip gap adjusting system.
The cooling roller in the step (3) adopts a multi-spiral water inlet channel with a double-layer structure, and the cooling roller enters from the outside and is discharged from the inside; in order to allow the film exiting the die to be consolidated onto the chill roll, the film may also be treated by one or both of air knife or vacuum suction chamber methods.
And finally detecting the ETFE resin film product after cooling by a thickness meter and a tension tester, removing edges after the product is qualified, and winding the ETFE resin film product in an automatic winding device, wherein the width of the wound film material is 500-20000mm, the winding diameter is 800-1500mm, the winding speed is 5-500m/min, and the film thickness is 3-300 mu m.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the photochromic ETFE master batch is added in the processing process of the ETFE resin film, so that the modified ETFE resin film can change color along with the light intensity in the using process, the defect of single color of the ETFE film is effectively improved, on one hand, the intensity of indoor light can be changed by changing the color of the modified ETFE resin film, the healthy life of indoor personnel is ensured, the living quality level of people is improved, on the other hand, the colorfulness of the ETFE resin film is enhanced, and when the photochromic ETFE resin film is applied to landmark buildings such as large airports, gymnasiums and the like, the colorfulness of the landmark buildings can be increased, and the influence effect of the landmark buildings is increased.
2. The processing mode adopted by the invention mainly comprises multilayer melt coextrusion and composite film forming, ensures the comprehensive performance of the ETFE resin film to the maximum extent, and compared with single extrusion film forming, the processing mode avoids the possibility of the reduction of the overall performance of the ETFE resin film caused by different material properties of the functional auxiliary agent in the same film.
Detailed Description
The present invention will be further described with reference to the following examples.
All the starting materials used in the examples are commercially available unless otherwise specified.
Example 1
The photochromic ETFE resin film comprises the following raw materials in parts by mass:
Figure BDA0002493576210000031
the melt index of the ethylene-tetrafluoroethylene resin particles is 7g/10min, the melting point is 253 ℃, and the bulk density of the particles is 0.98 g/mL.
The photochromic ETFE master batch contains WO3Inorganic photochromic ETFE masterbatch.
The preparation method comprises the following steps:
adding 30 parts of ethylene-tetrafluoroethylene copolymer particles, 1 part of thermoplastic polyphenylene ether ketone and 2 parts of polytetrafluoroethylene micro powder into an inner layer of a 3-layer co-extrusion extruder, adding 40 parts of ethylene-tetrafluoroethylene copolymer particles and 15 parts of photochromic ETFE master batch into a middle layer of the 3-layer co-extrusion extruder, adding 30 parts of ethylene-tetrafluoroethylene copolymer particles, 2 parts of tetra (3, 5-di-tert-butyl-4-hydroxy) pentaerythritol phenylpropionate, 0.5 part of 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5-octyloxyphenol and 2 parts of quaternary ammonium maleimide copolymer into an outer layer of the 3-layer co-extrusion extruder; the size of the screw of the extruder is phi 24mm, L/D30, the temperature is set at 265 ℃, and the rotating speed of the screw is 180 rpm; after passing through each flow channel, the materials to be melt-extruded are jointed by a T-shaped machine head, and the jointed ETFE resin film is extruded by the T-shaped machine head; the extruded ETFE resin film is detected by a thickness meter and a tension tester, and then is rolled by an automatic rolling device, wherein the rolling requirement is 5000mm, the rolling diameter is 800mm, the rolling speed is 10m/min, and the film thickness is 120 mu m.
Example 2
The photochromic ETFE resin film comprises the following raw materials in parts by mass:
Figure BDA0002493576210000041
the melt index of the ethylene-tetrafluoroethylene resin particles is 9g/10min, the melting point is 253 ℃, and the bulk density of the particles is 0.99 g/mL.
The photochromic ETFE master batch is an inorganic photochromic ETFE master batch doped with Ce and calcium fluoride.
The preparation method comprises the following steps:
adding 30 parts by mass of ethylene-tetrafluoroethylene copolymer particles, 3 parts by mass of thermoplastic polyether sulfone and 3 parts by mass of ethylene bis stearamide into an inner layer of a 3-layer co-extrusion extruder, adding 40 parts by mass of ethylene-tetrafluoroethylene copolymer particles and 20 parts by mass of photochromic ETFE master batch into a middle layer of the 3-layer co-extrusion extruder, and adding 30 parts by mass of ethylene-tetrafluoroethylene copolymer particles, 3 parts by mass of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 2 parts by mass of 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxyphenol and 5 parts by mass of quaternary ammonium methacrylimide into an outer layer of the 3-layer co-extrusion extruder; the size of the screw of the extruder is phi 24mm, L/D30, the temperature is set at 265 ℃, and the rotating speed of the screw is 180 rpm; after passing through each flow channel, the materials to be melt-extruded are jointed by a T-shaped machine head, and the jointed ETFE resin film is extruded by the T-shaped machine head; the extruded ETFE resin film is detected by a thickness meter and a tension tester, and then is rolled by an automatic rolling device, wherein the rolling requirement is 5000mm, the rolling diameter is 800mm, the rolling speed is 10m/min, and the film thickness is 120 mu m.
Example 3
The photochromic ETFE resin film comprises the following raw materials in parts by mass:
Figure BDA0002493576210000051
the melt index of the ethylene-tetrafluoroethylene resin particles is 8g/10min, the melting point is 253 ℃, and the bulk density of the particles is 0.98 g/mL.
The photochromic ETFE master batch is an organic photochromic ETFE master batch containing spiroindolizine compounds.
The preparation method comprises the following steps:
adding 30 parts of ethylene-tetrafluoroethylene copolymer particles, 5 parts of ethylene-vinyl acetate copolymer and 3 parts of low molecular weight polypropylene into an inner layer of a 3-layer co-extrusion extruder, adding 40 parts of ethylene-tetrafluoroethylene copolymer particles and 20 parts of photochromic ETFE master batch into a middle layer of the 3-layer co-extrusion extruder, and adding 30 parts of ethylene-tetrafluoroethylene copolymer particles, 5 parts of 1,3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, 3 parts of 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester and 8 parts of quaternary ammonium base acrylate copolymer into an outer layer of the 3-layer co-extrusion extruder; the size of the screw of the extruder is phi 24mm, L/D30, the temperature is set at 265 ℃, and the rotating speed of the screw is 180 rpm; after passing through each flow channel, the materials to be melt-extruded are jointed by a T-shaped machine head, and the jointed ETFE resin film is extruded by the T-shaped machine head; the extruded ETFE resin film is detected by a thickness meter and a tension tester, and then is rolled by an automatic rolling device, wherein the rolling requirement is 5000mm, the rolling diameter is 800mm, the rolling speed is 10m/min, and the film thickness is 120 mu m.
Example 4
The photochromic ETFE resin film comprises the following raw materials in parts by mass:
Figure BDA0002493576210000052
Figure BDA0002493576210000061
the melt index of the ethylene-tetrafluoroethylene resin particles is 11g/10min, the melting point is 253 ℃, and the bulk density of the particles is 1.02 g/mL.
The photochromic ETFE master batch is an organic photochromic ETFE master batch of a tetrachloronaphthalenone compound.
The preparation method comprises the following steps:
adding 30 parts of ethylene-tetrafluoroethylene copolymer particles, 8 parts of ethylene-vinyl acetate copolymer and 5 parts of polytetrafluoroethylene micro powder into an inner layer of a 3-layer co-extrusion extruder, adding 40 parts of ethylene-tetrafluoroethylene copolymer particles and 30 parts of photochromic ETFE master batch into a middle layer of the 3-layer co-extrusion extruder, and adding 30 parts of ethylene-tetrafluoroethylene copolymer particles, 10 parts of tetra (3, 5-di-tert-butyl-4-hydroxy) pentaerythritol phenylpropionate, 5 parts of 2- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) -5-hexyloxyphenol and 10 parts of a quaternary ammonium maleimide-based maleimide/quaternary ammonium methyl acrylamide-based mixture into an outer layer of the 3-layer co-extrusion extruder; the size of the screw of the extruder is phi 24mm, L/D30, the temperature is set at 265 ℃, and the rotating speed of the screw is 180 rpm; after passing through each flow channel, the materials to be melt-extruded are jointed by a T-shaped machine head, and the jointed ETFE resin film is extruded by the T-shaped machine head; the extruded ETFE resin film is detected by a thickness meter and a tension tester, and then is rolled by an automatic rolling device, wherein the rolling requirement is 5000mm, the rolling diameter is 800mm, the rolling speed is 10m/min, and the film thickness is 120 mu m.
Comparative example 1
The photochromic ETFE resin film comprises the following raw materials in parts by mass:
Figure BDA0002493576210000062
the melt index of the ethylene-tetrafluoroethylene resin particles is 11g/10min, the melting point is 253 ℃, and the bulk density of the particles is 1.02 g/mL.
The photochromic ETFE masterbatch comparative example was not added.
The preparation method comprises the following steps:
by mass, adding 30 parts of ethylene-tetrafluoroethylene copolymer particles, 6 parts of thermoplastic polyether sulfone and 3 parts of low molecular weight polypropylene into an inner layer of a 3-layer co-extrusion extruder, adding 40 parts of ethylene-tetrafluoroethylene copolymer particles into a middle layer of the 3-layer co-extrusion extruder, adding 30 parts of ethylene-tetrafluoroethylene copolymer particles, 8 parts of tetra (3, 5-di-tert-butyl-4-hydroxy) pentaerythritol phenylpropionate, 4 parts of 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester and 8 parts of quaternary ammonium base methacrylamide copolymer into an outer layer of the 3-layer co-extrusion extruder; the size of the screw of the extruder is phi 24mm, L/D30, the temperature is set at 265 ℃, and the rotating speed of the screw is 180 rpm; after passing through each flow channel, the materials to be melt-extruded are jointed by a T-shaped machine head, and the jointed ETFE resin film is extruded by the T-shaped machine head; the extruded ETFE resin film is detected by a thickness meter and a tension tester, and then is rolled by an automatic rolling device, wherein the rolling requirement is 5000mm, the rolling diameter is 800mm, the rolling speed is 10m/min, and the film thickness is 120 mu m.
Performance testing
The photochromic ETFE resin films prepared in examples 1 to 4 and comparative example 1 were subjected to a performance test in which a yellowness value was measured by an UltraScan VIS of Shanghai communications and Union electronics, Inc., a Meits C64 hydraulic universal tester was used for tensile strength and elongation at break, a BMC-B1 standard drop impact tester of Jinan optical electro-mechanical technology, Inc. was used for impact performance, and a TLV-304-BP transmittance meter was used for light transmittance; the results are shown in Table 1.
TABLE 1 test results of photochromic ETFE resin films prepared in examples 1-4 and comparative example 1
Figure BDA0002493576210000071
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.

Claims (10)

1. A photochromic ETFE resin film, characterized in that: the composite material comprises the following raw materials in parts by mass:
Figure FDA0002493576200000011
2. the photochromic ETFE resin film according to claim 1, wherein: the melt index of the ethylene-tetrafluoroethylene copolymer particles is 3-30g/10min, the melting point is 230-265 ℃, and the bulk density is 0.8-1.2 g/mL.
3. The photochromic ETFE resin film according to claim 1, wherein: the photochromic ETFE master batch is prepared by mixing, melting, extruding and granulating a plurality of photochromic pigments and ETFE powder, wherein the adopted photochromic pigments are one or more of organic photochromic materials or inorganic photochromic materials.
4. The photochromic ETFE resin film of claim 3, wherein: the organic photochromic material is a spiropyran, diarylethene or azo compound; the inorganic photochromic material is a transition metal oxide, a metal halide or a rare earth complex compound.
5. The photochromic ETFE resin film according to claim 1, wherein: the antioxidant is one or more of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine or 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; the ultraviolet absorbent is one or more than one of 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine-2-yl) -5-octyloxyphenol, 2- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) -5-hexyloxyphenol or 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester; the toughening agent is one or more of carboxyl-terminated hyperbranched polyester, thermoplastic polyphenylene ether ketone, thermoplastic polyether sulfone or ethylene-vinyl acetate copolymer.
6. The photochromic ETFE resin film according to claim 1, wherein: the antistatic agent is one or more than one of quaternary ammonium base acrylate copolymer, quaternary ammonium base maleimide copolymer or quaternary ammonium base methacrylamide copolymer; the lubricant is one or more of polytetrafluoroethylene micro powder, ethylene bisstearamide or low molecular weight polypropylene.
7. A method for preparing a photochromic ETFE resin film according to any one of claims 1 to 6, wherein: the method comprises the following steps:
(1) adding ethylene-tetrafluoroethylene copolymer particles, a toughening agent and a lubricating agent into an inner layer of a 3-layer co-extrusion extruder, adding the ethylene-tetrafluoroethylene copolymer particles and photochromic ETFE master batch into a middle layer of the 3-layer co-extrusion extruder, adding the ethylene-tetrafluoroethylene copolymer particles, an antioxidant, an ultraviolet absorbent and an antistatic agent into an outer layer of the 3-layer co-extrusion extruder, and heating to melt and extrude the materials;
(2) laminating the melt-extruded materials through a machine head, and extruding the materials through a T-shaped machine head to obtain a composite ETFE resin film;
(3) and (3) cooling the composite ETFE resin film in a cooling roller to obtain a photochromic ETFE resin film product.
8. The method for producing a photochromic ETFE resin film according to claim 7, wherein: the mass ratio of the addition amount of the ethylene-tetrafluoroethylene copolymer particles in the step (1) in the inner layer, the middle layer and the outer layer of the 3-layer co-extrusion extruder is 3:4: 3.
9. The method for producing a photochromic ETFE resin film according to claim 7, wherein: in the step (1), the melt extrusion temperature is 230-.
10. The method for producing a photochromic ETFE resin film according to claim 7, wherein: the cooling roller in the step (3) adopts a multi-spiral water inlet channel with a double-layer structure, and the cooling roller enters from the outside and is discharged from the inside; the thickness of the photochromic ETFE resin film product is 3-300 μm.
CN202010411913.8A 2020-05-15 2020-05-15 Photochromic ETFE resin film and method for producing same Withdrawn CN111574769A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112812427A (en) * 2020-12-31 2021-05-18 苏州度辰新材料有限公司 Photoluminescent color-changing polyolefin master batch and preparation method thereof
CN113265098A (en) * 2021-05-13 2021-08-17 日氟荣高分子材料(上海)有限公司 High-transparency super-tough ETFE film and preparation method thereof
CN114378968A (en) * 2022-01-12 2022-04-22 深圳市多合盈新材料有限公司 Gas film with anti-counterfeiting effect and production method thereof
CN114790323A (en) * 2022-03-28 2022-07-26 金发科技股份有限公司 Photochromic material and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112812427A (en) * 2020-12-31 2021-05-18 苏州度辰新材料有限公司 Photoluminescent color-changing polyolefin master batch and preparation method thereof
CN113265098A (en) * 2021-05-13 2021-08-17 日氟荣高分子材料(上海)有限公司 High-transparency super-tough ETFE film and preparation method thereof
CN114378968A (en) * 2022-01-12 2022-04-22 深圳市多合盈新材料有限公司 Gas film with anti-counterfeiting effect and production method thereof
CN114790323A (en) * 2022-03-28 2022-07-26 金发科技股份有限公司 Photochromic material and preparation method and application thereof

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