CN113025031A - Light-transmitting film and manufacturing method thereof - Google Patents
Light-transmitting film and manufacturing method thereof Download PDFInfo
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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
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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
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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
- B32B27/18—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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
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Abstract
The invention provides a light-transmitting film and a manufacturing method thereof, wherein the light-transmitting film comprises a TPU thin film and a compensation film; the TPU film is prepared from raw materials including aliphatic diisocyanate, polyether polyol, polyester polyol, a catalyst, a chain extender and dopamine modified silicon dioxide; by adding the aliphatic diisocyanate, the polyether polyol, the polyester polyol and the dopamine modified silicon dioxide in specific parts, the mechanical property of the TPU film can be effectively improved, and the TPU film is compounded with a compensation film, so that a light-transmitting film with excellent mechanical property and high light transmittance is obtained, and the problems of anisotropy and distortion of the TPU film can be solved when the TPU film is applied to electronic products.
Description
Technical Field
The invention belongs to the technical field of films, and particularly relates to a light-transmitting film and a manufacturing method thereof.
Background
TPU (Thermoplastic polyurethane) is a novel organic polymer synthetic material, has better wear resistance and resilience than common polyurethane and PVC materials, has better aging resistance than rubber, and is an ideal material for replacing PVC and PU. The thermoplastic polyurethane has a wide application range, and can be used for shoes, garments, medicines, national defense products, sports products, industrial product materials, wire and cable sheath materials and the like, and also can be used for other applications such as mobile phone keys, plastic inflatable toys, bed sheets, table towels, shower curtains, furniture cloth, aprons, pianos, computer keyboards, film-coated fabrics, lining materials and the like. The composite material is prepared from the composite material and the compensation film, and can be suitable for surface films of electronic products.
Currently, there are many reports and studies on TPU materials. CN108059823A discloses a TPU material with thermal self-repair function and a preparation method thereof. The TPU material comprises the following raw materials in parts by mass: 50-60 parts of diisocyanate, 35-50 parts of polyol, 0.002-0.1 part of graphene, 0.002-0.2 part of carbon nano tube, 5-10 parts of 2-acrylamido-2-methyl-1-propanesulfonic acid, 15-30 parts of styrene-acrylonitrile copolymer, 2-8 parts of chain extender and 0.1-10 parts of catalyst. The TPU material optimizes the self-repairing capability of the material by introducing the carbon nano tube. CN104140517A discloses a high-transparency non-yellowing TPU material, which mainly comprises aliphatic or alicyclic diisocyanate, a small molecular diol chain extender, amorphous high molecular polyol, linear high molecular polyol and the like. The TPU material disclosed by the invention has the characteristics of high transparency and no yellowing, the light transmittance can reach 95%, and the yellowing resistance grade can reach 5. CN111320936A discloses a full laminating optical cement applied to touch screen and a preparation method thereof, the full laminating optical cement adopts one or more of EVA, EMA, POE, PE, TPE, TPO, TPU, EPDM elastomer resin as a base material, the total weight of the elastomer base material is 100 parts, the optical cement further comprises the following raw materials in parts by weight: 0-5 parts of photoinitiator, 0-5 parts of thermal initiator, 0.05-5 parts of polyfunctional group crosslinking agent, 0.01-2 parts of antioxidant, 0.01-2 parts of light stabilizer and 0.1-3 parts of tackifier. The optical cement is applied to the full-lamination field of touch screens, liquid crystal screens and naked eye 3D, has the advantages of low shrinkage rate, strong bonding capability, good sealing effect, simple lamination process, high production efficiency and the like, and also has excellent optical performance, hydrolysis resistance, weather resistance and the like.
However, the light-transmitting film prepared by using the TPU material has insufficient mechanical properties, and the light transmittance is still to be improved.
Therefore, it is very important to develop a light-transmitting film with excellent mechanical properties and high light transmittance.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention is directed to a light transmissive film and a method for manufacturing the same, the light transmissive film including a TPU thin film and a compensation film; the TPU film has excellent mechanical property and light transmittance by selecting specific parts of aliphatic diisocyanate and polyether polyol to match with polyester polyol and adding specific parts of dopamine modified silicon dioxide, and the TPU film and the compensation film are compounded to obtain the light-transmitting film which has excellent buffering and damping effects and high light transmittance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present disclosure provides a light transmissive film comprising a TPU thin film and a compensation film; the TPU film is prepared from the following raw materials in parts by weight:
the light-transmitting film provided by the invention comprises a TPU film and a compensation film, wherein the preparation raw material of the TPU film comprises the combination of alicyclic diisocyanate, polyether polyol and polyester polyol, the TPU film with higher light transmittance can be obtained by controlling the addition amount of the polyether polyol and the polyester polyol, and then the TPU film is compounded with the compensation film to obtain the light-transmitting film with high light transmittance; and secondly, the mechanical property of the TPU material can be effectively improved by adding the dopamine modified silicon dioxide, the compatibility of the dopamine modified silicon dioxide and a substrate is good, the color of the TPU material cannot be influenced by the dopamine modification, and the influence on the light transmittance of the TPU material is smaller compared with the influence of the modification of a common silane coupling agent, so that a TPU film with excellent mechanical property and high light transmittance is obtained.
The aliphatic diisocyanate may be 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, or 69 parts by weight, and specific points therebetween are not exhaustive, and the invention is not limited to the specific points included in the ranges for brevity and clarity.
The polyether polyol may be 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, or 19 parts by weight, and specific values therebetween are not intended to be exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges set forth.
The polyester polyol may be 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, or 19 parts by weight, and specific values therebetween are not intended to be exhaustive, and for the sake of brevity, the invention is not intended to be limited to the specific values encompassed by the scope disclosed.
The catalyst may be present in an amount of 1.3 parts by weight, 1.6 parts by weight, 1.9 parts by weight, 2.3 parts by weight, 2.6 parts by weight, 2.9 parts by weight, 3.3 parts by weight, 3.6 parts by weight, 3.9 parts by weight, 4.3 parts by weight, 4.6 parts by weight, or 4.9 parts by weight, and the like, and specific values therebetween, not to be limited by space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the ranges.
The chain extender may be 1.3, 1.6, 1.9, 2.3, 2.6, 2.9, 3.3, 3.6, 3.9, 4.3, 4.6, or 4.9 parts by weight, and specific points therebetween, not to be construed as space and for brevity, the invention is not exhaustive of the specific points included in the recited ranges.
The dopamine modified silica can be 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, or 9.5 parts by weight, and the specific values therebetween, limited to space and for the sake of brevity, are not exhaustive and are not intended to include the specific values within the recited ranges.
Preferably, the aliphatic diisocyanate comprises isophorone diisocyanate and/or cyclohexanedimethylene diisocyanate.
Preferably, the polyether polyol comprises any one of polyoxypropylene diol, polyoxypropylene triol or polytetrahydrofuran diol, or a combination of at least two thereof.
Preferably, the polyester polyol comprises any one of polybutylene succinate, polybutylene adipate, polyhexamethylene adipate or polybutylene adipate glycol or a combination of at least two of the foregoing.
Preferably, the mass ratio of the polyether polyol to the polyester polyol is 1 (0.5-1.5), such as 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, or 1: 1.4.
According to the preferable technical scheme, the TPU film with excellent mechanical property and high light transmittance can be prepared only by adopting the combination of the polyether polyol and the polyester polyol and controlling the mass ratio of the polyether polyol to the polyester polyol to be 1 (0.5-1.5), so that the light-transmitting film with excellent mechanical property and high light transmittance can be obtained. The polyether polyol has very good elastic modulus because the polyether is a non-polar block, thereby leading the foaming property of a loose porous structure, and the polyester polyol has high crosslinking density and high finished product hardness and high impact strength because the polyester polyol has high molecular weight and has a polar block inside. Therefore, the two are controlled to be matched and used in a proper range, the TPU material with excellent impact strength and higher elastic modulus can be obtained, and the light-transmitting film with excellent mechanical property can be further obtained.
Preferably, the catalyst is any one of stannous octoate, dibutyltin dioctoate or dibutyltin laurate or a combination of at least two of the stannous octoate, the dibutyltin dioctoate or the dibutyltin laurate.
Preferably, the chain extender is any one of ethylene glycol, ethylenediamine, 1, 3-propanediol, 1, 4-butanediol or 1, 6-hexanediol or a combination of at least two of the above.
Preferably, the dopamine modified silica is prepared by a method comprising: and mixing silicon dioxide and dopamine in a solvent to obtain the dopamine modified silicon dioxide.
Preferably, the mass ratio of the silicon dioxide to the dopamine is 1 (0.1-1), such as 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8 or 1: 0.9.
Preferably, the solvent comprises water and/or ethanol.
Preferably, the mixing is performed at a pH of 6 to 9 (e.g., 6.2, 6.3, 6.5, 6.9, 7, 7.2, 7.6, 7.9, 8, 8.2, 8.6, 8.9, etc.).
Preferably, the mixing time is 10-30 min, such as 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min or 28min, and the specific points between the above points are limited by space and for the sake of brevity, the invention is not exhaustive of the specific points included in the range.
Preferably, the temperature of the mixing is 20 to 80 ℃, for example, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the scope.
Preferably, the material of the TPU film further includes any one or a combination of at least two of a defoaming agent, a light diffusing agent, or a lubricant.
Preferably, the amount of the defoaming agent in the raw material for preparing the TPU film is 0.1 to 0.5 parts by weight, such as 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight or 0.45 part by weight, and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and conciseness.
The defoamer comprises an acrylic defoamer.
Preferably, the content of the light diffuser in the raw material for preparing the TPU film is 0.1 to 0.5 parts by weight, such as 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight or 0.45 parts by weight, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
The light diffusion agent comprises any one or the combination of at least two of barium sulfate, calcium carbonate, styrene resin or acrylic resin.
Preferably, the content of the lubricant in the raw material for preparing the TPU film is 0.1 to 0.5 parts by weight, such as 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight or 0.45 parts by weight, and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and conciseness.
Preferably, the lubricant comprises any one of glyceryl monostearate, stearamide, ethylene bis stearamide, E wax or oleamide or a combination of at least two thereof.
In a second aspect, the present invention provides a method for manufacturing a light-transmitting film according to the first aspect, the method comprising the steps of:
(1) reacting aliphatic diisocyanate, polyether polyol, polyester polyol and a catalyst to obtain a polyurethane prepolymer;
(2) reacting the polyurethane prepolymer obtained in the step (1), a chain extender, dopamine modified silica, an optional defoaming agent, an optional light diffusing agent and an optional lubricating agent to obtain a TPU material;
(3) coating the TPU material obtained in the step (2) on a base material, and curing to form a film and stripping to obtain a TPU film;
(4) and (4) compounding the TPU film obtained in the step (3) with a compensation film to obtain the light-transmitting film.
Preferably, the reaction temperature in step (1) is 100-120 ℃, for example, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃ or 118 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time of step (1) is 2-4 h, such as 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h or 3.8h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the range.
Preferably, the reaction temperature in the step (2) is 80-90 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃ or 89 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time in step (2) is 1-3 h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.3h, 2.6h or 2.9h, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the substrate of step (3) comprises a polytetrafluoroethylene plate or a glass plate.
Preferably, the temperature for curing to form the film in step (3) is 80-100 ℃, for example, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃ or 98 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the curing time of the film forming in step (3) is 30-90 min, such as 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min or 85min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the manufacturing method comprises the following steps:
(1) reacting alicyclic diisocyanate, polyether polyol, polyester polyol and a catalyst for 2-4 hours at 100-120 ℃ to obtain a polyurethane prepolymer;
(2) reacting the polyurethane prepolymer obtained in the step (1), a chain extender, dopamine modified silicon dioxide, an optional defoaming agent and an optional lubricant for 1-3 hours at 80-90 ℃ to obtain a TPU material;
(3) coating the TPU material obtained in the step (2) on a polytetrafluoroethylene plate or a glass plate, curing at 80-100 ℃ to form a film for 30-90 min, and stripping to obtain a TPU film;
(4) and (4) compounding the TPU film obtained in the step (3) with a compensation film to obtain the light-transmitting film.
Compared with the prior art, the invention has the following beneficial effects:
the light-transmitting film provided by the invention comprises a TPU film and a compensation film, wherein the preparation raw materials of the TPU film comprise aliphatic diisocyanate, polyether polyol and polyester polyol in specific parts, so that the TPU film with high light transmittance is obtained; secondly, dopamine modified silicon dioxide is added, so that the mechanical property of the TPU film can be effectively improved, and the TPU film is compounded with a compensation film to obtain a light-transmitting film with excellent mechanical property and high light transmittance; specifically, the light-transmitting film provided by the invention has excellent mechanical properties and high light transmittance, wherein the tensile strength is 90.2-94.3 MPa, the tear strength is 150-172 KN/m, the elongation rate is up to 870-930%, and the light transmittance is 98.1-99.6%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The reagents or materials used in the following examples are available from conventional manufacturers, with specific manufacturers and models as shown in table 1:
TABLE 1
| Name (R) | Manufacturer of the product | Model number |
| Isofluorone diisocyanates | Shandong Manghai chemical technology Co Ltd | GB13216 |
| Polyoxypropylene diol | Suzhou Sen Fei Da chemical Co., Ltd | / |
| Polybutylene succinate | Shandong Yiwei Anhua Industrial and scientific Co Ltd | / |
| Acrylic defoaming agent | Shanghai Yueywan New Material Co Ltd | Z3614 |
| Glyceryl monostearate | Zhengzhou Baisute food additive Co., Ltd | / |
Example 1
A light-transmitting film comprising a TPU thin film and a compensation film (dirui co.); the TPU film is prepared from the following raw materials in parts by weight:
the preparation method of the dopamine modified silicon dioxide comprises the following steps: and mixing the silicon dioxide and the dopamine with the mass ratio of 1:0.5 in ethanol at the pH value of 7 and the temperature of 60 ℃ for 20min to obtain the dopamine modified silicon dioxide.
The preparation method of the light-transmitting film comprises the following steps:
(1) reacting isophorone diisocyanate, polyoxypropylene glycol, polybutylene succinate and stannous octoate for 3 hours at 110 ℃ to obtain a polyurethane prepolymer;
(2) reacting the polyurethane prepolymer obtained in the step (1), ethylene glycol, dopamine modified silicon dioxide, an acrylic defoaming agent, barium sulfate and glyceryl monostearate for 2 hours at 85 ℃ to obtain a TPU material;
(3) coating the TPU material obtained in the step (2) on a polytetrafluoroethylene plate, curing for 60min at 90 ℃, and stripping to obtain a TPU film;
(4) and (4) compounding the TPU film obtained in the step (3) with a compensation film to obtain the light-transmitting film.
Example 2
A light-transmitting film comprising a TPU thin film and a compensation film (dirui co.); the TPU film is prepared from the following raw materials in parts by weight:
the preparation method of the dopamine modified silicon dioxide comprises the following steps: mixing silicon dioxide and dopamine with a mass ratio of 1:0.1 in ethanol at a pH value of 6 and a temperature of 20 ℃ for 30min to obtain the dopamine modified silicon dioxide.
The preparation method of the light-transmitting film comprises the following steps:
(1) reacting isophorone diisocyanate, polyoxypropylene glycol, polybutylene succinate and stannous octoate for 4 hours at 100 ℃ to obtain a polyurethane prepolymer;
(2) reacting the polyurethane prepolymer obtained in the step (1), ethylene glycol, dopamine modified silicon dioxide, an acrylic defoaming agent, barium sulfate and glyceryl monostearate for 3 hours at 80 ℃ to obtain a TPU material;
(3) coating the TPU material obtained in the step (2) on a polytetrafluoroethylene plate, curing for 90min at 80 ℃, and stripping to obtain a TPU film;
(4) and (4) compounding the TPU film obtained in the step (3) with a compensation film to obtain the light-transmitting film.
Example 3
A light-transmitting film comprising a TPU thin film and a compensation film (dirui co.); the TPU film is prepared from the following raw materials in parts by weight:
the preparation method of the dopamine modified silicon dioxide comprises the following steps: mixing silicon dioxide and dopamine with the mass ratio of 1:1 in ethanol at the pH value of 9 and the temperature of 80 ℃ for 10min to obtain the dopamine modified silicon dioxide.
The preparation method of the light-transmitting film comprises the following steps:
(1) reacting isophorone diisocyanate, polyoxypropylene glycol, polybutylene succinate and stannous octoate for 2 hours at 120 ℃ to obtain a polyurethane prepolymer;
(2) reacting the polyurethane prepolymer obtained in the step (1), ethylene glycol, dopamine modified silicon dioxide, an acrylic defoaming agent, barium sulfate and glyceryl monostearate for 1h at 90 ℃ to obtain a TPU material;
(3) coating the TPU material obtained in the step (2) on a polytetrafluoroethylene plate, curing for 30min at 100 ℃, and stripping to obtain a TPU film;
(4) and (4) compounding the TPU film obtained in the step (3) with a compensation film to obtain the light-transmitting film.
Example 4
A light-transmitting film which is different from example 1 in that polyoxypropylene glycol was added in an amount of 12 parts by weight, polybutylene succinate was added in an amount of 18 parts by weight, and other components, amounts and steps were the same as in example 1.
Example 5
A light-transmitting film which is different from example 1 in that polyoxypropylene glycol was added in an amount of 18 parts by weight, polybutylene succinate was added in an amount of 12 parts by weight, and other components, amounts and steps were the same as in example 1.
Example 6
A light-transmitting film which is different from example 1 in that polyoxypropylene glycol was added in an amount of 10 parts by weight, polybutylene succinate was added in an amount of 20 parts by weight, and other components, amounts and steps were the same as in example 1.
Example 7
A light-transmitting film which is different from example 1 in that polyoxypropylene glycol was added in an amount of 20 parts by weight, polybutylene succinate was added in an amount of 10 parts by weight, and other components, amounts and steps were the same as in example 1.
Comparative example 1
A light-transmitting film which is different from example 1 in that polyoxypropylene glycol was added in an amount of 25 parts by weight, polybutylene succinate was added in an amount of 5 parts by weight, and other components, amounts and steps were the same as in example 1.
Comparative example 2
A light-transmitting film which is different from example 1 in that polyoxypropylene glycol was added in an amount of 5 parts by weight, polybutylene succinate was added in an amount of 25 parts by weight, and other components, amounts and steps were the same as in example 1.
Comparative example 3
A light-transmitting film which is different from example 1 in that dopamine-modified silica is not added, and other components, amounts and steps are the same as those of example 1.
Comparative example 4
A light-transmitting film is different from example 1 in that dopamine-modified silica is replaced by silane coupling agent-modified silica (the preparation method comprises the steps of mixing a silane coupling agent KH570 and silica in an ethanol solution according to a mass ratio of 1:2 for 4 hours to obtain the silane coupling agent-modified silica), and other components, the using amount and the steps are the same as those in example 1.
And (3) performance testing:
cutting the light-transmitting films obtained in the examples 1-7 and the comparative examples 1-4 into samples to be tested, wherein the sample is 25mm multiplied by 25 mm;
(1) mechanical properties: mechanical property testing was carried out according to the method of GB/T528-1998(ISO37: 2005);
(2) light transmittance: and (3) directly irradiating the sample to be tested for 150 days in the sun, and then testing the light transmittance of the sample according to the method of GB/T2410-2008.
The test method is used for testing the sample to be tested, and the test result is shown in table 3:
TABLE 3
According to the data in the table 3, the light-transmitting film provided by the invention has excellent mechanical properties and high light transmittance, wherein the tensile strength is 90.2-94.3 MPa, the tear strength is 150-172 KN/m, the elongation is up to 870-930%, and the light transmittance is 98.1-99.6%.
Comparing example 1, comparative example 1 and comparative example 2, it can be found that when the polyether polyol and polyester polyol qualities are not in specific ranges, the mechanical properties and light transmittance of the resulting light-transmitting film are reduced; comparing example 1 with comparative example 3, it is seen that the tear strength and tensile strength of the light-transmitting film obtained without adding dopamine-modified silica are reduced; comparing example 1 with comparative example 4, it is seen that the light transmittance of the light transmitting film obtained by adding the silane coupling agent-modified silica is somewhat lowered.
Further, it can be found by comparing example 1 and examples 4 to 7 that when the mass ratio of the polyether polyol and the polyester polyol is within a specific range, the light transmittance and mechanical properties of the obtained light-transmitting film are more excellent.
The applicant states that the present invention is described by the above embodiments as a light-transmitting film and a method for manufacturing the same, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented by the above embodiments. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A light transmissive film comprising a TPU film and a compensation film; the TPU film is prepared from the following raw materials in parts by weight:
2. a light-transmitting film as recited in claim 1, wherein the aliphatic diisocyanate comprises isophorone diisocyanate and/or cyclohexanedimethylene diisocyanate.
3. The light-transmitting film of claim 1 or 2 wherein the polyether polyol comprises any one of, or a combination of at least two of, polyoxypropylene diol, polyoxypropylene triol, or polytetrahydrofuran diol;
preferably, the polyester polyol comprises any one of or a combination of at least two of polybutylene succinate, polybutylene adipate, polyhexamethylene adipate or polyethylene glycol adipate;
preferably, the mass ratio of the polyether polyol to the polyester polyol is 1 (0.5-1.5).
4. The light-transmitting film of any one of claims 1-3 wherein the catalyst is any one of stannous octoate, dibutyltin dioctoate or dibutyltin laurate or a combination of at least two of the stannous octoate, the dibutyltin dioctoate and the dibutyltin laurate;
preferably, the chain extender is any one of ethylene glycol, ethylenediamine, 1, 3-propanediol, 1, 4-butanediol or 1, 6-hexanediol or a combination of at least two of the above.
5. The light-transmitting film according to any one of claims 1 to 4, wherein the dopamine-modified silica is prepared by a method comprising: mixing silicon dioxide and dopamine in a solvent to obtain dopamine modified silicon dioxide;
preferably, the mass ratio of the silicon dioxide to the dopamine is 1 (0.1-1);
preferably, the solvent comprises water and/or ethanol;
preferably, the mixing is carried out under the condition that the pH value is 6-9;
preferably, the mixing time is 10-30 min;
preferably, the mixing temperature is 20-80 ℃.
6. The light-transmitting film according to any one of claims 1 to 5, wherein the raw material for preparing the TPU film further comprises any one or a combination of at least two of a defoaming agent, a light diffusing agent or a lubricant;
preferably, the content of the defoaming agent in the raw materials for preparing the TPU film is 0.1-0.5 part by weight;
the defoamer comprises an acrylic defoamer;
preferably, the content of the light diffusant in the preparation raw material of the TPU film is 0.1-0.5 part by weight;
preferably, the light diffusing agent comprises any one of barium sulfate, calcium carbonate, styrene resin or acrylic resin or a combination of at least two of the same;
preferably, the content of the lubricant in the preparation raw materials of the TPU film is 0.1-0.5 part by weight;
preferably, the lubricant comprises any one of glyceryl monostearate, stearamide, ethylene bis stearamide, E wax or oleamide or a combination of at least two thereof.
7. A method for manufacturing a light-transmitting film as claimed in any one of claims 1 to 6, comprising the steps of:
(1) reacting aliphatic diisocyanate, polyether polyol, polyester polyol and a catalyst to obtain a polyurethane prepolymer;
(2) reacting the polyurethane prepolymer obtained in the step (1), a chain extender, dopamine modified silica, an optional defoaming agent, an optional light diffusing agent and an optional lubricating agent to obtain a TPU material;
(3) coating the TPU material obtained in the step (2) on a base material, and curing to form a film and stripping to obtain a TPU film;
(4) and (4) compounding the TPU film obtained in the step (3) with a compensation film to obtain the light-transmitting film.
8. The method according to claim 7, wherein the reaction temperature in the step (1) is 100 to 120 ℃;
preferably, the reaction time in the step (1) is 2-4 h;
preferably, the reaction temperature in the step (2) is 80-90 ℃;
preferably, the reaction time in the step (2) is 1-3 h.
9. The manufacturing method according to claim 7 or 8, wherein the substrate of step (3) comprises a polytetrafluoroethylene sheet or a glass sheet;
preferably, the temperature for curing and film forming in the step (3) is 80-100 ℃;
preferably, the time for curing and film forming in the step (3) is 30-90 min.
10. The manufacturing method according to any one of claims 7 to 9, characterized by comprising the steps of:
(1) reacting alicyclic diisocyanate, polyether polyol, polyester polyol and a catalyst for 2-4 hours at 100-120 ℃ to obtain a polyurethane prepolymer;
(2) reacting the polyurethane prepolymer obtained in the step (1), a chain extender, dopamine modified silicon dioxide, an optional defoamer, an optional light diffusant and an optional lubricant for 1-3 hours at 80-90 ℃ to obtain a TPU material;
(3) coating the TPU material obtained in the step (2) on a polytetrafluoroethylene plate or a glass plate, curing at 80-100 ℃ to form a film for 30-90 min, and stripping to obtain a TPU film;
(4) and (4) compounding the TPU film obtained in the step (3) with a compensation film to obtain the light-transmitting film.
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