WO2022142305A1 - Colorless transparent polyimide thin film and preparation method therefor, and led film screen - Google Patents

Colorless transparent polyimide thin film and preparation method therefor, and led film screen Download PDF

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WO2022142305A1
WO2022142305A1 PCT/CN2021/108698 CN2021108698W WO2022142305A1 WO 2022142305 A1 WO2022142305 A1 WO 2022142305A1 CN 2021108698 W CN2021108698 W CN 2021108698W WO 2022142305 A1 WO2022142305 A1 WO 2022142305A1
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dianhydride
polyimide film
transparent polyimide
colorless transparent
thermally conductive
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PCT/CN2021/108698
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French (fr)
Chinese (zh)
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金亚东
张远豪
祝炬烨
李智文
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宁波长阳科技股份有限公司
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Publication of WO2022142305A1 publication Critical patent/WO2022142305A1/en

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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
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the present application relates to the technical field of films, in particular to a colorless transparent polyimide film, a preparation method thereof, and an LED film-coated screen.
  • the LED film screen integrates all the advantages of the outdoor high-definition LED display, and maximizes the transparency at the appearance level to eliminate the negative factors that affect the building as much as possible. Even when the screen is not lit, it will not affect the wall, with high transparency, light weight, no space, no steel structure, unique display, 3D stereoscopic look and feel, easy installation, environmental protection and energy saving, etc.
  • the LED film screen is mainly made of colorless and transparent substrate (film) material, but the above-mentioned substrate (film) material still has some defects, such as low transmittance and elastic modulus, poor heat resistance, poor dimensional stability at high temperature, heat dissipation Poor sex, etc. The above defects directly affect the improvement of the performance of the LED film screen.
  • the first object of the present application is to provide a colorless transparent polyimide film, so as to alleviate the low transmittance and elastic modulus of the film material in the prior art, poor heat resistance, poor dimensional stability at high temperature, Technical problems such as poor heat dissipation.
  • the second object of the present application is to provide a method for preparing the above-mentioned colorless transparent polyimide film.
  • the third object of the present application is to provide an LED film-coated screen.
  • a colorless transparent polyimide film provided by the application is mainly made of the following raw materials: polyimide resin and thermally conductive filler;
  • the polyimide resin is mainly obtained by polycondensation of dianhydride and diamine under the action of a dehydrating agent and a catalyst;
  • the dianhydride includes dianhydride A, and the dianhydride A includes 4,4'-hexafluoroisopropyl phthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride or 1,2,3,4-cyclopentanetetra Any one or a combination of at least two of the carboxylic dianhydrides;
  • the diamine includes diamine A, and the diamine A includes 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1, 3-Cyclohexanediamine, 1,3-cyclohexanedimethylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-aminopheny
  • the thermally conductive filler includes unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers, and the mass of the thermally conductive fillers accounts for 5%-60% of the total mass of the colorless transparent polyimide film;
  • the transmittance of the colorless transparent polyimide film is 60%-87%, and the thermal conductivity is 0.4-4.5W/m ⁇ K.
  • the dianhydride includes dianhydride A with a mole fraction of 50%-100% and dianhydride B with a mole fraction of 0%-50%;
  • the dianhydride B includes pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxobisphthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Any one or at least one of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bisphenol A dianhydride or bisphenol F dianhydride a combination of the two;
  • the diamine includes diamine A with a mole fraction of 50%-100% and diamine B with a mole fraction of 0%-50%;
  • the diamine B includes 1,3-diaminobenzene, 1,4-diaminobenzene, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine , 1,3-cyclohexanedimethylamine, 4,4'-diaminodiphenyl ether, 3,3'-oxybenzidine, 3-aminobenzylamine, 3,3'-methylenediphenylamine, 2, 7-diaminofluorene, 1,3-xylylenediamine, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 2,2-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4
  • the dehydrating agent comprises any one or a combination of at least two of acetic anhydride, propionic anhydride or butyric anhydride;
  • the catalyst includes any one or a combination of at least two of pyridine, 3-picoline, triethylamine or isoquinoline.
  • the preparation method of the polyimide resin comprises the following steps:
  • the dianhydride, the diamine and the organic solvent are mixed and stirred, and then a dehydrating agent and a catalyst are added to carry out a polycondensation reaction to obtain a polyimide resin.
  • the molar ratio of the diamine and the dianhydride is 0.9:1-1.1:1;
  • the organic solvent includes any one or at least two of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or ⁇ -butyrolactone. combination;
  • the molar ratio of the dehydrating agent and the dianhydride is 0.5:1-2:1;
  • the molar ratio of the catalyst and the dianhydride is 0.5:1-2:1;
  • the temperature of the polycondensation reaction is 4°C-40°C, and the time of the polycondensation reaction is 4h-24h;
  • the polycondensation reaction is carried out under an inert atmosphere
  • the obtained crude resin is removed from impurities and dried to obtain a polyimide resin.
  • the average particle size of the thermally conductive filler is 0.05 ⁇ m-5 ⁇ m;
  • the unmodified inorganic thermally conductive filler includes any one or a combination of at least two of ⁇ -alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphene;
  • the modified inorganic thermally conductive filler is an inorganic thermally conductive filler whose surface is modified by a coupling agent;
  • the amount of the coupling agent is 1%-5% of the total mass of the modified inorganic thermally conductive filler
  • the coupling agent includes a silane coupling agent, optionally including ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ aminopropyltrimethoxysilane or ⁇ -aminopropyltrimethoxysilane any one in glycidyl ether oxypropyl trimethoxysilane;
  • the inorganic thermally conductive filler includes any one or a combination of at least two of ⁇ -alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphene.
  • the thickness of the colorless transparent polyimide film is 25 ⁇ m-100 ⁇ m.
  • the present application also provides a method for preparing the above-mentioned colorless transparent polyimide film, comprising the following steps:
  • thermally conductive paste formed from thermally conductive fillers and organic polar solvents
  • polyimide slurry formed by polyimide resin and organic polar solvent Provide polyimide slurry formed by polyimide resin and organic polar solvent
  • the thermally conductive paste and the polyimide paste are mixed to form a film to obtain a colorless and transparent polyimide film.
  • the organic polar solvent includes N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or ⁇ -butyrolactone any one or a combination of at least two of the esters;
  • the mass fraction of the polyimide resin in the polyimide slurry is 10%-20%;
  • the preparation method of the colorless transparent polyimide film includes the following steps: after mixing the thermally conductive paste and the polyimide paste, defoaming, casting, drying, stretching and shaping , a colorless transparent polyimide film was obtained.
  • the application also provides an LED film-mounted screen, which is made by using the colorless transparent polyimide film or the colorless transparent polyimide film prepared by the above-mentioned preparation method of the colorless transparent polyimide film.
  • a colorless transparent polyimide film provided by this application is mainly made of raw materials such as polyimide resin and thermally conductive filler, wherein the polyimide resin is mainly composed of dianhydride and diamine in a dehydrating agent.
  • the thermally conductive fillers include unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers; through the limitation of the above-mentioned specific raw materials, the prepared colorless transparent polyimide film has high permeability. Over rate and excellent thermal conductivity, it will not affect the appearance of the building wall after it is made into an LED film screen. At the same time, the heat generated when the LED emits light can be quickly conducted, and the heat will not accumulate and cause the temperature to rise, thus affecting the LED film. the luminous efficiency of the screen.
  • the colorless transparent polyimide film also has the characteristics of high elastic modulus, good heat resistance, not easy to deform at high temperature, that is, good dimensional stability at high temperature, etc. characteristic.
  • the above-mentioned colorless transparent polyimide film has flexibility, can be bent and folded, can meet the application of different occasions, and is more beautiful.
  • the present application provides a method for preparing the above-mentioned colorless transparent polyimide film, which is easy to operate, stable in process, and suitable for large-scale industrial production.
  • the present application provides an LED film-mounted screen, which is made of the colorless transparent polyimide film prepared by the above-mentioned colorless transparent polyimide film or the preparation method of the colorless transparent polyimide film.
  • the LED film screen using it also has the same advantages.
  • the properties of the polyimide film are directly related to the chemical structure of the polyimide, and the chemical structure of the polyimide is related to the selected monomer.
  • a specific type of monomer By selecting a specific type of monomer, a polyimide with a specific structure can be obtained, so that the polyimide film can exhibit specific properties and be applied to a specific field, so this application is proposed.
  • a colorless transparent polyimide film is provided, mainly made from the following raw materials: polyimide resin and thermally conductive filler;
  • polyimide resin is mainly obtained by polycondensation of dianhydride and diamine under the action of dehydrating agent and catalyst;
  • dianhydride includes dianhydride A
  • dianhydride A includes 4,4'-hexafluoroisopropylphthalic anhydride , 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride or 1,2,3,4-cyclopentanetetracarboxylic dianhydride Any one or a combination of at least two;
  • the diamine includes diamine A, and diamine A includes 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine, 1,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine, 3-Cyclohexanedimethylamine, 2,2-bis(3-amino-4-hydroxyphenyl
  • the thermally conductive fillers include unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers, and the mass of the thermally conductive fillers accounts for 5%-60% of the total mass of the colorless transparent polyimide film;
  • the transmittance of the colorless and transparent polyimide film is 60%-87%, and the thermal conductivity is 0.4W/m ⁇ K-4.5W/m ⁇ K.
  • the addition of the thermally conductive filler can effectively improve the thermal conductivity of the colorless transparent polyimide film.
  • the amount of thermally conductive filler is also limited. When the amount of thermally conductive filler is too low (less than 5%), the thermal conductivity of the colorless transparent polyimide film is not significantly improved; when the amount of thermally conductive filler is too high (higher than 60%), it is easy to cause poly The transparency of the imide film decreases, which affects its subsequent application, so the thermally conductive filler should be limited to a specific value range.
  • the typical but non-limiting mass fraction of the colorless transparent polyimide film of the thermally conductive filler is 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% %, 50%, 55% or 60%.
  • Thermally conductive fillers include unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers. Among them, the unmodified inorganic thermally conductive filler is relative to the modified inorganic thermally conductive filler. The difference between the unmodified inorganic thermally conductive filler and the modified inorganic thermally conductive filler is whether the inorganic thermally conductive filler has undergone surface modification treatment. Adding unmodified inorganic thermally conductive fillers and modified inorganic thermally conductive fillers into the film material can both improve the heat dissipation performance of the film material. The modified inorganic thermally conductive filler obtained after surface modification has better compatibility with the polyimide resin, which is more favorable for the thermally conductive filler to be dispersed in the polyimide film and prevent its agglomeration.
  • the thermal filler can include only unmodified inorganic thermally conductive fillers, or only modified inorganic thermally conductive fillers, and can also include both unmodified inorganic thermally conductive fillers and modified inorganic thermally conductive fillers.
  • the film made of polyimide resin is yellow, and this application uses specific kinds of monomers (ie, dianhydride and diamine), and the film made of polyimide resin obtained by polycondensation method It is colorless and transparent, that is, it has good transmittance, which provides a basis for its application in LED film screen.
  • Typical but non-limiting transmittance of colorless transparent polyimide film is 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85% or 87%.
  • the colorless transparent polyimide film provided in this application has good heat dissipation performance, and the typical but non-limiting thermal conductivity is 0.4W/m ⁇ K, 0.5W/m ⁇ K, 1.0W/m ⁇ K, 1.5W /m ⁇ K, 2.0W/m ⁇ K, 2.5W/m ⁇ K, 3.0W/m ⁇ K, 3.5W/m ⁇ K, 4.0W/m ⁇ K, or 4.5W/m ⁇ K.
  • the colorless and transparent polyimide film provided by this application is mainly made of raw materials such as polyimide resin and thermally conductive filler; wherein, the polyimide resin is mainly polycondensed by dianhydride and diamine under the action of dehydrating agent and catalyst. Obtained, the thermally conductive filler includes unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers.
  • the above-mentioned colorless and transparent polyimide film has high transmittance and excellent thermal conductivity. It will not affect the appearance of the building wall after it is made into an LED film screen. At the same time, the heat generated when the LED emits light can be quickly conducted.
  • the colorless transparent polyimide film also has the characteristics of high elastic modulus, good heat resistance, not easy to deform at high temperature, that is, good dimensional stability at high temperature, etc. characteristic.
  • the polyimide resin obtained from the above-mentioned specific types of monomers has a specific molecular structure, so as to give the colorless transparent film a certain flexibility, so that the colorless transparent film can be bent and folded to meet the application of different occasions. beautiful.
  • dianhydrides there are many types of dianhydrides.
  • the dianhydrides in this application are mainly composed of specific types of dianhydrides (ie, dianhydride A and dianhydride B).
  • the dianhydride includes dianhydride A with a mole fraction of 50-100% and dianhydride B with a mole fraction of 0-50%.
  • dianhydride A includes 4,4'-hexafluoroisopropylphthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetra Any one or a combination of at least two of formic acid dianhydride or 1,2,3,4-cyclopentatetracarboxylic dianhydride;
  • Dianhydride B includes pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3' ,4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxobisphthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2, Any one or a combination of at least two of 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bisphenol A dianhydride or bisphenol F dianhydride .
  • Typical but non-limiting amounts (molar fraction) of dianhydride A are 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%.
  • Typical but non-limiting amounts (molar fractions) of dianhydride B are 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%.
  • diamines matching with dianhydrides There are many kinds of diamines matching with dianhydrides.
  • the diamines in this application are mainly composed of specific kinds of diamines (ie, diamine A and diamine B).
  • the diamine includes diamine A with a mole fraction of 50-100% and diamine B with a mole fraction of 0-50%;
  • diamine A includes 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine, 1,3-cyclohexanedimethylamine, 2,2-bis(3 -Amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-tolyl)hexafluoropropane, 3, Any one or a combination of at least two in 5-diaminotrifluorotoluene;
  • Diamine B includes 1,3-diaminobenzene, 1,4-diaminobenzene, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine, 1,3 -Cyclohexanedimethylamine, 4,4'-diaminodiphenyl ether, 3,3'-oxybenzidine, 3-aminobenzylamine, 3,3'-methylenediphenylamine, 2,7-diamino Fluorene, 1,3-xylylenediamine, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2- Bis(3-aminophenyl)hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 2,2-bis(3-aminophenoxy)benzene, 2,2-bis(3-aminophen
  • Typical but non-limiting amounts of diamine A are 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% by mole.
  • Typical but non-limiting amounts of diamine B are 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% by mole fraction.
  • dehydrating agent and catalyst directly affects the progress of the polycondensation reaction.
  • the dehydrating agent includes any one or a combination of at least two of acetic anhydride, propionic anhydride or butyric anhydride.
  • the catalyst comprises any one or a combination of at least two of pyridine, 3-picoline, triethylamine or isoquinoline.
  • the polyimide films prepared from the above-mentioned raw materials have the characteristics of colorless transparency, high elastic modulus and dimensional stability.
  • the preparation method of the polyimide resin directly affects the structure and properties of the polyimide resin.
  • the preparation method of polyimide resin comprises the following steps:
  • the dianhydride, the diamine and the organic solvent are mixed and stirred, and then a dehydrating agent and a catalyst are added to carry out a polycondensation reaction to obtain a polyimide resin.
  • Dianhydride and diamine first react to generate polyamic acid, polyamic acid will generate polyimide and water under the action of catalyst, and water reacts with dehydrating agent, so that the original chemical equilibrium is moved forward, thereby obtaining polyimide resin.
  • the molar ratio of diamine and dianhydride is 0.9:1-1.1:1; typical but non-limiting molar ratios of diamine and dianhydride are 0.9:1, 0.95:1, 1.0:1, 1.05:1 or 1.1:1.
  • the organic solvent includes any one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or ⁇ -butyrolactone or a combination of at least two.
  • the molar ratio of dehydrating agent and dianhydride is 0.5:1-2:1, and the typical but non-limiting molar ratio of dehydrating agent and dianhydride is 0.5:1, 0.6:1, 0.8:1, 1.0:1, 1.2:1, 1.4:1, 1.5:1, 1.6:1, 1.8:1 or 2:1.
  • the molar ratio of catalyst and dianhydride is 0.5:1-2:1; typical but non-limiting molar ratios of catalyst and dianhydride are 0.5:1, 0.6:1, 0.8: 1, 1.0:1, 1.2:1, 1.4:1, 1.5:1, 1.6:1, 1.8:1 or 2:1.
  • the temperature of the polycondensation reaction is 4°C-40°C, and the time of the polycondensation reaction is 4h-24h.
  • Typical but non-limiting polycondensation temperatures are 4°C, 5°C, 10°C, 12°C, 15°C, 18°C, 20°C, 24°C, 25°C, 30°C, 35°C or 40°C.
  • Typical but non-limiting times for the polycondensation reaction are 4h, 5h, 8h, 10h, 12h, 14h, 15h, 18h, 20h or 24h.
  • the polycondensation reaction is carried out under an inert atmosphere.
  • An inert atmosphere is used to prevent oxidation or hydrolysis and ensure the complete reaction of dianhydride and diamine.
  • the obtained crude resin is removed from impurities and dried to obtain a polyimide resin.
  • the preparation method of polyimide resin comprises the following steps:
  • the thermally conductive filler is also one of the key components.
  • the average particle size of the thermally conductive filler is 0.05 ⁇ m-5 ⁇ m.
  • Typical but non-limiting particle sizes of thermally conductive fillers are 0.05 ⁇ m, 0.1 ⁇ m, 0.5 ⁇ m, 1.0 ⁇ m, 1.5 ⁇ m, 2.0 ⁇ m, 2.5 ⁇ m, 3.0 ⁇ m, 3.5 ⁇ m, 4.0 ⁇ m, 4.5 ⁇ m or 5.0 ⁇ m.
  • the unmodified inorganic thermally conductive filler includes any one or a combination of at least two of ⁇ -alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphene .
  • the modified inorganic thermally conductive filler is an inorganic thermally conductive filler whose surface is modified by a coupling agent;
  • the amount of the coupling agent is 1-5% of the total mass of the modified inorganic thermally conductive filler; the typical but non-limiting amount of the coupling agent is 1%, 1.5%, 2%, 2.5%, 3%, 3.5% %, 4%, 4.5% or 5%.
  • the coupling agent includes a silane coupling agent, optionally including ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ aminopropyltrimethoxysilane or ⁇ -glycidyl any one of etheroxypropyl trimethoxysilane;
  • the inorganic thermally conductive filler includes any one or a combination of at least two of ⁇ -alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphene.
  • the coupling agent can fully modify the surface of the inorganic thermally conductive filler, so that the modified inorganic thermally conductive filler and polyimide Amine resins have good compatibility.
  • the thickness of the colorless transparent polyimide film is 25 ⁇ m-100 ⁇ m.
  • Typical but non-limiting thicknesses of colorless transparent polyimide films are 25 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m or 100 ⁇ m.
  • the colorless transparent polyimide film has both transmittance and elastic modulus.
  • thermally conductive paste formed from thermally conductive fillers and organic polar solvents
  • polyimide slurry formed by polyimide resin and organic polar solvent Provide polyimide slurry formed by polyimide resin and organic polar solvent
  • the thermally conductive paste and the polyimide paste are mixed to form a film to obtain a colorless and transparent polyimide film.
  • the preparation method of the above-mentioned colorless transparent polyimide film provided by the present application has the advantages of simple operation and stable process, and is suitable for large-scale industrial production.
  • the mass fraction of the polyimide resin in the polyimide slurry is 10%-20%.
  • the typical but non-limiting mass fraction of the polyimide resin in the polyimide paste is 10%, 12%, 14%, 15%, 16%, 18% or 20%.
  • the organic polar solvent includes any one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or ⁇ -butyrolactone one or a combination of at least two.
  • the preparation method of the colorless transparent polyimide film includes the following steps: after mixing the thermally conductive paste and the polyimide paste, defoaming, casting, drying, Stretching and setting to obtain a colorless transparent polyimide film.
  • an LED film sticking screen is also provided, which is a colorless and transparent polyimide obtained by using the above-mentioned colorless transparent polyimide film or the preparation method of a colorless and transparent polyimide film. Made of film.
  • the LED film screen using it also has the same advantages.
  • the colorless and transparent polyimide film is not limited to the application of LED film screen, but also can be applied to LED lighting or LED display or flexible solar cells, so as to endow the above devices with corresponding characteristics, which is conducive to the heat dissipation of the devices and improved performance.
  • This embodiment provides a colorless transparent polyimide film, which is mainly made of the following raw materials: polyimide resin and thermally conductive filler; wherein, the polyimide resin is mainly composed of dianhydride A (1,2,3 ,4-cyclobutanetetracarboxylic dianhydride) and diamine A (2,2'-bis(trifluoromethyl)diaminobiphenyl) are obtained by polycondensation under the action of dehydrating agent (acetic anhydride) and catalyst (pyridine);
  • the thermally conductive filler is a modified inorganic thermally conductive filler, namely ⁇ -alumina modified by ⁇ -aminopropyltriethoxysilane, and the mass of the thermally conductive filler accounts for 60% of the total mass of the colorless transparent polyimide film.
  • thermoly conductive paste formed from thermally conductive fillers and organic polar solvents
  • the obtained crude polyimide slurry is slowly added to water to separate out, to obtain crude polyimide resin, and the crude polyimide resin is then added to water above 80°C and boiled for 2 hours for impurity removal and separation, and then put into Vacuum drying in a vacuum drying oven to obtain polyimide resin;
  • the composite slurry is subjected to vacuum defoaming treatment, and then cast on a steel strip through a slit die head.
  • the steel strip is divided into 3 temperature zones, the temperatures are 100 ° C, 130 ° C, and 80 ° C, respectively, and a nitrogen atmosphere is used to remove a part of the solvent.
  • the vertical drawing temperature is 150 ° C
  • the vertical drawing ratio is 1.1
  • the horizontal drawing temperature is 250 ° C, 300 ° C, 200 ° C
  • the horizontal drawing ratio is 1.02
  • the roll was wound to obtain a colorless and transparent polyimide film with a thickness of 50 ⁇ m.
  • This embodiment provides a colorless transparent polyimide film, except that the average particle size of the thermally conductive filler is changed from 0.05 ⁇ m to 0.5 ⁇ m, and other raw materials, dosages and preparation methods are the same as those in Embodiment 1.
  • This embodiment provides a colorless transparent polyimide film, except that the average particle size of the thermally conductive filler is changed from 0.05 ⁇ m to 1.0 ⁇ m, and other raw materials, dosages and preparation methods are the same as those in Embodiment 1.
  • This example provides a colorless transparent polyimide film, except that the average particle size of the thermally conductive filler is changed from 0.05 ⁇ m to 5.0 ⁇ m, and the rest of the raw materials, dosage and preparation method are the same as those in Example 1.
  • This embodiment provides a colorless transparent polyimide film, except that the thermally conductive filler is replaced by ⁇ -alumina with aluminum nitride, the average particle size of aluminum nitride is 2.0 ⁇ m, and the mass of the thermally conductive filler accounts for the colorless and transparent polyimide film. 30% of the total mass of the imine film, the thickness of the colorless and transparent polyimide film is 25 ⁇ m, and the remaining raw materials, dosages and preparation methods are the same as those in Example 1.
  • This embodiment provides a colorless transparent polyimide film, except that the thickness of the colorless transparent polyimide film is replaced from 25 ⁇ m to 50 ⁇ m, and other raw materials, dosages and preparation methods are the same as those in Embodiment 5.
  • This embodiment provides a colorless transparent polyimide film, except that the thickness of the colorless transparent polyimide film is replaced from 25 ⁇ m to 75 ⁇ m, and other raw materials, dosages and preparation methods are the same as those in Embodiment 5.
  • This embodiment provides a colorless transparent polyimide film, except that the thickness of the colorless transparent polyimide film is replaced from 25 ⁇ m to 100 ⁇ m, and other raw materials, dosages and preparation methods are the same as those in Embodiment 5.
  • This embodiment provides a colorless transparent polyimide film, except that the thermally conductive filler is replaced by ⁇ -alumina with graphene, the average particle size of graphene is 5.0 ⁇ m, and the mass of the thermally conductive filler accounts for the colorless transparent polyimide 5% of the total mass of the film, and the remaining raw materials, dosages and preparation methods are the same as in Example 1.
  • This embodiment provides a colorless transparent polyimide film, except that the percentage of the mass of the thermally conductive filler in the total mass of the colorless transparent polyimide film is replaced by 5% to 15%, the remaining raw materials, dosages and preparation methods are the same as Example 9 is the same.
  • This embodiment provides a colorless transparent polyimide film, except that the percentage of the mass of the thermally conductive filler in the total mass of the colorless transparent polyimide film is replaced by 5% to 30%, the remaining raw materials, dosage and preparation method are the same as Example 9 is the same.
  • This embodiment provides a colorless and transparent polyimide film, except that the mass of the thermally conductive filler accounts for 50% of the total mass of the colorless and transparent polyimide film, and other raw materials, dosages and preparation methods are the same as Example 9 is the same.
  • This embodiment provides a colorless and transparent polyimide film, in addition to changing the type of dianhydride, that is, replacing 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 4,4 with a mole fraction of 90% '-hexafluoroisopropylphthalic anhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride with a molar fraction of 10%, the remaining raw materials, dosages and preparation methods are the same as in Example 1.
  • This embodiment provides a colorless and transparent polyimide film, in addition to changing the type of dianhydride, that is, replacing 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 4,4 with a mole fraction of 50% '-Hexafluoroisopropylphthalic anhydride (dianhydride A) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (dianhydride B) with a mole fraction of 50%, the remaining raw materials, dosage and
  • the preparation method is the same as that of Example 1.
  • This embodiment provides a colorless and transparent polyimide film, in addition to changing the type of dianhydride, that is, replacing 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 1,2 with a mole fraction of 80% , 3,4-cyclopentatetracarboxylic dianhydride (dianhydride A) and bisphenol A dianhydride (dianhydride B) with a mole fraction of 20%, the remaining raw materials, dosage and preparation method are the same as in Example 1.
  • This embodiment provides a colorless transparent polyimide film, in addition to changing the type of diamine, that is, replacing 2,2'-bis(trifluoromethyl)diaminobiphenyl (diamine A) with a mole fraction of 50% of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (diamine A) and 50% of 2,7-diaminofluorene (diamine B) in mole fraction, the rest of the raw materials,
  • the dosage and preparation method are the same as those in Example 1.
  • This embodiment provides a colorless transparent polyimide film, in addition to changing the type of diamine, that is, replacing 2,2'-bis(trifluoromethyl)diaminobiphenyl (diamine A) with a mole fraction of 75% of 1,3-cyclohexanedimethylamine (diamine A) and 25% of 4,4'-bis(3-aminophenoxy)diphenylsulfone (diamine B) in mole fraction, the rest of the raw materials , dosage and preparation method are the same as in Example 1.
  • This embodiment provides a colorless transparent polyimide film, except that the thermally conductive filler is replaced by a modified inorganic thermally conductive filler ( ⁇ -aminopropyltriethoxysilane-modified ⁇ -alumina) with an unmodified one
  • a modified inorganic thermally conductive filler ⁇ -aminopropyltriethoxysilane-modified ⁇ -alumina
  • the inorganic thermally conductive filler ⁇ -alumina that is, the surface of the ⁇ -alumina has not been surface-modified, and the remaining raw materials and dosages are the same as those in Example 1.
  • Embodiments 19-36 respectively provide an LED film-coated screen, which is made of the colorless and transparent polyimide films provided in Embodiments 1-18, respectively.
  • This comparative example provides a polyimide film, except that no thermally conductive filler is added to the raw materials, and the types and amounts of other raw materials are the same as those in Example 1.
  • step (a) is not performed, and the polyimide slurry is directly formed into a film in step (c).
  • This comparative example provides a polyimide film, except that the thickness of the polyimide film is changed from 50 ⁇ m to 100 ⁇ m, and the remaining steps are the same as those of Comparative Example 1.
  • This comparative example provides a polyimide film, in addition to changing the type of dianhydride, that is, replacing 1,2,3,4-cyclobutanetetracarboxylic dianhydride (dianhydride A) with a homogenate with a mole fraction of 50%
  • dianhydride A 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • dianhydride B 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • dianhydride B 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the preparation method of the polyimide film provided by this comparative example comprises the following steps:
  • thermoly conductive paste formed from thermally conductive fillers and organic polar solvents
  • dianhydride B '-biphenyltetracarboxylic dianhydride
  • This comparative example provides a polyimide film, in addition to changing the type of diamine, that is, replacing 2,2'-bis(trifluoromethyl)diaminobiphenyl (diamine A) with 4,4'-diamine Amino diphenyl ether (diamine B), other raw materials and dosages are the same as those in Example 1.
  • the preparation method of the polyimide film provided in this comparative example is the same as that of the comparative example 3.
  • the thickness, transmittance, thermal conductivity, dimensional stability (thermal shrinkage), elastic modulus and other properties of the polyimide films provided in Examples 1-18 and Comparative Examples 1-4 were tested.
  • the thickness of the polyimide film was measured by a micrometer, and the detection method was based on GB/T 6672-2001; the transmittance was measured by an ultraviolet-visible light spectrophotometer with a wavelength of 550 nm, and the detection method was based on GB/T 2410.
  • the thermal conductivity is measured by the laser thermal conductivity meter LFA 467 to measure the thermal conductivity in the horizontal direction, and the detection method is based on ASTM E1461-2013; the thermal shrinkage is detected by a vernier caliper with an accuracy higher than 0.01 ⁇ m, and the detection method is based on ASTM D2305-2018; The universal tensile testing machine is used for testing, and the testing method is based on GBT1040.3-2006. The specific results are shown in Table 1.
  • the colorless transparent polyimide film provided by this application has better comprehensive properties.
  • the colorless transparent polyimide film provided in Example 12 has the largest thermal conductivity
  • the colorless transparent polyimide film provided in Example 5 has higher thermal conductivity and higher transmittance.
  • Comparative Examples 3-4 are all the control experiments of Example 1. Since different kinds of dianhydrides or diamines were selected in Comparative Examples 3 and 4, the obtained polyimide film was yellow, which was not suitable for use as an LED film-coated screen.

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Abstract

A colorless transparent polyimide thin film and a preparation method therefor, and an LED film screen. The colorless transparent polyimide thin film comprises the following raw materials: polyimide resin and a thermally conductive filler, wherein the polyimide resin is mainly obtained by polycondensation of dianhydride and diamine under the action of a dehydrating agent and a catalyst; the thermally conductive filler comprises an unmodified inorganic thermally conductive filler and/or a modified inorganic thermally conductive filler, and the mass of the thermally conductive filler accounts for 5% to 60% of the total mass of the colorless transparent polyimide thin film; the colorless transparent polyimide thin film has transmittance of 60% to 87% and a coefficient of thermal conductivity of 0.4 W/m·K to 4.5 W/m·K.

Description

无色透明聚酰亚胺薄膜及其制备方法和LED贴膜屏Colorless transparent polyimide film and preparation method thereof, and LED film screen
相关申请Related applications
本申请要求2020年12月31日申请的，申请号为202011628354.2，发明名称为“无色透明聚酰亚胺薄膜及其制备方法和LED贴膜屏”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on December 31, 2020, the application number is 202011628354.2, and the invention name is "colorless transparent polyimide film and its preparation method and LED film screen", the entire content of which is passed Reference is incorporated in this application.
技术领域technical field
本申请涉及薄膜技术领域，尤其是涉及一种无色透明聚酰亚胺薄膜及其制备方法和LED贴膜屏。The present application relates to the technical field of films, in particular to a colorless transparent polyimide film, a preparation method thereof, and an LED film-coated screen.
背景技术Background technique
近年来随着新型显示技术的发展，户外LED显示屏开始大量投放，代替传统的纸质广告牌。LED显示屏可以显示动画影像，内容更换方便，色彩鲜艳，引人注目，因此受到极大青睐。但是传统的LED显示屏安装在建筑外墙，完全挡住室外光线，屏体本身的重量考验建筑物本身的安全性。另外，户外LED显示屏在未进行广告投放时，整块黑色屏体对建筑墙体的外观造成了不利影响。In recent years, with the development of new display technology, outdoor LED display screens have begun to be put into large quantities, replacing traditional paper billboards. The LED display screen can display animated images, the content is easy to change, the color is bright and eye-catching, so it is greatly favored. However, the traditional LED display is installed on the outer wall of the building, which completely blocks the outdoor light. The weight of the screen itself tests the safety of the building itself. In addition, when the outdoor LED display is not advertised, the entire black screen has an adverse effect on the appearance of the building wall.
为了解决这个问题，LED贴膜屏融合了户外高清LED显示屏的所有优点，并在外观层面最大程度通透化，尽可能消除对建筑造成影响的负面因素。即便在屏面没有被点亮的时候，也不会对墙体造成影响，具有高通透、重量轻、不占空间、无需钢结构、显示独特、3D立体般观感、安装简便、环保节能等特点。LED贴膜屏主要由无色透明基板(薄膜)材料制成，但是上述基板(薄膜)材料还存在一些缺陷，例如透过率和弹性模量较低、耐热性差、高温下尺寸稳定性差、散热性差等。上述缺陷直接影响LED贴膜屏性能的提升。In order to solve this problem, the LED film screen integrates all the advantages of the outdoor high-definition LED display, and maximizes the transparency at the appearance level to eliminate the negative factors that affect the building as much as possible. Even when the screen is not lit, it will not affect the wall, with high transparency, light weight, no space, no steel structure, unique display, 3D stereoscopic look and feel, easy installation, environmental protection and energy saving, etc. Features. The LED film screen is mainly made of colorless and transparent substrate (film) material, but the above-mentioned substrate (film) material still has some defects, such as low transmittance and elastic modulus, poor heat resistance, poor dimensional stability at high temperature, heat dissipation Poor sex, etc. The above defects directly affect the improvement of the performance of the LED film screen.
有鉴于此，特提出本申请以解决上述技术问题中的至少一个。In view of this, the present application is made to solve at least one of the above technical problems.
发明内容SUMMARY OF THE INVENTION
本申请的第一目的在于提供一种无色透明聚酰亚胺薄膜，以缓解了现有技术中存在的薄膜材料透过率和弹性模量较低、耐热性差、高温下尺寸稳定性差、散热性差等的技术问题。The first object of the present application is to provide a colorless transparent polyimide film, so as to alleviate the low transmittance and elastic modulus of the film material in the prior art, poor heat resistance, poor dimensional stability at high temperature, Technical problems such as poor heat dissipation.
本申请的第二目的在于提供上述无色透明聚酰亚胺薄膜的制备方法。The second object of the present application is to provide a method for preparing the above-mentioned colorless transparent polyimide film.
本申请的第三目的在于提供一种LED贴膜屏。The third object of the present application is to provide an LED film-coated screen.
为了实现上述目的，本申请的技术方案如下：In order to achieve the above object, the technical scheme of the application is as follows:
本申请提供的一种无色透明聚酰亚胺薄膜，主要采用以下原料制成：聚酰亚胺树脂和导热填料；A colorless transparent polyimide film provided by the application is mainly made of the following raw materials: polyimide resin and thermally conductive filler;
其中，所述聚酰亚胺树脂主要由二酐、二胺在脱水剂和催化剂作用下缩聚得到；所述二酐包括二酐A，所述二酐A包括4,4'-六氟异丙基邻苯二甲酸酐、1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐或1,2,3,4-环戊四羧酸二酐中的任意一种或至少两种的组合；所述二胺包括二胺A，所述二胺A包括2,2'-二(三氟甲基)二氨基联苯、1,3-环己烷二胺、1,3-环己二甲胺、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、2,2-双(3-氨基-4-甲苯基)六氟丙烷或3,5-二氨基三氟甲苯中的任意一种或至少两种的组合；Wherein, the polyimide resin is mainly obtained by polycondensation of dianhydride and diamine under the action of a dehydrating agent and a catalyst; the dianhydride includes dianhydride A, and the dianhydride A includes 4,4'-hexafluoroisopropyl phthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride or 1,2,3,4-cyclopentanetetra Any one or a combination of at least two of the carboxylic dianhydrides; the diamine includes diamine A, and the diamine A includes 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1, 3-Cyclohexanediamine, 1,3-cyclohexanedimethylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl) Any one or a combination of at least two of hexafluoropropane, 2,2-bis(3-amino-4-tolyl)hexafluoropropane or 3,5-diaminotrifluorotoluene;
所述导热填料包括未改性无机导热填料和/或改性无机导热填料，所述导热填料的质量占无色透明聚酰亚胺薄膜总质量的5％-60％；The thermally conductive filler includes unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers, and the mass of the thermally conductive fillers accounts for 5%-60% of the total mass of the colorless transparent polyimide film;
所述无色透明聚酰亚胺薄膜的透过率为60％-87％，导热系数为0.4-4.5W/m·K。The transmittance of the colorless transparent polyimide film is 60%-87%, and the thermal conductivity is 0.4-4.5W/m·K.
进一步，在本申请上述技术方案的基础之上，所述二酐包括摩尔分数为50％-100％的二酐A和摩尔分数为0％-50％的二酐B；Further, on the basis of the above technical solutions of the present application, the dianhydride includes dianhydride A with a mole fraction of 50%-100% and dianhydride B with a mole fraction of 0%-50%;
其中，所述二酐B包括均苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、2,3,3',4-联苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、4,4'-氧代双邻苯二甲酸酐、1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐、1,2,3,4-环戊四羧酸二酐、双酚A二酐或双酚F二酐中的任意一种或至少两种的组合；Wherein, the dianhydride B includes pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxobisphthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Any one or at least one of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bisphenol A dianhydride or bisphenol F dianhydride a combination of the two;
可选的，所述二胺包括摩尔分数为50％-100％的二胺A和摩尔分数为0％-50％的二胺B；Optionally, the diamine includes diamine A with a mole fraction of 50%-100% and diamine B with a mole fraction of 0%-50%;
其中，所述二胺B包括1,3-二氨基苯、1,4-二氨基苯、2,2'-二(三氟甲基)二氨基联苯、1,3-环己烷二胺、1,3-环己二甲胺、4,4'-二氨基二苯醚、3,3'-氧联二苯胺、3-氨基苄胺、3,3'-甲撑二苯胺、2,7-二氨基芴、1,3-苯二甲胺、1,3-双(3-氨基苯氧基)苯、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、1,4-双(3-氨基苯氧基)苯、2,2-双(3-氨基-4-甲苯基)六氟丙烷、3,3'-二氨基二苯砜、4,4'-双(3-氨基苯氧基)二苯基砜、3,3'-二氨基二苯甲酮、3,4'-二氨基二苯基甲烷、3,5-二氨基三氟甲苯或1,2-双(3-氨基苯基)苯胺中的任意一种或至少两种的组合。Wherein, the diamine B includes 1,3-diaminobenzene, 1,4-diaminobenzene, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine , 1,3-cyclohexanedimethylamine, 4,4'-diaminodiphenyl ether, 3,3'-oxybenzidine, 3-aminobenzylamine, 3,3'-methylenediphenylamine, 2, 7-diaminofluorene, 1,3-xylylenediamine, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4-tolyl)hexafluoropropane, 3,3'-diaminodiphenylsulfone, 4,4'-bis(3-aminophenoxy)diphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenylsulfone Any one or a combination of at least two of phenylmethane, 3,5-diaminotrifluorotoluene or 1,2-bis(3-aminophenyl)aniline.
进一步，在本申请上述技术方案的基础之上，所述脱水剂包括乙酸酐、丙酸酐或丁酸酐中的任意一种或至少两种的组合；Further, on the basis of the above technical solutions of the present application, the dehydrating agent comprises any one or a combination of at least two of acetic anhydride, propionic anhydride or butyric anhydride;
可选的，所述催化剂包括吡啶、3-甲基吡啶、三乙胺或异喹啉中的任意一种或至少两种的组合。Optionally, the catalyst includes any one or a combination of at least two of pyridine, 3-picoline, triethylamine or isoquinoline.
进一步，在本申请上述技术方案的基础之上，所述聚酰亚胺树脂的制备方法包括以下步骤：Further, on the basis of the above technical solutions of the present application, the preparation method of the polyimide resin comprises the following steps:
将二酐、二胺和有机溶剂混合搅拌，然后加入脱水剂和催化剂，使进行缩聚反应，得到聚酰亚胺树脂。The dianhydride, the diamine and the organic solvent are mixed and stirred, and then a dehydrating agent and a catalyst are added to carry out a polycondensation reaction to obtain a polyimide resin.
进一步，在本申请上述技术方案的基础之上，所述二胺和二酐的摩尔比为0.9：1-1.1：1；Further, on the basis of the above technical solutions of the present application, the molar ratio of the diamine and the dianhydride is 0.9:1-1.1:1;
可选的，所述有机溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或γ-丁内酯中的任意一种或至少两种的组合；Optionally, the organic solvent includes any one or at least two of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or γ-butyrolactone. combination;
可选的，所述脱水剂和二酐的摩尔比为0.5：1-2：1；Optionally, the molar ratio of the dehydrating agent and the dianhydride is 0.5:1-2:1;
可选的，所述催化剂和二酐的摩尔比为0.5：1-2：1；Optionally, the molar ratio of the catalyst and the dianhydride is 0.5:1-2:1;
可选的，缩聚反应的温度为4℃-40℃，缩聚反应的时间为4h-24h；Optionally, the temperature of the polycondensation reaction is 4°C-40°C, and the time of the polycondensation reaction is 4h-24h;
可选的，缩聚反应在惰性气氛下进行；Optionally, the polycondensation reaction is carried out under an inert atmosphere;
可选的，缩聚反应结束后将得到的粗树脂除杂，干燥，得到聚酰亚胺树脂。Optionally, after the polycondensation reaction is completed, the obtained crude resin is removed from impurities and dried to obtain a polyimide resin.
进一步，在本申请上述技术方案的基础之上，所述导热填料的平均粒径为0.05μm-5μm；Further, on the basis of the above technical solutions of the present application, the average particle size of the thermally conductive filler is 0.05 μm-5 μm;
可选的，所述未改性无机导热填料包括α-氧化铝、氮化铝、氮化硼、碳化硅、碳化氮或石墨烯中的任意一种或至少两种的组合；Optionally, the unmodified inorganic thermally conductive filler includes any one or a combination of at least two of α-alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphene;
可选的，所述改性无机导热填料为经过偶联剂进行表面改性的无机导热填料；Optionally, the modified inorganic thermally conductive filler is an inorganic thermally conductive filler whose surface is modified by a coupling agent;
可选的，所述偶联剂的用量为所述改性无机导热填料总质量的1％-5％；Optionally, the amount of the coupling agent is 1%-5% of the total mass of the modified inorganic thermally conductive filler;
可选的，所述偶联剂包括硅烷偶联剂，可选包括γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-α 氨丙基三甲氧基硅烷或γ-缩水甘油醚氧丙基三甲氧基硅烷中的任意一种；Optionally, the coupling agent includes a silane coupling agent, optionally including γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-αaminopropyltrimethoxysilane or γ-aminopropyltrimethoxysilane any one in glycidyl ether oxypropyl trimethoxysilane;
可选的，所述无机导热填料包括α-氧化铝、氮化铝、氮化硼、碳化硅、碳化氮或石墨烯中的任意一种或至少两种的组合。Optionally, the inorganic thermally conductive filler includes any one or a combination of at least two of α-alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphene.
进一步，在本申请上述技术方案的基础之上，所述无色透明聚酰亚胺薄膜的厚度为25μm-100μm。Further, on the basis of the above technical solutions of the present application, the thickness of the colorless transparent polyimide film is 25 μm-100 μm.
本申请还提供了上述无色透明聚酰亚胺薄膜的制备方法，包括以下步骤：The present application also provides a method for preparing the above-mentioned colorless transparent polyimide film, comprising the following steps:
提供导热填料和有机极性溶剂形成的导热浆料；Provide thermally conductive paste formed from thermally conductive fillers and organic polar solvents;
提供聚酰亚胺树脂和有机极性溶剂形成的聚酰亚胺浆料；Provide polyimide slurry formed by polyimide resin and organic polar solvent;
将导热浆料和聚酰亚胺浆料混合后制膜，得到无色透明聚酰亚胺薄膜。The thermally conductive paste and the polyimide paste are mixed to form a film to obtain a colorless and transparent polyimide film.
进一步，在本申请上述技术方案的基础之上，所述有机极性溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或γ-丁内酯中的任意一种或至少两种的组合；Further, on the basis of the above technical solutions of the present application, the organic polar solvent includes N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or γ-butyrolactone any one or a combination of at least two of the esters;
可选的，聚酰亚胺树脂占聚酰亚胺浆料的质量分数为10％-20％；Optionally, the mass fraction of the polyimide resin in the polyimide slurry is 10%-20%;
可选的，所述无色透明聚酰亚胺薄膜的制备方法，包括以下步骤：将导热浆料和聚酰亚胺浆料混合后，再经消泡、流延、干燥、拉伸和定型，得到无色透明聚酰亚胺薄膜。Optionally, the preparation method of the colorless transparent polyimide film includes the following steps: after mixing the thermally conductive paste and the polyimide paste, defoaming, casting, drying, stretching and shaping , a colorless transparent polyimide film was obtained.
本申请还提供了一种LED贴膜屏，采用上述无色透明聚酰亚胺薄膜或无色透明聚酰亚胺薄膜的制备方法制得的无色透明聚酰亚胺薄膜制成。The application also provides an LED film-mounted screen, which is made by using the colorless transparent polyimide film or the colorless transparent polyimide film prepared by the above-mentioned preparation method of the colorless transparent polyimide film.
与现有技术相比，本申请具有以下有益效果：Compared with the prior art, the present application has the following beneficial effects:
(1)本申请提供的一种无色透明聚酰亚胺薄膜，主要采用聚酰亚胺树脂和导热填料等原料制成，其中，聚酰亚胺树脂主要由二酐、二胺在脱水剂和催化剂作用下缩聚得到，导热填料包括未改性无机导热填料和/或改性无机导热填料；通过对上述特定原料的限定，使得所制得的无色透明聚酰亚胺薄膜具有较高透过率和优异的导热性能，将其制成LED贴膜屏后不会影响建筑墙体的外观，同时LED发光时产生的热量能快速被传导，热量不会集聚造成温度升高，从而影响LED贴膜屏的发光效率。(1) A colorless transparent polyimide film provided by this application is mainly made of raw materials such as polyimide resin and thermally conductive filler, wherein the polyimide resin is mainly composed of dianhydride and diamine in a dehydrating agent. The thermally conductive fillers include unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers; through the limitation of the above-mentioned specific raw materials, the prepared colorless transparent polyimide film has high permeability. Over rate and excellent thermal conductivity, it will not affect the appearance of the building wall after it is made into an LED film screen. At the same time, the heat generated when the LED emits light can be quickly conducted, and the heat will not accumulate and cause the temperature to rise, thus affecting the LED film. the luminous efficiency of the screen.
另外，该无色透明聚酰亚胺薄膜还具有弹性模量高、耐热性好，高温下不易变形即高温尺寸稳定性好等特点，使得应用其的LED贴膜屏具有透明且使用寿命长的特性。且上述无色透明聚酰亚胺薄膜具有柔性，可以进行弯曲、折叠，满足不同场合的应用，更加美观。In addition, the colorless transparent polyimide film also has the characteristics of high elastic modulus, good heat resistance, not easy to deform at high temperature, that is, good dimensional stability at high temperature, etc. characteristic. In addition, the above-mentioned colorless transparent polyimide film has flexibility, can be bent and folded, can meet the application of different occasions, and is more beautiful.
(2)本申请提供了上述无色透明聚酰亚胺薄膜的制备方法，操作简便，工艺稳定，适合规模化工业生产。(2) The present application provides a method for preparing the above-mentioned colorless transparent polyimide film, which is easy to operate, stable in process, and suitable for large-scale industrial production.
(3)本申请提供了一种LED贴膜屏，采用上述无色透明聚酰亚胺薄膜或无色透明聚酰亚胺薄膜的制备方法制得的无色透明聚酰亚胺薄膜制成。鉴于上述无色透明聚酰亚胺薄膜所具有的优势，使得应用其的LED贴膜屏也具有同样的优势。(3) The present application provides an LED film-mounted screen, which is made of the colorless transparent polyimide film prepared by the above-mentioned colorless transparent polyimide film or the preparation method of the colorless transparent polyimide film. In view of the advantages of the above-mentioned colorless and transparent polyimide film, the LED film screen using it also has the same advantages.
具体实施方式Detailed ways
下面将结合实施对本申请的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The technical solutions of the present application will be clearly and completely described below with reference to the implementation. Obviously, the described embodiments are part of the embodiments of the present application, but not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.
发明人发现，聚酰亚胺薄膜的性能与聚酰亚胺的化学结构有直接关系，聚酰亚胺的化学结构又与所选用的单体有关。可通过选择特定种类的单体，从而得到特定结构的聚酰亚胺，进而使得聚酰亚胺薄膜表现出特定的性能以应用到特定的领域，故提出本申请。The inventors found that the properties of the polyimide film are directly related to the chemical structure of the polyimide, and the chemical structure of the polyimide is related to the selected monomer. By selecting a specific type of monomer, a polyimide with a specific structure can be obtained, so that the polyimide film can exhibit specific properties and be applied to a specific field, so this application is proposed.
根据本申请的第一个方面，提供了一种无色透明聚酰亚胺薄膜，主要采用以下原料制 成：聚酰亚胺树脂和导热填料；According to a first aspect of the present application, a colorless transparent polyimide film is provided, mainly made from the following raw materials: polyimide resin and thermally conductive filler;
其中，聚酰亚胺树脂主要由二酐、二胺在脱水剂和催化剂作用下缩聚得到；二酐包括二酐A，二酐A包括4,4'-六氟异丙基邻苯二甲酸酐、1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐或1,2,3,4-环戊四羧酸二酐中的任意一种或至少两种的组合；二胺包括二胺A，二胺A包括2,2'-二(三氟甲基)二氨基联苯、1,3-环己烷二胺、1,3-环己二甲胺、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、2,2-双(3-氨基-4-甲苯基)六氟丙烷或3,5-二氨基三氟甲苯中的任意一种或至少两种的组合；Among them, polyimide resin is mainly obtained by polycondensation of dianhydride and diamine under the action of dehydrating agent and catalyst; dianhydride includes dianhydride A, and dianhydride A includes 4,4'-hexafluoroisopropylphthalic anhydride , 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride or 1,2,3,4-cyclopentanetetracarboxylic dianhydride Any one or a combination of at least two; the diamine includes diamine A, and diamine A includes 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine, 1,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine, 3-Cyclohexanedimethylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis( 3-amino-4-tolyl) hexafluoropropane or 3,5-diaminotrifluorotoluene any one or a combination of at least two;
导热填料包括未改性无机导热填料和/或改性无机导热填料，所述导热填料的质量占无色透明聚酰亚胺薄膜总质量的5％-60％；The thermally conductive fillers include unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers, and the mass of the thermally conductive fillers accounts for 5%-60% of the total mass of the colorless transparent polyimide film;
无色透明聚酰亚胺薄膜的透过率为60％-87％，导热系数为0.4W/m·K-4.5W/m·K。The transmittance of the colorless and transparent polyimide film is 60%-87%, and the thermal conductivity is 0.4W/m·K-4.5W/m·K.
具体的，导热填料的加入，可有效提高无色透明聚酰亚胺薄膜的导热性能。Specifically, the addition of the thermally conductive filler can effectively improve the thermal conductivity of the colorless transparent polyimide film.
导热填料的用量也有一定的限定。当导热填料的用量过低(低于5％)，则其对于无色透明聚酰亚胺薄膜的导热性能提升不明显；当导热填料的用量过高(高于60％)，则容易导致聚酰亚胺薄膜的透明度下降，影响其后续应用，故导热填料应该限定在特定的数值范围内。在本申请中，导热填料占无色透明聚酰亚胺薄膜典型但非限制性的质量分数为5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％或60％。通过对导热填料的用量的限定，使得上述薄膜在具有良好散热性能的同时，还具有较高的光透过率。The amount of thermally conductive filler is also limited. When the amount of thermally conductive filler is too low (less than 5%), the thermal conductivity of the colorless transparent polyimide film is not significantly improved; when the amount of thermally conductive filler is too high (higher than 60%), it is easy to cause poly The transparency of the imide film decreases, which affects its subsequent application, so the thermally conductive filler should be limited to a specific value range. In this application, the typical but non-limiting mass fraction of the colorless transparent polyimide film of the thermally conductive filler is 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% %, 50%, 55% or 60%. By limiting the amount of the thermally conductive filler, the above-mentioned film has good heat dissipation performance and high light transmittance.
导热填料包括未改性无机导热填料和/或改性无机导热填料。其中，未改性无机导热填料是相对于改性无机导热填料而言的，未改性无机导热填料和改性无机导热填料的区别在于无机导热填料是否经过表面改性处理。将未改性无机导热填料、改性无机导热填料加入到薄膜材料中均能提升薄膜材料的散热性能。经过表面改性后得到的改性无机导热填料与聚酰亚胺树脂的相容性更好，更有利于导热填料分散在聚酰亚胺薄膜中，防止其团聚。Thermally conductive fillers include unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers. Among them, the unmodified inorganic thermally conductive filler is relative to the modified inorganic thermally conductive filler. The difference between the unmodified inorganic thermally conductive filler and the modified inorganic thermally conductive filler is whether the inorganic thermally conductive filler has undergone surface modification treatment. Adding unmodified inorganic thermally conductive fillers and modified inorganic thermally conductive fillers into the film material can both improve the heat dissipation performance of the film material. The modified inorganic thermally conductive filler obtained after surface modification has better compatibility with the polyimide resin, which is more favorable for the thermally conductive filler to be dispersed in the polyimide film and prevent its agglomeration.
此处的“和/或”是指导热填料可以只包括未改性无机导热填料，也可以只包括改性无机导热填料，还可以同时包括未改性无机导热填料和改性无机导热填料。The "and/or" here indicates that the thermal filler can include only unmodified inorganic thermally conductive fillers, or only modified inorganic thermally conductive fillers, and can also include both unmodified inorganic thermally conductive fillers and modified inorganic thermally conductive fillers.
通常情况下，聚酰亚胺树脂制成的薄膜呈黄色，而本申请通过采用特定种类的单体(即二酐和二胺)，通过缩聚方法制得的聚酰亚胺树脂制成的薄膜呈无色透明，即具有良好的透过率，为其应用于LED贴膜屏提供了基础。Under normal circumstances, the film made of polyimide resin is yellow, and this application uses specific kinds of monomers (ie, dianhydride and diamine), and the film made of polyimide resin obtained by polycondensation method It is colorless and transparent, that is, it has good transmittance, which provides a basis for its application in LED film screen.
无色透明聚酰亚胺薄膜典型但非限制性的透过率为60％、62％、65％、68％、70％、72％、75％、78％、80％、82％、85％或87％。Typical but non-limiting transmittance of colorless transparent polyimide film is 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85% or 87%.
本申请提供的无色透明聚酰亚胺薄膜具有良好的散热性能，典型但非限制性的导热系数为0.4W/m·K、0.5W/m·K、1.0W/m·K、1.5W/m·K、2.0W/m·K、2.5W/m·K、3.0W/m·K、3.5W/m·K、4.0W/m·K或4.5W/m·K。The colorless transparent polyimide film provided in this application has good heat dissipation performance, and the typical but non-limiting thermal conductivity is 0.4W/m·K, 0.5W/m·K, 1.0W/m·K, 1.5W /m·K, 2.0W/m·K, 2.5W/m·K, 3.0W/m·K, 3.5W/m·K, 4.0W/m·K, or 4.5W/m·K.
本申请提供的无色透明聚酰亚胺薄膜，主要采用聚酰亚胺树脂和导热填料等原料制成；其中，聚酰亚胺树脂主要由二酐、二胺在脱水剂和催化剂作用下缩聚得到，导热填料包括未改性无机导热填料和/或改性无机导热填料。上述无色透明聚酰亚胺薄膜具有较高透过率和优异的导热性能，将其制成LED贴膜屏后不会影响建筑墙体的外观，同时LED发光时产生的热量能快速被传导，热量不会集聚造成温度升高，从而影响LED贴膜屏的发光效率。另外，该无色透明聚酰亚胺薄膜还具有弹性模量高、耐热性好，高温下不易变形即高温尺寸稳定性好等特点，使得应用其的LED贴膜屏具有透明且使用寿命长的特性。且上 述特定种类的单体制得的聚酰亚胺树脂具有特定的分子结构，从而赋予该无色透明薄膜一定的柔性，使得该无色透明薄膜可以进行弯曲、折叠，满足不同场合的应用，更加美观。The colorless and transparent polyimide film provided by this application is mainly made of raw materials such as polyimide resin and thermally conductive filler; wherein, the polyimide resin is mainly polycondensed by dianhydride and diamine under the action of dehydrating agent and catalyst. Obtained, the thermally conductive filler includes unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers. The above-mentioned colorless and transparent polyimide film has high transmittance and excellent thermal conductivity. It will not affect the appearance of the building wall after it is made into an LED film screen. At the same time, the heat generated when the LED emits light can be quickly conducted. The heat will not accumulate and cause the temperature to rise, thus affecting the luminous efficiency of the LED film screen. In addition, the colorless transparent polyimide film also has the characteristics of high elastic modulus, good heat resistance, not easy to deform at high temperature, that is, good dimensional stability at high temperature, etc. characteristic. And the polyimide resin obtained from the above-mentioned specific types of monomers has a specific molecular structure, so as to give the colorless transparent film a certain flexibility, so that the colorless transparent film can be bent and folded to meet the application of different occasions. beautiful.
本申请所述的“主要由……制成”，意指其除所述原料外，还可以包括聚酰亚胺薄膜领域可接受的其他原料，这些其他原料可赋予无色透明聚酰亚胺薄膜不同的特性。除此之外，本申请所述的“主要由……制成”，还可以替换为封闭式的“为”或“由……制成”。In this application, "mainly made of" means that in addition to the above-mentioned raw materials, it may also include other raw materials acceptable in the field of polyimide films, and these other raw materials can impart colorless and transparent polyimide Films with different properties. Besides, "mainly made of" mentioned in this application can also be replaced with closed "is" or "made of".
二酐的种类有很多，可选地，本申请中的二酐主要由特定种类的二酐(即，二酐A和二酐B)复合而成。There are many types of dianhydrides. Optionally, the dianhydrides in this application are mainly composed of specific types of dianhydrides (ie, dianhydride A and dianhydride B).
作为本申请的一种可选实施方式，二酐包括摩尔分数为50-100％的二酐A和摩尔分数为0-50％的二酐B。As an optional embodiment of the present application, the dianhydride includes dianhydride A with a mole fraction of 50-100% and dianhydride B with a mole fraction of 0-50%.
其中，二酐A包括4,4'-六氟异丙基邻苯二甲酸酐、1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐或1,2,3,4-环戊四羧酸二酐中的任意一种或至少两种的组合；Among them, dianhydride A includes 4,4'-hexafluoroisopropylphthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetra Any one or a combination of at least two of formic acid dianhydride or 1,2,3,4-cyclopentatetracarboxylic dianhydride;
二酐B包括均苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、2,3,3',4-联苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、4,4'-氧代双邻苯二甲酸酐、1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐、1,2,3,4-环戊四羧酸二酐、双酚A二酐或双酚F二酐中的任意一种或至少两种的组合。Dianhydride B includes pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3' ,4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxobisphthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2, Any one or a combination of at least two of 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bisphenol A dianhydride or bisphenol F dianhydride .
二酐A典型但非限制性的用量(摩尔分数)为50％、55％、60％、65％、70％、75％、80％、85％、90％、95％或100％。二酐B典型但非限制性的用量(摩尔分数)为0％、5％、10％、15％、20％、25％、30％、35％、40％、45％或50％。Typical but non-limiting amounts (molar fraction) of dianhydride A are 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%. Typical but non-limiting amounts (molar fractions) of dianhydride B are 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%.
与二酐匹配的二胺的种类有很多，可选地，本申请中的二胺主要由特定种类的二胺(即，二胺A和二胺B)复合而成。There are many kinds of diamines matching with dianhydrides. Optionally, the diamines in this application are mainly composed of specific kinds of diamines (ie, diamine A and diamine B).
作为本申请的一种可选实施方式，二胺包括摩尔分数为50-100％的二胺A和摩尔分数为0-50％的二胺B；As an optional embodiment of the present application, the diamine includes diamine A with a mole fraction of 50-100% and diamine B with a mole fraction of 0-50%;
其中，二胺A包括2,2'-二(三氟甲基)二氨基联苯、1,3-环己烷二胺、1,3-环己二甲胺、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、2,2-双(3-氨基-4-甲苯基)六氟丙烷、3,5-二氨基三氟甲苯中的任意一种或至少两种的组合；Wherein, diamine A includes 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine, 1,3-cyclohexanedimethylamine, 2,2-bis(3 -Amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-tolyl)hexafluoropropane, 3, Any one or a combination of at least two in 5-diaminotrifluorotoluene;
二胺B包括1,3-二氨基苯、1,4-二氨基苯、2,2'-二(三氟甲基)二氨基联苯、1,3-环己烷二胺、1,3-环己二甲胺、4,4'-二氨基二苯醚、3,3'-氧联二苯胺、3-氨基苄胺、3,3'-甲撑二苯胺、2,7-二氨基芴、1,3-苯二甲胺、1,3-双(3-氨基苯氧基)苯、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、1,4-双(3-氨基苯氧基)苯、2,2-双(3-氨基-4-甲苯基)六氟丙烷、3,3'-二氨基二苯砜、4,4'-双(3-氨基苯氧基)二苯基砜、3,3'-二氨基二苯甲酮、3,4'-二氨基二苯基甲烷、3,5-二氨基三氟甲苯或1,2-双(3-氨基苯基)苯胺中的任意一种或至少两种的组合。Diamine B includes 1,3-diaminobenzene, 1,4-diaminobenzene, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine, 1,3 -Cyclohexanedimethylamine, 4,4'-diaminodiphenyl ether, 3,3'-oxybenzidine, 3-aminobenzylamine, 3,3'-methylenediphenylamine, 2,7-diamino Fluorene, 1,3-xylylenediamine, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2- Bis(3-aminophenyl)hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4-tolyl)hexafluoropropane, 3,3' -Diaminodiphenylsulfone, 4,4'-bis(3-aminophenoxy)diphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenylmethane, Any one or a combination of at least two of 3,5-diaminotrifluorotoluene or 1,2-bis(3-aminophenyl)aniline.
二胺A典型但非限制性的用量为摩尔分数为50％、55％、60％、65％、70％、75％、80％、85％、90％、95％或100％。二胺B典型但非限制性的用量为摩尔分数为0％、5％、10％、15％、20％、25％、30％、35％、40％、45％或50％。Typical but non-limiting amounts of diamine A are 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% by mole. Typical but non-limiting amounts of diamine B are 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% by mole fraction.
脱水剂和催化剂的具体种类直接影响到缩聚反应的进行。The specific type of dehydrating agent and catalyst directly affects the progress of the polycondensation reaction.
作为本申请的一种可选实施方式，脱水剂包括乙酸酐、丙酸酐或丁酸酐中的任意一种或至少两种的组合。As an optional embodiment of the present application, the dehydrating agent includes any one or a combination of at least two of acetic anhydride, propionic anhydride or butyric anhydride.
作为本申请的一种可选实施方式，催化剂包括吡啶、3-甲基吡啶、三乙胺或异喹啉中 的任意一种或至少两种的组合。As an optional embodiment of the present application, the catalyst comprises any one or a combination of at least two of pyridine, 3-picoline, triethylamine or isoquinoline.
通过对二酐、二胺具体种类以及摩尔配比、脱水剂和催化剂具体种类的限定，使得采用上述原料制得的聚酰亚胺薄膜具有无色透明、高弹性模量以及尺寸稳定的特性。By limiting the specific types and molar ratios of dianhydrides and diamines, as well as the specific types of dehydrating agents and catalysts, the polyimide films prepared from the above-mentioned raw materials have the characteristics of colorless transparency, high elastic modulus and dimensional stability.
聚酰亚胺树脂的制备方法直接影响聚酰亚胺树脂的结构以及特性。作为本申请的一种可选实施方式，聚酰亚胺树脂的制备方法包括以下步骤：The preparation method of the polyimide resin directly affects the structure and properties of the polyimide resin. As an optional embodiment of the present application, the preparation method of polyimide resin comprises the following steps:
将二酐、二胺和有机溶剂混合搅拌，然后加入脱水剂和催化剂，使进行缩聚反应，得到聚酰亚胺树脂。The dianhydride, the diamine and the organic solvent are mixed and stirred, and then a dehydrating agent and a catalyst are added to carry out a polycondensation reaction to obtain a polyimide resin.
二酐和二胺首先反应生成聚酰胺酸，聚酰胺酸在催化剂作用下会生成聚酰亚胺和水，水和脱水剂反应，使得原来化学平衡正向移动，从而得到聚酰亚胺树脂。Dianhydride and diamine first react to generate polyamic acid, polyamic acid will generate polyimide and water under the action of catalyst, and water reacts with dehydrating agent, so that the original chemical equilibrium is moved forward, thereby obtaining polyimide resin.
作为本申请的一种可选实施方式，二胺和二酐的摩尔比为0.9：1-1.1：1；二胺和二酐典型但非限制性的摩尔比为0.9：1、0.95：1、1.0：1、1.05：1或1.1：1。As an optional embodiment of the present application, the molar ratio of diamine and dianhydride is 0.9:1-1.1:1; typical but non-limiting molar ratios of diamine and dianhydride are 0.9:1, 0.95:1, 1.0:1, 1.05:1 or 1.1:1.
作为本申请的一种可选实施方式，有机溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或γ-丁内酯中的任意一种或至少两种的组合。As an optional embodiment of the present application, the organic solvent includes any one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or γ-butyrolactone or a combination of at least two.
作为本申请的一种可选实施方式，脱水剂和二酐的摩尔比为0.5：1-2：1，脱水剂和二酐典型但非限制性的摩尔比为0.5：1、0.6：1、0.8：1、1.0：1、1.2：1、1.4：1、1.5：1、1.6：1、1.8：1或2：1。As an optional embodiment of the present application, the molar ratio of dehydrating agent and dianhydride is 0.5:1-2:1, and the typical but non-limiting molar ratio of dehydrating agent and dianhydride is 0.5:1, 0.6:1, 0.8:1, 1.0:1, 1.2:1, 1.4:1, 1.5:1, 1.6:1, 1.8:1 or 2:1.
作为本申请的一种可选实施方式，催化剂和二酐的摩尔比为0.5：1-2：1；催化剂和二酐典型但非限制性的摩尔比为0.5：1、0.6：1、0.8：1、1.0：1、1.2：1、1.4：1、1.5：1、1.6：1、1.8：1或2：1。As an optional embodiment of the present application, the molar ratio of catalyst and dianhydride is 0.5:1-2:1; typical but non-limiting molar ratios of catalyst and dianhydride are 0.5:1, 0.6:1, 0.8: 1, 1.0:1, 1.2:1, 1.4:1, 1.5:1, 1.6:1, 1.8:1 or 2:1.
作为本申请的一种可选实施方式，缩聚反应的温度为4℃-40℃，缩聚反应的时间为4h-24h。典型但非限制性的缩聚反应的温度为4℃、5℃、10℃、12℃、15℃、18℃、20℃、24℃、25℃、30℃、35℃或40℃。典型但非限制性的缩聚反应的时间为4h、5h、8h、10h、12h、14h、15h、18h、20h或24h。As an optional embodiment of the present application, the temperature of the polycondensation reaction is 4°C-40°C, and the time of the polycondensation reaction is 4h-24h. Typical but non-limiting polycondensation temperatures are 4°C, 5°C, 10°C, 12°C, 15°C, 18°C, 20°C, 24°C, 25°C, 30°C, 35°C or 40°C. Typical but non-limiting times for the polycondensation reaction are 4h, 5h, 8h, 10h, 12h, 14h, 15h, 18h, 20h or 24h.
作为本申请的一种可选实施方式，缩聚反应在惰性气氛下进行。采用惰性气氛，防止氧化或者水解，保证二酐和二胺反应完全。As an optional embodiment of the present application, the polycondensation reaction is carried out under an inert atmosphere. An inert atmosphere is used to prevent oxidation or hydrolysis and ensure the complete reaction of dianhydride and diamine.
作为本申请的一种可选实施方式，缩聚反应结束后将得到的粗树脂除杂，干燥，得到聚酰亚胺树脂。As an optional embodiment of the present application, after the polycondensation reaction is completed, the obtained crude resin is removed from impurities and dried to obtain a polyimide resin.
作为本申请的一种可选实施方式，聚酰亚胺树脂的制备方法包括以下步骤：As an optional embodiment of the present application, the preparation method of polyimide resin comprises the following steps:
将二胺溶解在有机溶剂中，加入二酐，搅拌4h，再加入脱水剂和催化剂，搅拌4h，或者将二酐溶解在有机溶剂中，加入二胺，搅拌4h，再加入脱水剂和催化剂，搅拌4h，得到聚酰亚胺浆料；Dissolve diamine in organic solvent, add dianhydride, stir for 4h, then add dehydrating agent and catalyst, stir for 4h, or dissolve dianhydride in organic solvent, add diamine, stir for 4h, then add dehydrating agent and catalyst, Stir for 4h to obtain polyimide slurry;
将上述聚酰亚胺浆料缓慢加入水中析出，得到粗树脂，粗树脂加入80℃以上水中水煮0.5h-3h除杂，然后再将其放入真空干燥箱真空烘干，得到聚酰亚胺树脂。Slowly add the above polyimide slurry into water to separate out to obtain a crude resin, add the crude resin to water above 80°C and boil for 0.5h-3h to remove impurities, and then put it into a vacuum drying box for vacuum drying to obtain a polyimide Amine resin.
在本申请中，除了聚酰亚胺树脂，导热填料也是关键组分之一。In this application, besides the polyimide resin, the thermally conductive filler is also one of the key components.
作为本申请的一种可选实施方式，导热填料的平均粒径为0.05μm-5μm。导热填料典型但非限制性的粒径为0.05μm、0.1μm、0.5μm、1.0μm、1.5μm、2.0μm、2.5μm、3.0μm、3.5μm、4.0μm、4.5μm或5.0μm。As an optional embodiment of the present application, the average particle size of the thermally conductive filler is 0.05 μm-5 μm. Typical but non-limiting particle sizes of thermally conductive fillers are 0.05 μm, 0.1 μm, 0.5 μm, 1.0 μm, 1.5 μm, 2.0 μm, 2.5 μm, 3.0 μm, 3.5 μm, 4.0 μm, 4.5 μm or 5.0 μm.
作为本申请的一种可选实施方式，未改性无机导热填料包括α-氧化铝、氮化铝、氮化硼、碳化硅、碳化氮或石墨烯中的任意一种或至少两种的组合。As an optional embodiment of the present application, the unmodified inorganic thermally conductive filler includes any one or a combination of at least two of α-alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphene .
作为本申请的一种可选实施方式，改性无机导热填料为经过偶联剂进行表面改性的无机导热填料；As an optional embodiment of the present application, the modified inorganic thermally conductive filler is an inorganic thermally conductive filler whose surface is modified by a coupling agent;
可选的，偶联剂的用量为改性无机导热填料总质量的1-5％；偶联剂典型但非限制性的用量为1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％或5％。Optionally, the amount of the coupling agent is 1-5% of the total mass of the modified inorganic thermally conductive filler; the typical but non-limiting amount of the coupling agent is 1%, 1.5%, 2%, 2.5%, 3%, 3.5% %, 4%, 4.5% or 5%.
可选的，偶联剂包括硅烷偶联剂，可选包括γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-α氨丙基三甲氧基硅烷或γ-缩水甘油醚氧丙基三甲氧基硅烷中的任意一种；Optionally, the coupling agent includes a silane coupling agent, optionally including γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-αaminopropyltrimethoxysilane or γ-glycidyl any one of etheroxypropyl trimethoxysilane;
可选的，无机导热填料包括α-氧化铝、氮化铝、氮化硼、碳化硅、碳化氮或石墨烯中的任意一种或至少两种的组合。Optionally, the inorganic thermally conductive filler includes any one or a combination of at least two of α-alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphene.
通过对改性无机导热填料中偶联剂具体种类、用量以及无机导热填料具体种类的限定，使得偶联剂对无机导热填料的表面进行充分改性，从而使得改性无机导热填料与聚酰亚胺树脂有良好的相容性。By limiting the specific type and dosage of the coupling agent in the modified inorganic thermally conductive filler and the specific type of the inorganic thermally conductive filler, the coupling agent can fully modify the surface of the inorganic thermally conductive filler, so that the modified inorganic thermally conductive filler and polyimide Amine resins have good compatibility.
作为本申请的一种可选实施方式，无色透明聚酰亚胺薄膜的厚度为25μm-100μm。无色透明聚酰亚胺薄膜典型但非限制性的厚度为25μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm或100μm。As an optional embodiment of the present application, the thickness of the colorless transparent polyimide film is 25 μm-100 μm. Typical but non-limiting thicknesses of colorless transparent polyimide films are 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm.
通过对厚度的限定，使得无色透明聚酰亚胺薄膜兼顾透过率与弹性模量。By limiting the thickness, the colorless transparent polyimide film has both transmittance and elastic modulus.
根据本申请的第二个方面，还提供了上述无色透明聚酰亚胺薄膜的制备方法，包括以下步骤：According to the second aspect of the present application, there is also provided a method for preparing the above-mentioned colorless transparent polyimide film, comprising the following steps:
提供导热填料和有机极性溶剂形成的导热浆料；Provide thermally conductive paste formed from thermally conductive fillers and organic polar solvents;
提供聚酰亚胺树脂和有机极性溶剂形成的聚酰亚胺浆料；Provide polyimide slurry formed by polyimide resin and organic polar solvent;
将导热浆料和聚酰亚胺浆料混合后制膜，得到无色透明聚酰亚胺薄膜。The thermally conductive paste and the polyimide paste are mixed to form a film to obtain a colorless and transparent polyimide film.
本申请提供的上述无色透明聚酰亚胺薄膜的制备方法，操作简便，工艺稳定，适合规模化工业生产。The preparation method of the above-mentioned colorless transparent polyimide film provided by the present application has the advantages of simple operation and stable process, and is suitable for large-scale industrial production.
作为本申请的一种可选实施方式，聚酰亚胺树脂占聚酰亚胺浆料的质量分数为10％-20％。As an optional embodiment of the present application, the mass fraction of the polyimide resin in the polyimide slurry is 10%-20%.
聚酰亚胺树脂占聚酰亚胺浆料典型但非限制性的质量分数为10％、12％、14％、15％、16％、18％或20％。The typical but non-limiting mass fraction of the polyimide resin in the polyimide paste is 10%, 12%, 14%, 15%, 16%, 18% or 20%.
有机极性溶剂的具体种类不作具体限定，只要确保其对导热填料和聚酰亚胺树脂具有良好的溶解能力即可。作为本申请的一种可选实施方式，有机极性溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或γ-丁内酯中的任意一种或至少两种的组合。The specific type of the organic polar solvent is not particularly limited, as long as it has good dissolving ability to the thermally conductive filler and polyimide resin. As an optional embodiment of the present application, the organic polar solvent includes any one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or γ-butyrolactone one or a combination of at least two.
作为本申请的一种可选实施方式，无色透明聚酰亚胺薄膜的制备方法包括以下步骤：将导热浆料和聚酰亚胺浆料混合后，再经消泡、流延、干燥、拉伸和定型，得到无色透明聚酰亚胺薄膜。As an optional embodiment of the present application, the preparation method of the colorless transparent polyimide film includes the following steps: after mixing the thermally conductive paste and the polyimide paste, defoaming, casting, drying, Stretching and setting to obtain a colorless transparent polyimide film.
具体的制膜工艺为本领域常用的技术手段，此处不再赘述。The specific film-forming process is a technical means commonly used in the art, and details are not described here.
根据本申请的第三个方面，还提供了一种LED贴膜屏，采用上述无色透明聚酰亚胺薄膜或无色透明聚酰亚胺薄膜的制备方法制得的无色透明聚酰亚胺薄膜制成。According to the third aspect of the present application, an LED film sticking screen is also provided, which is a colorless and transparent polyimide obtained by using the above-mentioned colorless transparent polyimide film or the preparation method of a colorless and transparent polyimide film. Made of film.
鉴于上述无色透明聚酰亚胺薄膜所具有的优势，使得应用其的LED贴膜屏也具有同样的优势。In view of the advantages of the above-mentioned colorless and transparent polyimide film, the LED film screen using it also has the same advantages.
另外，需要说明的是，无色透明聚酰亚胺薄膜不限应用于LED贴膜屏，还可以应用于LED照明或LED显示或柔性太阳能电池，从而赋予上述器件相应的特性，有利于器件的 散热以及性能的提升。In addition, it should be noted that the colorless and transparent polyimide film is not limited to the application of LED film screen, but also can be applied to LED lighting or LED display or flexible solar cells, so as to endow the above devices with corresponding characteristics, which is conducive to the heat dissipation of the devices and improved performance.
下面结合具体实施例和对比例，对本申请作进一步说明。The present application will be further described below in conjunction with specific embodiments and comparative examples.
实施例1Example 1
本实施例提供了一种无色透明聚酰亚胺薄膜，主要采用以下原料制成：聚酰亚胺树脂和导热填料；其中，聚酰亚胺树脂主要由二酐A(1,2,3,4-环丁烷四甲酸二酐)、二胺A(2,2'-二(三氟甲基)二氨基联苯)在脱水剂(乙酸酐)和催化剂(吡啶)作用下缩聚得到；导热填料为改性无机导热填料，即γ-氨丙基三乙氧基硅烷改性的α-氧化铝，导热填料的质量占无色透明聚酰亚胺薄膜总质量的60％。This embodiment provides a colorless transparent polyimide film, which is mainly made of the following raw materials: polyimide resin and thermally conductive filler; wherein, the polyimide resin is mainly composed of dianhydride A (1,2,3 ,4-cyclobutanetetracarboxylic dianhydride) and diamine A (2,2'-bis(trifluoromethyl)diaminobiphenyl) are obtained by polycondensation under the action of dehydrating agent (acetic anhydride) and catalyst (pyridine); The thermally conductive filler is a modified inorganic thermally conductive filler, namely α-alumina modified by γ-aminopropyltriethoxysilane, and the mass of the thermally conductive filler accounts for 60% of the total mass of the colorless transparent polyimide film.
本实施例提供的上述无色透明聚酰亚胺薄膜的制备方法，包括以下步骤：The preparation method of the above-mentioned colorless transparent polyimide film provided in this embodiment includes the following steps:
(a)提供导热填料和有机极性溶剂形成的导热浆料(a) Provide a thermally conductive paste formed from thermally conductive fillers and organic polar solvents
在氮气气氛下，在0.5L反应器中添加200g N,N-二甲基乙酰胺作为有机极性溶剂，再添加48.5gα-氧化铝作为导热填料(平均粒径0.05μm)，1.5gγ-氨丙基三乙氧基硅烷为偶联剂，搅拌2h制备得到导热浆料；In a nitrogen atmosphere, 200g N,N-dimethylacetamide was added as an organic polar solvent in a 0.5L reactor, 48.5g α-alumina was added as a thermally conductive filler (average particle size: 0.05μm), 1.5g γ-ammonia Propyl triethoxysilane was used as coupling agent, and the thermal conductive slurry was prepared by stirring for 2 h;
(b)提供聚酰亚胺树脂和有机极性溶剂形成的聚酰亚胺浆料(b) Provide polyimide slurry formed by polyimide resin and organic polar solvent
在氮气氛围下，在70g N,N-二甲基乙酰胺(有机溶剂)里加入9.3029g(0.0291mol)2,2'-二(三氟甲基)二氨基联苯，搅拌使其溶解，待溶解完后加入5.6971g(0.0291mol)1,2,3,4-环丁烷四甲酸二酐，机械搅拌4h，再加入30g乙酸酐(11.8631g)和吡啶(4.5958g)的N,N-二甲基乙酰胺混合溶液，继续搅拌4h，得到粗聚酰亚胺浆料；Under nitrogen atmosphere, add 9.3029g (0.0291mol) 2,2'-bis(trifluoromethyl)diaminobiphenyl to 70g N,N-dimethylacetamide (organic solvent), stir to dissolve, After dissolving, add 5.6971g (0.0291mol) 1,2,3,4-cyclobutanetetracarboxylic dianhydride, stir mechanically for 4h, then add 30g acetic anhydride (11.8631g) and pyridine (4.5958g) N,N - The dimethylacetamide mixed solution was stirred for 4h to obtain a crude polyimide slurry;
将得到的粗聚酰亚胺浆料缓慢加入水中析出，得到粗聚酰亚胺树脂，粗聚酰亚胺树脂再加入80℃以上水中水煮2h以进行除杂分离，然后再将其放入真空干燥箱真空烘干，得到聚酰亚胺树脂；The obtained crude polyimide slurry is slowly added to water to separate out, to obtain crude polyimide resin, and the crude polyimide resin is then added to water above 80°C and boiled for 2 hours for impurity removal and separation, and then put into Vacuum drying in a vacuum drying oven to obtain polyimide resin;
将聚酰亚胺树脂溶解在N,N-二甲基乙酰胺中，形成聚酰亚胺浆料；Dissolving polyimide resin in N,N-dimethylacetamide to form polyimide slurry;
(c)制膜(c) Film making
将步骤(a)得到的导热浆料和步骤(b)得到的聚酰亚胺浆料混合得到复合浆料；Mixing the thermally conductive paste obtained in step (a) and the polyimide paste obtained in step (b) to obtain a composite paste;
将复合浆料经真空脱泡处理，然后经狭缝式模头流延到钢带上，钢带分3个温度区域，温度分别为100℃、130℃、80℃，氮气气氛，除去一部分溶剂，接着从钢带上揭下薄膜并经纵拉和横拉处理并亚胺化，纵拉温度150℃，纵拉比1.1，横拉温度250℃、300℃、200℃，横拉比1.02，最后收卷，得到厚度为50μm无色透明聚酰亚胺薄膜。The composite slurry is subjected to vacuum defoaming treatment, and then cast on a steel strip through a slit die head. The steel strip is divided into 3 temperature zones, the temperatures are 100 ° C, 130 ° C, and 80 ° C, respectively, and a nitrogen atmosphere is used to remove a part of the solvent. , and then peel off the film from the steel strip and undergo longitudinal drawing and horizontal drawing treatment and imidization, the vertical drawing temperature is 150 ° C, the vertical drawing ratio is 1.1, the horizontal drawing temperature is 250 ° C, 300 ° C, 200 ° C, and the horizontal drawing ratio is 1.02, Finally, the roll was wound to obtain a colorless and transparent polyimide film with a thickness of 50 μm.
实施例2Example 2
本实施例提供了一种无色透明聚酰亚胺薄膜，除了导热填料的平均粒径由0.05μm变为0.5μm，其余原料、用量以及制备方法与实施例1相同。This embodiment provides a colorless transparent polyimide film, except that the average particle size of the thermally conductive filler is changed from 0.05 μm to 0.5 μm, and other raw materials, dosages and preparation methods are the same as those in Embodiment 1.
实施例3Example 3
本实施例提供了一种无色透明聚酰亚胺薄膜，除了导热填料的平均粒径由0.05μm变为1.0μm，其余原料、用量以及制备方法与实施例1相同。This embodiment provides a colorless transparent polyimide film, except that the average particle size of the thermally conductive filler is changed from 0.05 μm to 1.0 μm, and other raw materials, dosages and preparation methods are the same as those in Embodiment 1.
实施例4Example 4
本实施例提供了一种无色透明聚酰亚胺薄膜，除了导热填料的平均粒径由0.05μm变为5.0μm，其余原料、用量以及制备方法与实施例1相同。This example provides a colorless transparent polyimide film, except that the average particle size of the thermally conductive filler is changed from 0.05 μm to 5.0 μm, and the rest of the raw materials, dosage and preparation method are the same as those in Example 1.
实施例5Example 5
本实施例提供了一种无色透明聚酰亚胺薄膜，除了导热填料由α-氧化铝替换为氮化 铝，氮化铝平均粒径为2.0μm，导热填料的质量占无色透明聚酰亚胺薄膜总质量的30％，无色透明聚酰亚胺薄膜的厚度为25μm，其余原料、用量以及制备方法与实施例1相同。This embodiment provides a colorless transparent polyimide film, except that the thermally conductive filler is replaced by α-alumina with aluminum nitride, the average particle size of aluminum nitride is 2.0 μm, and the mass of the thermally conductive filler accounts for the colorless and transparent polyimide film. 30% of the total mass of the imine film, the thickness of the colorless and transparent polyimide film is 25 μm, and the remaining raw materials, dosages and preparation methods are the same as those in Example 1.
实施例6Example 6
本实施例提供了一种无色透明聚酰亚胺薄膜，除了无色透明聚酰亚胺薄膜的厚度由25μm替换为50μm，其余原料、用量以及制备方法与实施例5相同。This embodiment provides a colorless transparent polyimide film, except that the thickness of the colorless transparent polyimide film is replaced from 25 μm to 50 μm, and other raw materials, dosages and preparation methods are the same as those in Embodiment 5.
实施例7Example 7
本实施例提供了一种无色透明聚酰亚胺薄膜，除了无色透明聚酰亚胺薄膜的厚度由25μm替换为75μm，其余原料、用量以及制备方法与实施例5相同。This embodiment provides a colorless transparent polyimide film, except that the thickness of the colorless transparent polyimide film is replaced from 25 μm to 75 μm, and other raw materials, dosages and preparation methods are the same as those in Embodiment 5.
实施例8Example 8
本实施例提供了一种无色透明聚酰亚胺薄膜，除了无色透明聚酰亚胺薄膜的厚度由25μm替换为100μm，其余原料、用量以及制备方法与实施例5相同。This embodiment provides a colorless transparent polyimide film, except that the thickness of the colorless transparent polyimide film is replaced from 25 μm to 100 μm, and other raw materials, dosages and preparation methods are the same as those in Embodiment 5.
实施例9Example 9
本实施例提供了一种无色透明聚酰亚胺薄膜，除了导热填料由α-氧化铝替换为石墨烯，石墨烯平均粒径为5.0μm，导热填料的质量占无色透明聚酰亚胺薄膜总质量的5％，其余原料、用量以及制备方法与实施例1相同。This embodiment provides a colorless transparent polyimide film, except that the thermally conductive filler is replaced by α-alumina with graphene, the average particle size of graphene is 5.0 μm, and the mass of the thermally conductive filler accounts for the colorless transparent polyimide 5% of the total mass of the film, and the remaining raw materials, dosages and preparation methods are the same as in Example 1.
实施例10Example 10
本实施例提供了一种无色透明聚酰亚胺薄膜，除了导热填料的质量占无色透明聚酰亚胺薄膜总质量的百分比由5％替换为15％，其余原料、用量以及制备方法与实施例9相同。This embodiment provides a colorless transparent polyimide film, except that the percentage of the mass of the thermally conductive filler in the total mass of the colorless transparent polyimide film is replaced by 5% to 15%, the remaining raw materials, dosages and preparation methods are the same as Example 9 is the same.
实施例11Example 11
本实施例提供了一种无色透明聚酰亚胺薄膜，除了导热填料的质量占无色透明聚酰亚胺薄膜总质量的百分比由5％替换为30％，其余原料、用量以及制备方法与实施例9相同。This embodiment provides a colorless transparent polyimide film, except that the percentage of the mass of the thermally conductive filler in the total mass of the colorless transparent polyimide film is replaced by 5% to 30%, the remaining raw materials, dosage and preparation method are the same as Example 9 is the same.
实施例12Example 12
本实施例提供了一种无色透明聚酰亚胺薄膜，除了导热填料的质量占无色透明聚酰亚胺薄膜总质量的百分比由5％替换为50％，其余原料、用量以及制备方法与实施例9相同。This embodiment provides a colorless and transparent polyimide film, except that the mass of the thermally conductive filler accounts for 50% of the total mass of the colorless and transparent polyimide film, and other raw materials, dosages and preparation methods are the same as Example 9 is the same.
实施例13Example 13
本实施例提供了一种无色透明聚酰亚胺薄膜，除了改变二酐的种类，即将1,2,3,4-环丁烷四甲酸二酐替换为摩尔分数为90％的4,4'-六氟异丙基邻苯二甲酸酐和摩尔分数为10％的1,2,3,4-环丁烷四甲酸二酐，其余原料、用量以及制备方法与实施例1相同。This embodiment provides a colorless and transparent polyimide film, in addition to changing the type of dianhydride, that is, replacing 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 4,4 with a mole fraction of 90% '-hexafluoroisopropylphthalic anhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride with a molar fraction of 10%, the remaining raw materials, dosages and preparation methods are the same as in Example 1.
实施例14Example 14
本实施例提供了一种无色透明聚酰亚胺薄膜，除了改变二酐的种类，即将1,2,3,4-环丁烷四甲酸二酐替换为摩尔分数为50％的4,4'-六氟异丙基邻苯二甲酸酐(二酐A)和摩尔分数为50％的1,2,3,4-环丁烷四甲酸二酐(二酐B)，其余原料、用量以及制备方法与实施例1相同。This embodiment provides a colorless and transparent polyimide film, in addition to changing the type of dianhydride, that is, replacing 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 4,4 with a mole fraction of 50% '-Hexafluoroisopropylphthalic anhydride (dianhydride A) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (dianhydride B) with a mole fraction of 50%, the remaining raw materials, dosage and The preparation method is the same as that of Example 1.
实施例15Example 15
本实施例提供了一种无色透明聚酰亚胺薄膜，除了改变二酐的种类，即将1,2,3,4-环丁烷四甲酸二酐替换为摩尔分数为80％的1,2,3,4-环戊四羧酸二酐(二酐A)和摩尔分数为20％的双酚A二酐(二酐B)，其余原料、用量以及制备方法与实施例1相同。This embodiment provides a colorless and transparent polyimide film, in addition to changing the type of dianhydride, that is, replacing 1,2,3,4-cyclobutanetetracarboxylic dianhydride with 1,2 with a mole fraction of 80% , 3,4-cyclopentatetracarboxylic dianhydride (dianhydride A) and bisphenol A dianhydride (dianhydride B) with a mole fraction of 20%, the remaining raw materials, dosage and preparation method are the same as in Example 1.
实施例16Example 16
本实施例提供了一种无色透明聚酰亚胺薄膜，除了改变二胺的种类，即将2,2'-二(三氟 甲基)二氨基联苯(二胺A)替换为摩尔分数为50％的2,2-双(3-氨基-4-羟基苯基)六氟丙烷(二胺A)和摩尔分数为50％的2,7-二氨基芴(二胺B)，其余原料、用量以及制备方法与实施例1相同。This embodiment provides a colorless transparent polyimide film, in addition to changing the type of diamine, that is, replacing 2,2'-bis(trifluoromethyl)diaminobiphenyl (diamine A) with a mole fraction of 50% of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (diamine A) and 50% of 2,7-diaminofluorene (diamine B) in mole fraction, the rest of the raw materials, The dosage and preparation method are the same as those in Example 1.
实施例17Example 17
本实施例提供了一种无色透明聚酰亚胺薄膜，除了改变二胺的种类，即将2,2'-二(三氟甲基)二氨基联苯(二胺A)替换为摩尔分数为75％的1,3-环己二甲胺(二胺A)和摩尔分数为25％的4,4'-双(3-氨基苯氧基)二苯基砜(二胺B)，其余原料、用量以及制备方法与实施例1相同。This embodiment provides a colorless transparent polyimide film, in addition to changing the type of diamine, that is, replacing 2,2'-bis(trifluoromethyl)diaminobiphenyl (diamine A) with a mole fraction of 75% of 1,3-cyclohexanedimethylamine (diamine A) and 25% of 4,4'-bis(3-aminophenoxy)diphenylsulfone (diamine B) in mole fraction, the rest of the raw materials , dosage and preparation method are the same as in Example 1.
实施例18Example 18
本实施例提供了一种无色透明聚酰亚胺薄膜，除了将导热填料由改性无机导热填料(γ-氨丙基三乙氧基硅烷改性的α-氧化铝)替换为未改性无机导热填料α-氧化铝，即α-氧化铝表面未经表面改性，其余原料、用量与实施例1相同。This embodiment provides a colorless transparent polyimide film, except that the thermally conductive filler is replaced by a modified inorganic thermally conductive filler (γ-aminopropyltriethoxysilane-modified α-alumina) with an unmodified one The inorganic thermally conductive filler α-alumina, that is, the surface of the α-alumina has not been surface-modified, and the remaining raw materials and dosages are the same as those in Example 1.
本实施例提供的上述无色透明聚酰亚胺薄膜的制备方法，除了在导热浆料的制备过程中未添加硅烷偶联剂γ-氨丙基三乙氧基硅烷，其余步骤与实施例1相同。The preparation method of the above-mentioned colorless transparent polyimide film provided in this embodiment, except that the silane coupling agent γ-aminopropyltriethoxysilane is not added in the preparation process of the thermally conductive paste, the remaining steps are the same as those in Example 1 same.
实施例19-实施例36Example 19 - Example 36
实施例19-36分别提供了一种LED贴膜屏，分别采用实施例1-18提供的无色透明聚酰亚胺薄膜制成。Embodiments 19-36 respectively provide an LED film-coated screen, which is made of the colorless and transparent polyimide films provided in Embodiments 1-18, respectively.
对比例1Comparative Example 1
本对比例提供了一种聚酰亚胺薄膜，除了原料中未添加导热填料，其余原料种类、用量与实施例1相同。This comparative example provides a polyimide film, except that no thermally conductive filler is added to the raw materials, and the types and amounts of other raw materials are the same as those in Example 1.
本对比例提供的聚酰亚胺薄膜的制备方法，除了未进行步骤(a),且步骤(c)中直接将聚酰亚胺浆料进行制膜，其余步骤与实施例1相同。In the preparation method of the polyimide film provided by this comparative example, the remaining steps are the same as those in Example 1, except that step (a) is not performed, and the polyimide slurry is directly formed into a film in step (c).
对比例2Comparative Example 2
本对比例提供了一种聚酰亚胺薄膜，除了聚酰亚胺薄膜的厚度由50μm变为100μm，其余步骤与对比例1相同。This comparative example provides a polyimide film, except that the thickness of the polyimide film is changed from 50 μm to 100 μm, and the remaining steps are the same as those of Comparative Example 1.
对比例3Comparative Example 3
本对比例提供了一种聚酰亚胺薄膜，除了改变二酐的种类，即将1,2,3,4-环丁烷四甲酸二酐(二酐A)替换为摩尔分数为50％的均苯四甲酸二酐(二酐B)和摩尔分数为50％的3,3',4,4'-联苯四羧酸二酐(二酐B)，其余原料和用量与实施例1相同。This comparative example provides a polyimide film, in addition to changing the type of dianhydride, that is, replacing 1,2,3,4-cyclobutanetetracarboxylic dianhydride (dianhydride A) with a homogenate with a mole fraction of 50% The pyromellitic dianhydride (dianhydride B) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (dianhydride B) with a molar fraction of 50% are the same as in Example 1 for the remaining raw materials and dosage.
本对比例提供的聚酰亚胺薄膜的制备方法包括以下步骤：The preparation method of the polyimide film provided by this comparative example comprises the following steps:
(a)提供导热填料和有机极性溶剂形成的导热浆料(a) Provide a thermally conductive paste formed from thermally conductive fillers and organic polar solvents
在氮气气氛下，在100mL反应器中添加25.2g N,N-二甲基乙酰胺作为有机极性溶剂，再添加10.8gα-氧化铝作为导热填料(平均粒径0.05μm)，0.3340gγ-氨丙基三乙氧基硅烷为偶联剂，搅拌2h制备得到导热浆料；In a nitrogen atmosphere, 25.2g N,N-dimethylacetamide was added as an organic polar solvent in a 100mL reactor, 10.8g α-alumina was added as a thermal conductive filler (average particle size 0.05μm), 0.3340g γ-ammonia Propyl triethoxysilane was used as coupling agent, and the thermal conductive slurry was prepared by stirring for 2 h;
在氮气气氛下，向反应器中加入9.9912g(0.0312mol)2,2'-二(三氟甲基)二氨基联苯(二胺A)，再加入82g有机溶剂N,N-二甲基乙酰胺搅拌使之溶解，边冷却(温度为-25℃)边加入3.4027g(0.0312mol)均苯四甲酸二酐(二酐B)和4.5898g(0.0312mol)3,3',4,4'-联苯四羧酸二酐(二酐B)，低温下机械搅拌8h，得到粘度200000厘泊的聚酰胺酸浆料(含有18wt％的聚酰胺酸溶液)；Under nitrogen atmosphere, 9.9912g (0.0312mol) 2,2'-bis(trifluoromethyl)diaminobiphenyl (diamine A) was added to the reactor, and 82g organic solvent N,N-dimethyl Acetamide was stirred to dissolve, and 3.4027g (0.0312mol) of pyromellitic dianhydride (dianhydride B) and 4.5898g (0.0312mol) of 3,3',4,4 were added while cooling (the temperature was -25°C). '-biphenyltetracarboxylic dianhydride (dianhydride B), mechanically stirred at low temperature for 8h, to obtain a polyamic acid slurry with a viscosity of 200,000 centipoise (containing 18wt% of a polyamic acid solution);
(b)将导热浆料和聚酰胺酸浆料混合，继续低温搅拌1h，真空消泡，得到复合浆料；(b) mixing the thermally conductive slurry and the polyamic acid slurry, continuing to stir at a low temperature for 1 hour, and vacuum defoaming to obtain a composite slurry;
在氮气气氛下，将5.8113g(0.0624mol)催化剂3-甲基吡啶和6.3704g(0.0624mol)脱水剂乙酸酐溶解于20.8183g有机溶剂N,N-二甲基乙酰胺中，边冷却(温度为-25℃)边搅拌0.5h，得到催化液并保持处于低温状态(温度为-25℃)；Under nitrogen atmosphere, 5.8113g (0.0624mol) catalyst 3-picoline and 6.3704g (0.0624mol) dehydrating agent acetic anhydride were dissolved in 20.8183g organic solvent N,N-dimethylacetamide, while cooling (temperature Stir for 0.5h at -25°C) to obtain a catalytic liquid and keep it at a low temperature (temperature is -25°C);
(c)将复合浆料和催化液经混合器低温混合，然后经狭缝式模头流延到钢带上，钢带分3个温度区域，温度分别为100℃、130℃、80℃，氮气气氛，除去一部分溶剂，接着从钢带上揭下薄膜并经纵拉和横拉处理并亚胺化，纵拉温度为150℃，纵拉比为1.1，横拉温度250℃、450℃、250℃，横拉比为1.02，最后收卷，得到厚度为50μm黄色聚酰亚胺薄膜。(c) Mix the composite slurry and the catalytic liquid at a low temperature through a mixer, and then cast it onto a steel strip through a slit die head. Nitrogen atmosphere, remove a part of the solvent, then peel off the film from the steel strip and process and imidize through longitudinal drawing and horizontal drawing. At 250° C., the transverse draw ratio was 1.02, and finally the film was wound to obtain a yellow polyimide film with a thickness of 50 μm.
对比例4Comparative Example 4
本对比例提供了一种聚酰亚胺薄膜，除了改变二胺的种类，即将2,2'-二(三氟甲基)二氨基联苯(二胺A)替换为4,4'-二氨基二苯醚(二胺B)，其余原料和用量与实施例1相同。This comparative example provides a polyimide film, in addition to changing the type of diamine, that is, replacing 2,2'-bis(trifluoromethyl)diaminobiphenyl (diamine A) with 4,4'-diamine Amino diphenyl ether (diamine B), other raw materials and dosages are the same as those in Example 1.
本对比例提供的聚酰亚胺薄膜的制备方法与对比例3的制备方法相同。The preparation method of the polyimide film provided in this comparative example is the same as that of the comparative example 3.
为验证各实施例和对比例的技术效果，特进行以下实验。In order to verify the technical effect of each embodiment and comparative example, the following experiments are specially carried out.
实验例1Experimental example 1
对实施例1-18和对比例1-4提供的聚酰亚胺薄膜的厚度、透过率、导热系数、尺寸稳定性(热收缩)、弹性模量等性能进行检测。其中，聚酰亚胺薄膜厚度通过千分尺进行测定，检测方法依据GB/T 6672-2001；透过率通过紫外可见光分光光度计测定波长为550nm的光的透过率，检测方法依据GB/T 2410-2008；导热系数通过激光导热仪LFA 467测定水平方向导热系数，检测方法依据ASTM E1461-2013；热收缩通过精度高于0.01μm的游标卡尺进行检测，检测方法依据ASTM D2305-2018；弹性模量通过万能拉伸试验机进行检测，检测方法依据GBT1040.3-2006，具体结果如表1所示。The thickness, transmittance, thermal conductivity, dimensional stability (thermal shrinkage), elastic modulus and other properties of the polyimide films provided in Examples 1-18 and Comparative Examples 1-4 were tested. Among them, the thickness of the polyimide film was measured by a micrometer, and the detection method was based on GB/T 6672-2001; the transmittance was measured by an ultraviolet-visible light spectrophotometer with a wavelength of 550 nm, and the detection method was based on GB/T 2410. -2008; The thermal conductivity is measured by the laser thermal conductivity meter LFA 467 to measure the thermal conductivity in the horizontal direction, and the detection method is based on ASTM E1461-2013; the thermal shrinkage is detected by a vernier caliper with an accuracy higher than 0.01 μm, and the detection method is based on ASTM D2305-2018; The universal tensile testing machine is used for testing, and the testing method is based on GBT1040.3-2006. The specific results are shown in Table 1.
表1Table 1
Figure PCTCN2021108698-appb-000001
Figure PCTCN2021108698-appb-000001
从表1中数据可以看出，本申请提供的无色透明聚酰亚胺薄膜的综合性能较好。其中，实施例12提供的无色透明聚酰亚胺薄膜的导热系数最大，实施例5提供的无色透明聚酰亚胺薄膜具有较高的导热系数及较高的透过率。It can be seen from the data in Table 1 that the colorless transparent polyimide film provided by this application has better comprehensive properties. Among them, the colorless transparent polyimide film provided in Example 12 has the largest thermal conductivity, and the colorless transparent polyimide film provided in Example 5 has higher thermal conductivity and higher transmittance.
还需要说明的是，对比例3-4均为实施例1的对照实验。由于对比例3和4选择了不同种类的二酐或者二胺，使得所制得的聚酰亚胺薄膜呈黄色，不适合作为LED贴膜屏使用。It should also be noted that Comparative Examples 3-4 are all the control experiments of Example 1. Since different kinds of dianhydrides or diamines were selected in Comparative Examples 3 and 4, the obtained polyimide film was yellow, which was not suitable for use as an LED film-coated screen.
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, but not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present application. scope.

Claims (20)

  1. 一种无色透明聚酰亚胺薄膜，其特征在于，主要采用以下原料制成：聚酰亚胺树脂和导热填料；A colorless transparent polyimide film is characterized in that, it is mainly made of the following raw materials: polyimide resin and thermally conductive filler;
    其中，所述聚酰亚胺树脂主要由二酐、二胺在脱水剂和催化剂作用下缩聚得到；所述二酐包括二酐A，所述二酐A包括4,4'-六氟异丙基邻苯二甲酸酐、1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐或1,2,3,4-环戊四羧酸二酐中的任意一种或至少两种的组合；所述二胺包括二胺A，所述二胺A包括2,2'-二(三氟甲基)二氨基联苯、1,3-环己烷二胺、1,3-环己二甲胺、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、2,2-双(3-氨基-4-甲苯基)六氟丙烷或3,5-二氨基三氟甲苯中的任意一种或至少两种的组合；Wherein, the polyimide resin is mainly obtained by polycondensation of dianhydride and diamine under the action of a dehydrating agent and a catalyst; the dianhydride includes dianhydride A, and the dianhydride A includes 4,4'-hexafluoroisopropyl phthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride or 1,2,3,4-cyclopentanetetra Any one or a combination of at least two of the carboxylic dianhydrides; the diamine includes diamine A, and the diamine A includes 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1, 3-Cyclohexanediamine, 1,3-cyclohexanedimethylamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl) Any one or a combination of at least two of hexafluoropropane, 2,2-bis(3-amino-4-tolyl)hexafluoropropane or 3,5-diaminotrifluorotoluene;
    所述导热填料包括未改性无机导热填料和/或改性无机导热填料，所述导热填料的质量占无色透明聚酰亚胺薄膜总质量的5％-60％；The thermally conductive filler includes unmodified inorganic thermally conductive fillers and/or modified inorganic thermally conductive fillers, and the mass of the thermally conductive fillers accounts for 5%-60% of the total mass of the colorless transparent polyimide film;
    所述无色透明聚酰亚胺薄膜的透过率为60％-87％，导热系数为0.4W/m·K-4.5W/m·K。The transmittance of the colorless and transparent polyimide film is 60%-87%, and the thermal conductivity is 0.4W/m·K-4.5W/m·K.
  2. 根据权利要求1所述的无色透明聚酰亚胺薄膜，其中，所述二酐包括摩尔分数为50％-100％的二酐A和摩尔分数为0-50％的二酐B；The colorless transparent polyimide film according to claim 1, wherein the dianhydride comprises dianhydride A with a mole fraction of 50%-100% and dianhydride B with a mole fraction of 0-50%;
    其中，所述二酐B包括均苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、2,3,3',4-联苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、4,4'-氧代双邻苯二甲酸酐、1,2,4,5-环己烷四甲酸二酐、1,2,3,4-环丁烷四甲酸二酐、1,2,3,4-环戊四羧酸二酐、双酚A二酐或双酚F二酐中的任意一种或至少两种的组合。Wherein, the dianhydride B includes pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxobisphthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Any one or at least one of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bisphenol A dianhydride or bisphenol F dianhydride combination of the two.
  3. 根据权利要求2所述的无色透明聚酰亚胺薄膜，其中，所述二胺包括摩尔分数为50％-100％的二胺A和摩尔分数为0％-50％的二胺B；The colorless transparent polyimide film according to claim 2, wherein the diamine comprises a molar fraction of 50%-100% of diamine A and a molar fraction of 0%-50% of diamine B;
    其中，所述二胺B包括1,3-二氨基苯、1,4-二氨基苯、2,2'-二(三氟甲基)二氨基联苯、1,3-环己烷二胺、1,3-环己二甲胺、4,4'-二氨基二苯醚、3,3'-氧联二苯胺、3-氨基苄胺、3,3'-甲撑二苯胺、2,7-二氨基芴、1,3-苯二甲胺、1,3-双(3-氨基苯氧基)苯、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、2,2-双(3-氨基苯基)六氟丙烷、1,4-双(3-氨基苯氧基)苯、2,2-双(3-氨基-4-甲苯基)六氟丙烷、3,3'-二氨基二苯砜、4,4'-双(3-氨基苯氧基)二苯基砜、3,3'-二氨基二苯甲酮、3,4'-二氨基二苯基甲烷、3,5-二氨基三氟甲苯或1,2-双(3-氨基苯基)苯胺中的任意一种或至少两种的组合。Wherein, the diamine B includes 1,3-diaminobenzene, 1,4-diaminobenzene, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 1,3-cyclohexanediamine , 1,3-cyclohexanedimethylamine, 4,4'-diaminodiphenyl ether, 3,3'-oxybenzidine, 3-aminobenzylamine, 3,3'-methylenediphenylamine, 2, 7-diaminofluorene, 1,3-xylylenediamine, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 2,2-bis(3-amino-4-tolyl)hexafluoropropane, 3,3'-diaminodiphenylsulfone, 4,4'-bis(3-aminophenoxy)diphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenylsulfone Any one or a combination of at least two of phenylmethane, 3,5-diaminotrifluorotoluene or 1,2-bis(3-aminophenyl)aniline.
  4. 根据权利要求2所述的无色透明聚酰亚胺薄膜，其中，所述脱水剂包括乙酸酐、丙酸酐或丁酸酐中的任意一种或至少两种的组合。The colorless transparent polyimide film according to claim 2, wherein the dehydrating agent comprises any one or a combination of at least two of acetic anhydride, propionic anhydride or butyric anhydride.
  5. 根据权利要求2所述的无色透明聚酰亚胺薄膜，其中，所述催化剂包括吡啶、3-甲 基吡啶、三乙胺或异喹啉中的任意一种或至少两种的组合。The colorless transparent polyimide film according to claim 2, wherein the catalyst comprises any one or a combination of at least two of pyridine, 3-methylpyridine, triethylamine or isoquinoline.
  6. 根据权利要求2所述的无色透明聚酰亚胺薄膜，其中，所述聚酰亚胺树脂的制备方法包括以下步骤：The colorless transparent polyimide film according to claim 2, wherein the preparation method of the polyimide resin comprises the following steps:
    将二酐、二胺和有机溶剂混合搅拌，然后加入脱水剂和催化剂，使进行缩聚反应，得到聚酰亚胺树脂。The dianhydride, the diamine and the organic solvent are mixed and stirred, and then a dehydrating agent and a catalyst are added to carry out a polycondensation reaction to obtain a polyimide resin.
  7. 根据权利要求6所述的无色透明聚酰亚胺薄膜，其中，所述二胺和二酐的摩尔比为0.9：1-1.1：1。The colorless transparent polyimide film according to claim 6, wherein the molar ratio of the diamine and the dianhydride is 0.9:1-1.1:1.
  8. 根据权利要求6所述的无色透明聚酰亚胺薄膜，所述有机溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或γ-丁内酯中的任意一种或至少两种的组合。The colorless transparent polyimide film according to claim 6, wherein the organic solvent comprises N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or γ-butane Any one or a combination of at least two of the lactones.
  9. 根据权利要求6所述的无色透明聚酰亚胺薄膜，其中，所述脱水剂和二酐的摩尔比为0.5：1-2：1；The colorless transparent polyimide film according to claim 6, wherein the molar ratio of the dehydrating agent and the dianhydride is 0.5:1-2:1;
    优选的，所述催化剂和二酐的摩尔比为0.5：1-2：1。Preferably, the molar ratio of the catalyst and the dianhydride is 0.5:1-2:1.
  10. 根据权利要求6所述的无色透明聚酰亚胺薄膜，其中，缩聚反应的温度为4℃-40℃，缩聚反应的时间为4h-24h；The colorless transparent polyimide film according to claim 6, wherein the temperature of the polycondensation reaction is 4°C-40°C, and the time of the polycondensation reaction is 4h-24h;
    优选的，缩聚反应在惰性气氛下进行。Preferably, the polycondensation reaction is carried out under an inert atmosphere.
  11. 根据权利要求6所述的无色透明聚酰亚胺薄膜，缩聚反应结束后将得到的粗树脂除杂，干燥，得到聚酰亚胺树脂。According to the colorless transparent polyimide film according to claim 6, after the polycondensation reaction is completed, the obtained crude resin is removed from impurities and dried to obtain a polyimide resin.
  12. 根据权利要求1-11任意一项所述的无色透明聚酰亚胺薄膜，其中，所述导热填料的平均粒径为0.05μm-5μm。The colorless transparent polyimide film according to any one of claims 1-11, wherein the average particle size of the thermally conductive filler is 0.05 μm-5 μm.
  13. 根据权利要求1-11任意一项所述的无色透明聚酰亚胺薄膜，所述未改性无机导热填料包括α-氧化铝、氮化铝、氮化硼、碳化硅、碳化氮或石墨烯中的任意一种或至少两种的组合；和/或The colorless transparent polyimide film according to any one of claims 1-11, wherein the unmodified inorganic thermally conductive filler comprises α-alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphite any one or a combination of at least two of the alkenes; and/or
    所述改性无机导热填料包括经过偶联剂进行表面改性的无机导热填料；和/或The modified inorganic thermally conductive filler includes an inorganic thermally conductive filler whose surface is modified by a coupling agent; and/or
    所述无机导热填料包括α-氧化铝、氮化铝、氮化硼、碳化硅、碳化氮或石墨烯中的任意一种或至少两种的组合。The inorganic thermally conductive filler includes any one or a combination of at least two of α-alumina, aluminum nitride, boron nitride, silicon carbide, nitrogen carbide or graphene.
  14. 根据权利要求1-11任意一项所述的无色透明聚酰亚胺薄膜，所述偶联剂的用量为所述改性无机导热填料总质量的1％-5％；和/或The colorless transparent polyimide film according to any one of claims 1-11, wherein the amount of the coupling agent is 1%-5% of the total mass of the modified inorganic thermally conductive filler; and/or
    所述偶联剂包括硅烷偶联剂，优选包括γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-α氨丙基三甲氧基硅烷或γ-缩水甘油醚氧丙基三甲氧基硅烷中的任意一种。The coupling agent includes a silane coupling agent, preferably γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-αaminopropyltrimethoxysilane or γ-glycidyl ether oxypropyl Any of the trimethoxysilanes.
  15. 根据权利要求1-11任意一项所述的无色透明聚酰亚胺薄膜，其中，所述无色透明聚酰亚胺薄膜的厚度为25μm-100μm。The colorless and transparent polyimide film according to any one of claims 1-11, wherein the thickness of the colorless and transparent polyimide film is 25 μm-100 μm.
  16. 根据权利要求1-15任意一项所述的无色透明聚酰亚胺薄膜的制备方法，其特征在于，包括以下步骤：The preparation method of the colorless transparent polyimide film according to any one of claims 1-15, characterized in that, comprising the following steps:
    提供导热填料和有机极性溶剂形成的导热浆料；Provide thermally conductive paste formed from thermally conductive fillers and organic polar solvents;
    提供聚酰亚胺树脂和有机极性溶剂形成的聚酰亚胺浆料；Provide polyimide slurry formed by polyimide resin and organic polar solvent;
    将导热浆料和聚酰亚胺浆料混合后制膜，得到无色透明聚酰亚胺薄膜。The thermally conductive paste and the polyimide paste are mixed to form a film to obtain a colorless and transparent polyimide film.
  17. 根据权利要求16所述的无色透明聚酰亚胺薄膜的制备方法，其中，所述有机极性溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或γ-丁内酯中的任意一种或至少两种的组合。The method for preparing a colorless transparent polyimide film according to claim 16, wherein the organic polar solvent comprises N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylformamide Either one or a combination of at least two of ylacetamide or gamma-butyrolactone.
  18. 根据权利要求16所述的无色透明聚酰亚胺薄膜的制备方法，其中聚酰亚胺树脂占聚酰亚胺浆料的质量分数为10％-20％。The method for preparing a colorless transparent polyimide film according to claim 16, wherein the mass fraction of the polyimide resin in the polyimide slurry is 10%-20%.
  19. 根据权利要求16所述的无色透明聚酰亚胺薄膜的制备方法，其中所述无色透明聚酰亚胺薄膜的制备方法，包括以下步骤：将导热浆料和聚酰亚胺浆料混合后，再经消泡、流延、干燥、拉伸和定型，得到无色透明聚酰亚胺薄膜。The preparation method of the colorless transparent polyimide film according to claim 16, wherein the preparation method of the colorless transparent polyimide film comprises the following steps: mixing the thermally conductive paste and the polyimide paste After that, defoaming, casting, drying, stretching and shaping are carried out to obtain a colorless transparent polyimide film.
  20. 一种LED贴膜屏，其特征在于，采用根据权利要求1-15任意一项所述的无色透明聚酰亚胺薄膜或根据权利要求16-19任意一项所述的无色透明聚酰亚胺薄膜的制备方法制得的无色透明聚酰亚胺薄膜制成。An LED film screen, characterized in that the colorless transparent polyimide film according to any one of claims 1-15 or the colorless transparent polyimide film according to any one of claims 16-19 is used The colorless transparent polyimide film prepared by the preparation method of the amine film is made.
PCT/CN2021/108698 2020-12-31 2021-07-27 Colorless transparent polyimide thin film and preparation method therefor, and led film screen WO2022142305A1 (en)

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