WO2017071643A1 - 具有阻隔紫外线作用的透明聚酰亚胺薄膜及其制备和应用 - Google Patents

具有阻隔紫外线作用的透明聚酰亚胺薄膜及其制备和应用 Download PDF

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WO2017071643A1
WO2017071643A1 PCT/CN2016/103781 CN2016103781W WO2017071643A1 WO 2017071643 A1 WO2017071643 A1 WO 2017071643A1 CN 2016103781 W CN2016103781 W CN 2016103781W WO 2017071643 A1 WO2017071643 A1 WO 2017071643A1
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film
dianhydride
polyimide film
ultraviolet
effect according
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French (fr)
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屠国力
姜鹏飞
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武汉依麦德新材料科技有限责任公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

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  • the invention relates to a transparent polyimide film with ultraviolet shielding effect, which is applied to human body protection clothing, lamps, window films, glass films, car films or sunshade articles for preventing ultraviolet radiation.
  • Ultraviolet light refers to electromagnetic waves with a wavelength between 200 and 400 nanometers. It belongs to a part of the band of stellar luminescence and is widely present in the outer space. Due to the destruction of the Earth's ozone layer in recent decades, the intensity of ultraviolet radiation in the surface space has been increasing. In addition, commonly used artificial light sources, such as ultraviolet lamps, arcs, etc., also produce ultraviolet light. Science has confirmed that excessive ultraviolet radiation has different degrees of damage to the human body and to animals and plants. Excessive exposure to ultraviolet radiation in the human body can cause skin diseases and even skin cancer.
  • UV-resistant additives are commonly used to add anti-UV additives to materials.
  • Xu Longlin, Zhou Junhong et al. (CN101012343A) applied a resin coating containing inorganic particles and organic particles on an optical base film to obtain an anti-ultraviolet film.
  • CN102756522 introduced a UV-inhibitor such as benzotriazole or benzophenone to prepare a three-layer polyethylene composite film with UV blocking effect.
  • Gu Wenzhong prepared a UV-resistant plastic film by solution co-melting-dipping method using polyvinyl alcohol, sodium titanium phosphate and glycerol.
  • the addition of the anti-ultraviolet additive has the problem that it cannot be uniformly dispersed in the substrate, and there are problems such as aging deterioration of the anti-UV additive, and the current technology is difficult to overcome.
  • polyimide has the highest temperature resistance grade, and its aging resistance, radiation resistance and chemical resistance are superior to other polymer materials.
  • the film is a completely uniform polymer material, and the bulk material is used to absorb ultraviolet rays without adding any inorganic organic anti-UV additive.
  • the UV cutoff wavelength is between 380 and 400 nm, and the shorter wavelength band transmittance is 0, which is completely blocked.
  • the transmittance in the visible light range is above 75% on average, and does not affect the transmittance in the visible light band. It is a transparent film material that satisfies the need for shielding ultraviolet rays and transparent applications.
  • the polyimide film according to the present invention is characterized in that the film comprises a homopolymerized polyimide polymer and/or a copolymerized polyimide prepared by using a diamine compound and a dianhydride compound as a raw material. a molecule having the following chemical structure,
  • the residue D of the diamine compound belongs to an electron donor
  • the residue A of the dianhydride compound belongs to an electron acceptor.
  • the dianhydride compound contains an acid anhydride and has a strong electron-withdrawing action.
  • the residue D of the diamine compound belongs to the electron donor Dornor
  • the residue A of the dianhydride compound belongs to the electron acceptor Acceptor, and polycondensation forms a -D-A-repeat unit. After polycondensation, charge energy transfer occurs between D and A.
  • the charge transfer occurs in the intramolecular unit and also occurs in the interchain unit.
  • the charge energy transfer action has an absorption peak width of 280 nm to 500 nm.
  • the invention introduces a repeating unit-DA-structure into the polymer chain, fully utilizes the charge transfer effect, simultaneously adjusts the intensity of the charge energy transfer, controls the absorption peak width of the polymer, and the ultraviolet cutoff wavelength is in the range of 380-400 nm. In order to achieve a barrier to ultraviolet light.
  • the polyimide film of the present invention is obtained by polycondensation of a diamine compound and a dianhydride compound, and the diamine compound used is one or a combination of two or more of the following compounds: p-phenylenediamine, m-phenylenediamine , 1,4-diaminobenzotrifluoride, 3,5-diaminobenzotrifluoride, fluorop-phenylenediamine, 2,5-difluoro-p-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(3-substituent-4- Aminophenyl)anthracene, 9,9-bis(3,5-disubstituted-4-aminophenyl)
  • diamine compounds an important component thereof is 9,9-bis(3,5-disubstituted-4-aminophenyl)fluorene or 9,9-bis(3-substituted-4-amino group
  • phenyl fluorenes which are rigid structure diamine monomers, including a 3,5-position disubstituted structure, or a mono-substituent structure.
  • the two substituents may be the same or different.
  • the substituent includes a linear or isomeric substituent having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, pentyl, 3-methylbutyl, 2-methylbutyl or 2,2-dimethylbutyl, and the like.
  • An alkane substituted with 1 to 6 halogen atoms wherein a hydrogen atom in the above alkane substituent is replaced by 1 to 6 halogen atoms, such as a trifluoromethyl group, a pentafluoroethyl group or the like.
  • the monohalogen atom substituent includes a fluorine atom substituent group, a chlorine atom substituent group, a bromine atom substituent group, an iodine atom substituent group, and a hydroxyl group.
  • the substituent group is preferably a halogen atom substituent and a halogen atom-substituted alkane substitution, and more preferably a trifluoromethyl substituent.
  • the dianhydride monomer used for preparing the polycondensation of the transparent polyimide film comprises three types: biphenyl type tetracarboxylic dianhydride, fluorine-containing aromatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride.
  • the biphenyl type tetracarboxylic dianhydride includes a symmetric bridge type dianhydride and an asymmetric bridge type dianhydride
  • the symmetric bridge type is a 3, 3' position bridge and a 4, 4 position bridge, respectively: 3 , one or more of 3', 4, 4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, asymmetric bridge type 3,4 Bridging, 2,3,3',4'-biphenyltetracarboxylic dianhydride.
  • the fluorine-containing aromatic tetracarboxylic dianhydride has a fluorine atom number of 1-8 and a benzene ring number of 1-4, such as 4,4'-(hexafluoroisopropene) dicarboxylic anhydride, 9-methyl-9.
  • the alicyclic tetracarboxylic dianhydride has an alicyclic structure having a carbon number of 4-8, such as cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, Bicyclo[2,2,2]octane-tetracarboxylic dianhydride, cis-bicyclo[2,2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 2,8-dioxospiro[4 One or two or more of decane-1,3,7,9-tetraketone, preferably one or two of cyclobutanetetracarboxylic dianhydride and cyclohexanetetracarboxylic dianhydride the above.
  • cyclobutane tetracarboxylic dianhydride cyclopent
  • other copolymer group R groups represent a group having no -DA- group, including: an alkyl group having 1-8 carbon atoms, a vinyl group, an ethynyl group, a styryl group, an ether group, a sulfone group, and a benzene ring number. It is an aromatic phenyl group of 1-4, a pyridyl group, a quinolyl group, an isoquinolyl group.
  • the ratio of the dianhydride charge to the dianhydride monomer fluorinated aromatic tetracarboxylic dianhydride is from 1 to 80 mol% of the total amount of the dianhydride.
  • the dianhydride feed ratio, the dianhydride monomer biphenyl type tetracarboxylic dianhydride The proportion of the material accounts for 1-80 mol% of the total amount of dianhydride.
  • the ratio of the dianhydride charge to the dianhydride monomer alicyclic tetracarboxylic dianhydride is from 1 to 50 mol% based on the total amount of the dianhydride.
  • the ratio of the diamine compound to the dianhydride compound is 1:0.98-1.02.
  • the transparent polyimide film has an ultraviolet cut-off wavelength range of 380 nm to 400 nm, and a short-wave transmittance of 380 nm to 400 nm or less is 0, which is completely blocked, and can achieve the effect of blocking ultraviolet rays.
  • the transparent polyimide film has a transmittance of 70% or more in a visible light band of 400 nm to 780 nm, and is a transparent film.
  • the transparent polyimide film does not add any ultraviolet absorber, and absorbs ultraviolet rays by the charge energy transfer of the film body to achieve the effect of shielding ultraviolet rays.
  • an auxiliary material such as an anti-ultraviolet agent, an ultraviolet absorbing material, an inorganic filler, a dispersing agent, an antioxidant, a penetrating agent or the like is added on the basis of the technology of the present invention, the ultraviolet shielding effect can also be achieved. It can be understood that the modification work based on the technology of the present invention is established, and the basic material is the same as the present invention, and belongs to the scope of protection of the invention.
  • the transparent polyimide film is prepared by the following method:
  • the first step the diamine monomer is completely dissolved in the organic solvent in the reaction vessel, the dianhydride monomer is added to the reaction vessel, and the reaction is stirred for 5 to 48 hours to obtain a transparent and viscous polyamic acid solution;
  • the polyamic acid solution is evacuated for 1-48 hours to eliminate bubbles;
  • the second step casting the film on the glass, gradually heating to 350 ° C -450 ° C for 1-5 hours; natural cooling and stripping to obtain a polyimide film.
  • the second step of the above preparation method can be replaced by a method of preparing a film of a polyamic acid solution on a biaxially oriented polyimide film production line.
  • the transverse stretch ratio of the film was controlled to be 1:0.8-1.2, and the longitudinal stretch ratio was 1:1.1-1.6.
  • the preparation method of the transparent polyimide, the organic solvent used is N,N-dimethylformyl An amine, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone or ⁇ -butyrolactone, or a mixed solvent of two or more solvents.
  • the invention provides a transparent film material with ultraviolet blocking effect, and the advantages are as follows:
  • a diamine compound is used as an electron donor, and a dianhydride compound is used as an electron acceptor to introduce a polyimide polymer chain. Effectively adjust the intensity of the -D-A-structure charge transfer energy, allowing the material to block UV light efficiently without adding any UV absorber.
  • polyimide materials into the field of UV-blocking films, because polyimide has excellent mechanical properties, weather resistance and long service life. It has great application value in indoor and outdoor long-term exposure to ultraviolet light.
  • polyimide in the UV-blocking field provides excellent thermal, electrical and optical properties, providing an excellent processing window for further processing applications.
  • the polyimide film provided by the invention is applied to human body protection clothing, lamps, window films, glass films, car films or sunshade articles for preventing ultraviolet radiation.
  • the preparation method for the polyimide film is not limited in the present invention. Therefore, it is within the scope of the present invention to use a diamine monomer and a dianhydride monomer in the polyimide preparation formulation, but other preparations are employed. Methods, such as high temperature reaction one-step method, chemical imidization method, etc., and using other film-forming forms, such as uniaxial stretching lines or biaxial stretching lines to produce films, the core technology is within the scope of the present invention, so Polyimide films are intended to fall within the scope of the present invention.
  • Example 1 is a UV-visible transmittance curve corresponding to the film of Example 1;
  • Example 2 is a UV-visible transmittance curve corresponding to the film of Example 2;
  • Figure 3 is a UV-visible transmittance curve of Comparative Example 1 and Example 1 film
  • Figure 4 is a graph showing the UV-visible transmittance of Comparative Example 2 in comparison with the film of Example 1.
  • the mixture was degassed under vacuum for 5 hours to form a glass substrate coating film.
  • the step was raised to 80 ° C / 150 ° C / 250 ° C / 350 ° C, each step for 1 hour. After that, it was naturally cooled, and the film was immersed in water to obtain a transparent polyimide film.
  • the biphenyl type tetracarboxylic dianhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the fluorine-containing aromatic tetracarboxylic dianhydride is 4,4'-(hexafluoroisopropene).
  • the ultraviolet visible light transmission spectrum of the film was measured, and the scanning wavelength range was 200 nm to 850 nm. As a result, the cutoff wavelength of the film was 385 nm, and the average transmittance at 450 nm to 780 nm was 89% or more, as shown in FIG. As a result, the transmittance in the ultraviolet region below 380 nm was zero. Has a good UV shielding effect. At the same time, it has a high transmittance in the visible light range, and the film has excellent colorless transparency.
  • the glass transition temperature of the film sample was measured by a differential scanning calorimeter, the temperature range was 25-360 ° C, the heating rate was 10 ° C / min, the second temperature was raised, and the N 2 flow rate was 50 mL / min. As a result of the measurement, the glass transition temperature was 385 °C.
  • Thermogravimetric analysis determined that the film sample had a thermal decomposition temperature T 5% of 510 ° C and a T 10% of 550 ° C. The film is excellent in heat resistance.
  • the mixture was degassed under vacuum for 5 hours, and a cast film was formed on the steel sheet.
  • the step was raised to 80 ° C / 150 ° C / 250 ° C / 350 ° C, each step for 1 hour. After that, it was naturally cooled, and the film was immersed in water to obtain a transparent polyimide film.
  • biphenyl type tetracarboxylic dianhydride is 2,2',3,3'-biphenyltetracarboxylic dianhydride
  • fluorine-containing aromatic tetracarboxylic dianhydride is 4,4'-(hexafluoroisopropene).
  • the cutoff wavelength of the film was 392 nm, and the average transmittance at 450 nm to 780 nm was 88% or more, as shown in Fig. 2.
  • the transmittance in the ultraviolet region below 380 nm was zero.
  • the film has excellent UV shielding and excellent colorless transparency.
  • the glass transition temperature was 356 °C.
  • Thermogravimetric analysis determined that the thermal decomposition temperature T 5% of the film sample was 502 ° C and T 10% was 530 ° C.
  • the film has excellent heat resistance.
  • the mixture was degassed under vacuum for 5 hours, and a cast film was formed on the steel sheet.
  • the step was raised to 80 ° C / 150 ° C / 250 ° C / 350 ° C, each step for 1 hour. After that, it was naturally cooled, and the film was immersed in water to obtain a transparent polyimide film.
  • biphenyl type tetracarboxylic dianhydride is 2,3,3',4'-biphenyltetracarboxylic dianhydride
  • fluorine-containing aromatic tetracarboxylic dianhydride is 4,4'-(hexafluoroisopropene).
  • the cutoff wavelength of the film was found to be 400 nm, and the average transmittance at 450 nm to 780 nm was 88% or more. As a result, the transmittance in the ultraviolet region below 380 nm was zero.
  • the film has excellent UV shielding and excellent colorless transparency.
  • the measurement result was that the glass transition temperature was 350 °C.
  • Thermogravimetric analysis determined that the film sample had a thermal decomposition temperature T 5% of 516 ° C and a T 10% of 545 ° C.
  • the film has excellent heat resistance.
  • the mixture was degassed under vacuum for 5 hours, and a cast film was formed on the steel sheet.
  • the step was raised to 80 ° C / 150 ° C / 250 ° C / 350 ° C, each step for 1 hour. After that, it was naturally cooled, and the film was immersed in water to obtain a transparent polyimide film.
  • the biphenyl type tetracarboxylic dianhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the fluorine-containing aromatic tetracarboxylic dianhydride is 4,4'-(hexafluoroisopropene).
  • the film had a cutoff wavelength of 400 nm and an average transmittance of 89% or more at 450 nm to 780 nm. As a result, the transmittance in the ultraviolet region below 380 nm was zero.
  • the film has excellent UV shielding and excellent colorless transparency.
  • the method of measuring the thermal properties of the film in accordance with Example 1 was carried out. As a result of the measurement, the glass transition temperature was 358 °C. Thermogravimetric analysis determined that the film sample had a thermal decomposition temperature T 5% of 535 ° C and a T 10% of 575 ° C. The film has excellent heat resistance.
  • the mixture was degassed under vacuum for 5 hours, and a cast film was formed on the steel sheet.
  • the step was raised to 80 ° C / 150 ° C / 250 ° C / 350 ° C, each step for 1 hour. After that, it was naturally cooled, and the film was immersed in water to obtain a transparent polyimide film.
  • the biphenyl type tetracarboxylic dianhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the fluorine-containing aromatic tetracarboxylic dianhydride is 4,4'-(hexafluoroisopropene).
  • the cutoff wavelength of the film was 386 nm, and the average transmittance at 450 nm to 780 nm was 90% or more.
  • the transmittance in the ultraviolet region below 380 nm is zero.
  • the film has excellent UV shielding and excellent colorless transparency.
  • the method of measuring the thermal properties of the film in accordance with Example 1 was carried out. As a result of the measurement, the glass transition temperature was 400 °C. Thermogravimetric analysis determined that the thermal decomposition temperature T 5% of the film sample was 540 ° C and T 10% was 590 ° C. The film has excellent heat resistance.
  • the mixture was degassed under vacuum for 5 hours, and a cast film was formed on the steel sheet.
  • the step was raised to 80 ° C / 150 ° C / 250 ° C / 350 ° C, each step for 1 hour. After that, it was naturally cooled, and the film was immersed in water to obtain a transparent polyimide film.
  • the biphenyl type tetracarboxylic dianhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the fluorine-containing aromatic tetracarboxylic dianhydride is 4,4'-(hexafluoroisopropene).
  • the film had a cutoff wavelength of 390 nm and an average transmittance of 89% or more at 450 nm to 780 nm.
  • the transmittance in the ultraviolet region below 380 nm is zero.
  • the film has excellent UV shielding and excellent colorless transparency.
  • the method of measuring the thermal properties of the film in accordance with Example 1 was carried out. As a result of the measurement, the glass transition temperature was 396 °C. Thermogravimetric analysis determined that the thermal decomposition temperature T 5% of the film sample was 530 ° C and T 10% was 586 ° C. The film has excellent heat resistance.
  • the biphenyl type tetracarboxylic dianhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the fluorine-containing aromatic tetracarboxylic dianhydride is 4,4'-(hexafluoroisopropene).
  • the film had a cutoff wavelength of 384 nm and an average transmittance of 89% or more at 450 nm to 780 nm.
  • the transmittance in the ultraviolet region below 380 nm is zero.
  • the film has excellent UV shielding and excellent colorless transparency.
  • the method of measuring the thermal properties of the film in accordance with Example 1 was carried out. As a result of the measurement, the glass transition temperature was 372 °C. Thermogravimetric analysis determined that the thermal decomposition temperature T 5% of the film sample was 520 ° C and T 10% was 560 ° C. The film has excellent heat resistance.
  • the polyamic acid solution was prepared according to the formulation in the first embodiment, and the film was produced by using the biaxially stretched polyimide film production line.
  • the basic process parameters of the heat treatment were as follows: the upper temperature of the casting section was 150 ° C, the lower temperature was 180 ° C, and the highest imidization temperature was 380. °C, draw ratio: 1:1 in the transverse direction and 1:1.2 in the longitudinal direction.
  • the prepared film had an ultraviolet cut-off wavelength of 385 nm and an average transmittance of 87% or more at 450 nm to 780 nm. Excellent UV blocking effect.
  • the thermal performance test gave a glass transition temperature of 375 °C. T 5% is 515 ° C and T 10% is 557 ° C. The film is excellent in heat resistance.
  • the polyamic acid solution was prepared according to the formula in the first embodiment, and the film was produced by using the biaxially stretched polyimide film production line.
  • the basic process parameters of the heat treatment were as follows: the upper temperature of the casting section was 120 ° C, the lower temperature was 220 ° C, and the maximum imidization temperature was 400. °C, draw ratio: lateral 1:0.8, longitudinal 1:1.1.
  • the prepared film has an ultraviolet cutoff wavelength of 387 nm and an average transmittance of 85% or more at 450 nm to 780 nm. Excellent UV blocking effect.
  • the thermal performance test gave a glass transition temperature of 375 °C. T 5% is 519 ° C and T 10% is 567 ° C.
  • the film is excellent in heat resistance.
  • the polyamic acid solution was prepared according to the formula in the first embodiment, and the film was produced by using the biaxially stretched polyimide film production line.
  • the basic process parameters of the heat treatment were as follows: the upper temperature of the casting section was 140 ° C, the lower temperature was 190 ° C, and the maximum imidization temperature was 360. °C, draw ratio: 1:1.2 in the transverse direction and 1:1.6 in the longitudinal direction.
  • the prepared film had an ultraviolet cutoff wavelength of 389 nm and an average transmittance of 83% or more at 450 nm to 780 nm. Excellent UV blocking effect.
  • the thermal performance test gave a glass transition temperature of 379 °C. T 5% is 525 ° C and T 10% is 571 ° C. The film is excellent in heat resistance.
  • the polyamic acid solution was prepared according to the formulation in the first embodiment, and the film was produced by using the biaxially stretched polyimide film production line.
  • the basic process parameters of the heat treatment were as follows: the upper temperature of the casting section was 160 ° C, the lower temperature was 210 ° C, and the maximum imidization temperature was 350. °C, draw ratio: 1:0.9 in the transverse direction and 1:1.4 in the longitudinal direction.
  • the prepared film had an ultraviolet cutoff wavelength of 381 nm and an average transmittance of 86% or more at 450 nm to 780 nm. Excellent UV blocking effect.
  • the thermal performance test gave a glass transition temperature of 371 °C. T 5% is 505 ° C and T 10% is 565 ° C. The film is excellent in heat resistance.
  • the second step the obtained polyamic acid solution was allowed to stand for 24 hours, and after the bubbles were removed, the film was coated on the cleaned glass and placed in a high temperature oven. Bake at 80 ° C for 2 hours, step temperature to 100 ° C, 140 ° C, 180 ° C, 220 ° C, 260 ° C for each step for 30 minutes, then to 300 ° C for 1 hour, then naturally cooled to room temperature, the glass plate The film was removed in water to obtain a polyimide film.
  • the ultraviolet-visible light transmission spectrum of the film was measured, and the scanning wavelength range was 200 nm to 850 nm.
  • the film had a cutoff wavelength of 398 nm, a transmittance of 40% at 450 nm, and a transmittance of 62% at 550 nm.
  • the transmittances of Example 1 and Comparative Example 1 are shown in FIG. Although the cutoff wavelength did not differ much, compared with Example 1, the film obtained by the comparative example was dark yellow in visible light. The band absorption is strong, not a colorless transparent film.
  • the UV-visible transmission spectrum of the film was measured.
  • the scanning wavelength range was 200 nm-850 nm.
  • the cut-off wavelength of the film was 297 nm, the transmittance at 30 nm was 30%, and the transmittance at 350 nm was 80% at 400 nm.
  • the transmission rate is 96%.
  • the transmittance of Comparative Example 2 and Example 1 is as shown in Fig. 4. In this comparative example, the average transmittance in the wavelength band of 380 nm or less exceeded 60%, and there was no blocking effect on ultraviolet rays.
  • the mixture was degassed under vacuum for 5 hours to form a glass substrate coating film.
  • the step was raised to 80 ° C / 150 ° C / 250 ° C / 350 ° C, each step for 1 hour. After that, it was naturally cooled, and the film was immersed in water to obtain a transparent polyimide film.
  • the biphenyl type tetracarboxylic dianhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the fluorine-containing aromatic tetracarboxylic dianhydride is 4,4'-(hexafluoroisopropene).
  • Diacetic anhydride compared with Example 1, not added Alicyclic dianhydride.
  • the ultraviolet visible light transmission spectrum of the film was measured, and the scanning wavelength range was 200 nm to 850 nm. As a result, the cutoff wavelength of the film was 400 nm, and the average transmittance at 450 nm to 780 nm was 70%. In contrast to the film of Example 1, the transmittance in the visible light region was lowered to obtain a yellow film.
  • the mixture was degassed under vacuum for 5 hours, and a cast film was formed on the steel sheet.
  • the step was raised to 80 ° C / 150 ° C / 250 ° C / 350 ° C, each step for 1 hour. After that, it was naturally cooled, and the film was immersed in water to obtain a transparent polyimide film.
  • biphenyl type tetracarboxylic dianhydride is 2,3,3',4'-biphenyltetracarboxylic dianhydride
  • alicyclic tetracarboxylic dianhydride is cyclopentane tetracarboxylic dianhydride
  • examples 3 comparison, no fluorine-containing aromatic dianhydride was added.
  • the ultraviolet visible light transmission spectrum of the film was measured, and the scanning wavelength range was 200 nm to 850 nm.
  • the cutoff wavelength of the film was 400 nm, and the average transmittance at 450 nm to 780 nm was 74%.
  • the results showed that the film had a lower transmittance in the visible light range than in Example 3 and was a pale yellow film.

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Abstract

本发明涉及一种具有阻隔紫外线作用的透明聚酰亚胺薄膜，该聚酰亚胺薄膜的紫外截止波长380-400nm之间，更短波波段透过率为0，完全阻隔。该聚酰亚胺薄膜包括以二胺类化合物与二酐类化合物为原料制备的均聚物和/或共聚物聚酰亚胺高分子，其具有重复单元-D-A-，D表示二胺类化合物残基，A表示二酐类化合物残基，D结构单元属于电子给体，A结构单元属于电子受体，-D-A-结构之间存在电荷能量转移吸收作用，吸收峰在380-400nm以下短波范围。本发明提供的聚酰亚胺薄膜，制备方法简单，其高效阻隔紫外线，无需添加任何紫外吸收剂，同时可应用于防紫外线辐射的人体保护服饰、灯具、窗膜，玻璃贴膜，车膜或遮阳用具。

Description

具有阻隔紫外线作用的透明聚酰亚胺薄膜及其制备和应用 技术领域
本发明涉及一种具有阻隔紫外线作用的透明聚酰亚胺薄膜，应用于防紫外线辐射的人体保护服饰、灯具、窗膜，玻璃贴膜，车膜或遮阳用具。
背景技术
紫外线是指波长介于200-400纳米之间的电磁波，属于恒星发光的一部分波段，广泛存在于外太空间。由于近几十年来地球臭氧层的破坏，在地表空间紫外线辐射强度不断提高。此外，普遍应用的人造光源，比如紫外灯，电弧等，也会产生紫外线。科学已经证实过量的紫外线辐射对人体，对动植物都有不同程度的伤害。人体接受过量紫外线辐射会诱发皮肤病，甚至皮肤癌。此外，强辐射性的紫外线会破坏材料结构性能，尤其是有机材料，会加速现代文明中大量应用的光电子器件老化，缩短器件寿命，带来不同程度的经济损失。为此，人类发明了多种抗紫外线材料，降低紫外线的辐射强度。
目前，普遍采用的是在材料中添加抗紫外线添加剂。主要是无机添加剂和有机添加剂两种。在制备抗紫外线薄膜中添加不同配方的抗紫外线添加剂达到抗紫外效果。许龙麟，周俊宏等(CN101012343A)在光学基膜上涂上一层包含无机粒子和有机粒子的树脂涂料，制得抗紫外薄膜。陈建峰、曾晓飞等(CN101555340A)通过溶液共混法或溶液-熔融共混法制备了含有金属氧化物纳米粒子、高分子助剂等抗紫外高透明光学薄膜。杨炳文、江涛等(CN102756522)引入苯三唑、苯酮等紫外线抑制剂，制备了三层聚乙烯复合薄膜，具备紫外线阻隔效果。顾文中(CN104371233A)采用聚乙烯醇、磷酸钛钠和丙三醇通过溶液共溶-浸渍提拉法制备了抗紫外线塑料薄膜。
抗紫外线添加剂加入都存在在基材中无法均匀分散的问题，此外存在抗紫外添加剂的老化衰退等问题，目前技术难以克服。在已经报道的发明专利 中，透明薄膜采用聚乙烯，聚碳酸酯，聚甲基丙烯酸甲酯等作为基础材料，存在耐温性以及耐老化性能的限制，无法在耐高温的光电子器件领域发挥作用。
在聚合物材料中，聚酰亚胺具备最高的耐温等级，同时耐老化性、耐辐射性、耐化学性优于其他聚合物材料。
发明内容
本发明的目的是提供一种具备阻隔紫外线作用的透明聚酰亚胺薄膜，薄膜是完全均一的聚合物材料，依靠本体材料吸收紫外线，无需加入任何无机有机抗紫外线添加剂。紫外截止波长380-400nm之间，更短波波段透过率为0，完全阻隔。可见光波段透过率平均在75％以上，不影响可见光波段的透过率，是种透明的薄膜材料，满足需要屏蔽紫外线，同时透明应用领域。
本发明所述的聚酰亚胺薄膜，其特征在于：薄膜包括以二胺类化合物与二酐类化合物为原料制备的均聚型聚酰亚胺高分子和/或共聚型聚酰亚胺高分子，具有如下化学结构简式，
Figure PCTCN2016103781-appb-000001
所述的聚酰亚胺薄膜，二胺类化合物残基D属于电子给体，二酐类化合物残基A属于电子受体。二胺类化合物中含有氨基，具有孤对电子对，电子 云密度高。而二酐类化合物中含有酸酐，具备强吸电子作用。缩聚反应后，二胺类化合物残基D属于电子给体Dornor，二酐类化合物残基A属于电子受体Acceptor，缩聚后形成-D-A-重复单元。缩聚后，D和A两者之间发生电荷能量转移作用，电荷转移作用发生在高分子链内单元，同时也发生在高分子链间单元。电荷能量转移作用吸收峰宽280nm-500nm。本发明在高分子链中引入重复单元-D-A-结构，充分利用电荷转移作用，同时调节电荷能量转移作用的强弱程度，控制高分子聚合物吸收峰宽，紫外截止波长在380-400nm波段范围，从而达到阻隔紫外线作用。
本发明的聚酰亚胺薄膜由二胺类化合物与二酐类化合物缩聚制备得到，所用的二胺类化合物为以下化合物中一种或二种以上的组合：对苯二胺、间苯二胺、1,4-二氨基三氟甲苯、3,5-二氨基三氟甲苯，氟代对苯二胺、2,5-二氟对苯二胺、4,4’-二氨基二苯醚、3,3’-二氨基二苯醚、4,4’-二氨基二苯硫醚、9,9-双(4-氨基苯基)芴、9,9-双(3-取代基-4-氨基苯基)芴、9,9-双(3，5-二取代基-4-氨基苯基)芴、二氨基二苯砜、4,4’-二氨基联苯、m,m’-二氨基联苯、4,4’-二氨基-3,3’-二甲基联苯、4,4’-二氨基-3,3’-二(三氟甲基)联苯、4,4’-二氨基-2,2’-二(三氟甲基)联苯、2,2’-二氟联苯二胺、2,2’-二氯联苯二胺、2,2’-二溴联苯二胺、八氟联苯胺、3,5,3’,5’-四甲基联苯二胺、2,6,2’,6’-四甲基联苯二胺、2,2’-双三氟甲基-4,4’-二苯醚二胺、2,2’-双三氟甲基-4,4’-二苯硫醚二胺、2,2’-双三氟甲基-4,4’-二苯砜二胺、4,4’-二氨基二苯甲烷、3,4’-二氨基二苯甲烷、3,3’-二甲基-4,4’-二氨基二苯甲烷。
所述的二胺类化合物中，其中重要组分是9,9-双(3，5-二取代基-4-氨基苯基)芴或9,9-双(3-取代基-4-氨基苯基)芴中一种或二种以上，属于刚性结构的二胺单体，包括3,5位双取代基结构，或者单取代基结构。双取代基结构情况下两个取代基可以相同也可以不相同。取代基包括碳原子数1-5个烷烃直链或者异构取代基，如甲基、乙基、丙基、异丙基、正丁基、 异丁基、特丁基、戊基、3-甲基丁基、2-甲基丁基或2,2-二甲基丁基等等。含有1-6个卤素原子的烷烃取代，上述烷烃取代基中氢原子被1-6个卤素原子替代所得，如三氟甲基，五氟乙基等。单卤素原子取代基，包括氟原子取代基团、氯原子取代基团、溴原子取代基团、碘原子取代基团，羟基。其中，取代基团中优选为卤素原子取代基以及含卤素原子取代的烷烃取代，再优选为三氟甲基取代基。
所述的透明聚酰亚胺薄膜制备缩聚所用的二酐单体包含三类：联苯型四羧酸二酐、含氟芳香型四羧酸二酐、脂环族四羧酸二酐。
其中，联苯型四羧酸二酐包括对称桥联型二酐和不对称桥联型二酐，对称桥联型为3,3’位桥联和4,4位桥联，分别为：3,3’,4,4’-联苯四甲酸二酐、2,2’,3,3’-联苯四甲酸二酐中的一种或二种以上，不对称桥联型为3,4位桥联，2,3,3’,4’-联苯四甲酸二酐。
其中，含氟芳香型四羧酸二酐含氟原子数为1-8，苯环数为1-4，如4,4'-(六氟异丙烯)二酞酸酐、9-甲基-9-三氟甲基氧杂蒽二酐、9,9-二(三氟甲基)氧杂蒽二酐、9-三氟甲基-9-五氟乙基氧杂蒽二酐中的一种或二种以上，优选为4,4'-(六氟异丙烯)二酞酸酐。
其中，脂环族四羧酸二酐中脂环结构含碳数为4-8，如环丁烷四羧酸二酐、环戊烷四羧酸二酐、环己烷四羧酸二酐，双环[2,2,2]辛烷-四酸二酐，顺式-双环[2,2.1]庚烷-2,3,5,6-四酸二酐，2,8-二氧螺[4,5]癸烷-1,3,7,9-四酮中的一种或二种以上，优选环丁烷四羧酸二酐和环己烷四羧酸二酐中的一种或二种以上。
其中，其它共聚基团R基团表示不具备-D-A-基团，包括：碳原子数为1-8的烷基，乙烯基，乙炔基，苯乙烯基，醚基，砜基，苯环数为1-4的芳香苯基，吡啶基，喹啉基，异喹啉基。
具体的，所述的二酐投料比，二酐单体含氟芳香型四羧酸二酐投料比例占二酐总量的1-80mol％。所述的二酐投料比，二酐单体联苯型四羧酸二酐投 料比例占二酐总量的1-80mol％。所述的二酐投料比，二酐单体脂环族四甲酸二酐投料比例占二酐总量的1-50mol％。
具体的，二胺类化合物和二酐类化合物的投料比例为1:0.98-1.02。
所述的透明聚酰亚胺薄膜紫外截止波长范围是380nm-400nm，380nm-400nm以下短波透过率为0，完全阻隔，能够达到阻隔紫外线的效果。
所述的透明聚酰亚胺薄膜在400nm-780nm可见光波段透过率为70％以上，属于透明薄膜。
所述的透明聚酰亚胺薄膜无添加任何紫外线吸收剂，通过薄膜本体电荷能量转移吸收紫外线达到屏蔽紫外线的效果。在该技术具体实施过程中，如果在本发明技术的基础上再添加抗紫外剂、紫外线吸收材料、无机填料，分散剂，抗氧化剂，增透剂等辅助材料，同样能够达到紫外屏蔽的效果，可以理解为建立在本发明技术的基础上做的修饰工作，基础材料与本发明相同，属于在发明的保护范围。
所述的透明聚酰亚胺薄膜采用以下方法制备：
第一步：在反应容器中二胺单体完全溶解于有机溶剂中，将二酐单体加入反应容器，搅拌反应5-48小时，得到透明、粘稠状的聚酰胺酸溶液；将所得的聚酰胺酸溶液抽真空1-48小时消除气泡；
第二步：在玻璃上流延涂膜，用1-5小时逐渐升温至350℃-450℃；自然冷却后脱膜得到聚酰亚胺薄膜。
上述制备方法的第二步可由如下方法替代：将聚酰胺酸溶液在双向拉伸聚酰亚胺薄膜生产线上制备薄膜。
具体的，双向拉伸聚酰亚胺薄膜生产线流延机流延段温度控制范围120℃-220℃；双向拉伸聚酰亚胺薄膜生产线流延机亚胺炉最高温度控制范围300℃-400℃，亚胺化温度升温阶梯10℃-100℃。控制薄膜横向拉伸比1:0.8-1.2,纵向拉伸比1:1.1-1.6。
所述的透明聚酰亚胺的制备方法，所用的有机溶剂为N,N-二甲基甲酰 胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮或γ-丁内酯，或者二种以上溶剂的混合溶剂。
本发明提供一种具备阻隔紫外线的透明薄膜材料,优点在于如下：
1.将二胺类化合物作为电子给体，二酐类化合物作为电子受体，引入聚酰亚胺高分子链。有效地调节-D-A-结构电荷转移能量的强弱，使得材料高效阻隔紫外线，无需添加任何紫外吸收剂。
2.将聚酰亚胺材料引入挡紫外薄膜领域，由于聚酰亚胺具备优异的机械性能，耐候性能，使用寿命长。在室内室外长期接触紫外线区域具备巨大的应用价值。
3.将聚酰亚胺应用于挡紫外领域，优异的热性能、电学性能、光学性能，为该材料进一步加工应用提供极好的加工窗口。
4.本发明提供的聚酰亚胺薄膜应用于防紫外线辐射的人体保护服饰、灯具、窗膜，玻璃贴膜，车膜或遮阳用具。
本发明中并未对针对聚酰亚胺薄膜的制备方法进行限定，因此，在聚酰亚胺制备配方中采用二胺单体和二酐单体在本发明的保护范围内，但是采用其他制备方法，比如高温反应一步法，化学亚胺化法等，以及采用其他成膜形式，比如单向拉伸生产线或者双向拉伸生产线上生产薄膜，核心技术在本发明的保护范围内，所以得到的聚酰亚胺薄膜应该属于本发明的保护范围内。
附图说明
图1是实施例1薄膜对应的紫外可见透过率曲线；
图2是实施例2薄膜对应的紫外可见透过率曲线；
图3是对比实例1与实施例1薄膜对比的紫外可见透过率曲线；
图4是对比实例2与实施例1薄膜对比的紫外可见透过率曲线。
具体实施方式
下面结合附图及具体实施例，进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。此外，在阅读了本发明阐述的内容之后，本领域技术人员对本发明作各种修改，这些等价形式同样属于本申请所附权利求书所限定的范围之内。
实施例1
在反应容器内，将3.212g间苯二胺、1.475g二氨基二苯砜、11.510g9,9-双(3-三氟甲基-4-氨基苯基)芴共混溶解于150g N,N-二甲基乙酰胺溶剂中，溶解完毕后，加入13.212g 4,4'-(六氟异丙烯)二酞酸酐，反应完全后缓慢加入1.166g环丁烷四甲酸二酐，最后加入7.5g3,3',4,4'-联苯四羧酸二酐，反应18小时后停止搅拌。
过滤后真空脱泡5小时，进行玻璃基板涂膜。阶梯升温，80℃/150℃/250℃/350℃，每个阶梯停留1小时。之后自然冷却，水中浸泡脱膜，得到透明聚酰亚胺薄膜。
此配方中联苯型四羧酸二酐采用3,3',4,4'-联苯四羧酸二酐，含氟芳香型四羧酸二酐采用4,4'-(六氟异丙烯)二酞酸酐，脂环族四羧酸二酐采用环丁烷四甲酸二酐。
测定薄膜的紫外可见光透过光谱，测试扫描波长范围是200nm-850nm,结果得到薄膜的截止波长为385nm，在450nm-780nm平均透过率为89％以上，见附图1。结果显示，紫外光区380nm以下透过率为0。具备很好的紫外屏蔽效果。同时，在可见光波段具有很高的透过率，薄膜具备优异的无色透明度。
差示扫描量热仪测定薄膜样品的玻璃化转变温度，温度范围25-360℃，升温速率10℃/min，二次升温，N2流量50mL/min。测定得到结果是玻璃化转变温度是385℃。热重分析测定薄膜样品的热分解温度T5％为510℃，T10％为550℃。薄膜的耐热性能优异。
实施例2
在反应容器内，将10.00g 2,2’-双三氟甲基-4,4’-二苯醚二胺、14.407g 9,9’-双(3-三氟甲基-4-氨基苯基)芴共混溶解于220g N,N-二甲基乙酰胺/N-甲基吡咯烷酮(1:2)混合溶剂中，溶解完毕后，加入13.212g4,4'-(六氟异丙烯)二酞酸酐，反应完全后缓慢加入3.333g 1,2,4,5-环己烷四甲酸二酐，最后加入4.375g2,2',3,3'-联苯四羧酸二酐，反应12小时后停止搅拌。
过滤后真空脱泡5小时，进行钢板上流延涂膜。阶梯升温，80℃/150℃/250℃/350℃，每个阶梯停留1小时。之后自然冷却，水中浸泡脱膜，得到透明聚酰亚胺薄膜。
此配方中联苯型四羧酸二酐采用2,2',3,3'-联苯四羧酸二酐，含氟芳香型四羧酸二酐采用4,4'-(六氟异丙烯)二酞酸酐，脂环族四羧酸二酐采用1,2,4,5-环己烷四甲酸二酐。
按照实施例1中测定薄膜的紫外可见光透过光谱的方法，结果得到薄膜的截止波长为392nm，在450nm-780nm平均透过率为88％以上，见附图2。结果显示，紫外光区380nm以下透过率为0。薄膜具备很好的紫外屏蔽效果，同时具备优异的无色透明度。
按照实施1中测定薄膜热性能的方法得到结果是玻璃化转变温度是356℃。热重分析测定薄膜样品的热分解温度T5％为502℃，T10％为530℃。薄膜具备优异的耐热性能。
实施例3
在反应容器内，将6.484g 4,4’-二苯醚二胺、14.407g 9,9’-双(3-三氟甲基-4-氨基苯基)芴共混溶解于220g N-甲基吡咯烷酮中，溶解完毕后，加入13.212g 4,4'-(六氟异丙烯)二酞酸酐，反应完全后缓慢加入3.125g环戊烷四甲酸二酐，最后加入4.375g2,3,3',4'-联苯四羧酸二酐，反应13小时后停止搅拌。
过滤后真空脱泡5小时，进行钢板上流延涂膜。阶梯升温，80℃/150℃/250℃/350℃，每个阶梯停留1小时。之后自然冷却，水中浸泡脱膜，得到透明聚酰亚胺薄膜。
此配方中联苯型四羧酸二酐采用2,3,3',4'-联苯四羧酸二酐，含氟芳香型四羧酸二酐采用4,4'-(六氟异丙烯)二酞酸酐，脂环族四羧酸二酐采用环戊烷四甲酸二酐。
按照实施例1中测定薄膜的紫外可见光透过光谱的方法，结果得到薄膜的截止波长为400nm，在450nm-780nm平均透过率为88％以上。结果显示，紫外光区380nm以下透过率为0。薄膜具备很好的紫外屏蔽效果，同时具备优异的无色透明度。
按照实施例1中测定薄膜热性能的方法，测定得到结果是玻璃化转变温度是350℃。热重分析测定薄膜样品的热分解温度T5％为516℃，T10％为545℃。薄膜具备优异的耐热性能。
实施例4
在反应容器内，将10.00g 2,2’-双三氟甲基-4,4’-二苯醚二胺、1.453g 9,9’-双(3-三氟甲基-4-氨基苯基)芴共混溶解于100g N-甲基吡咯烷酮中，溶解完毕后，加入7.340g 4,4'-(六氟异丙烯)二酞酸酐，反应完全后缓慢加入0.740g 1,2,4,5-环己烷四甲酸二酐，最后加入3.884g2,2',3,3'-联苯四羧酸二酐，反应10小时后停止搅拌。
过滤后真空脱泡5小时，进行钢板上流延涂膜。阶梯升温，80℃/150℃/250℃/350℃，每个阶梯停留1小时。之后自然冷却，水中浸泡脱膜，得到透明聚酰亚胺薄膜。
此配方中联苯型四羧酸二酐采用3,3',4,4'-联苯四羧酸二酐，含氟芳香型四羧酸二酐采用4,4'-(六氟异丙烯)二酞酸酐，脂环族四羧酸二酐采用1,2,4,5-环己烷四甲酸二酐。
按照实施例1中测定薄膜的紫外可见光透过光谱的方法，结果得到薄膜的截止波长为400nm，在450nm-780nm平均透过率为89％以上。结果显示，紫外光区380nm以下透过率为0。薄膜具备很好的紫外屏蔽效果，同时具备优异的无色透明度。
按照实施例1中测定薄膜热性能的方法。测定得到结果是玻璃化转变温度是358℃。热重分析测定薄膜样品的热分解温度T5％为535℃，T10％为575℃。薄膜具备优异的耐热性能。
实施例5
在反应容器内，将4.924g3,5-二氨基三氟甲苯、14.533g 9,9’-双(3-三氟甲基-4-氨基苯基)芴共混溶解于150g N,N-二甲基甲酰胺中，溶解完毕后，加入15.993g 4,4'-(六氟异丙烯)二酞酸酐，反应完全后缓慢加入2.354g环丁烷四甲酸二酐，最后加入3.531g3,3',4,4'-联苯四羧酸二酐，反应12小时后停止搅拌。
过滤后真空脱泡5小时，进行钢板上流延涂膜。阶梯升温，80℃/150℃/250℃/350℃，每个阶梯停留1小时。之后自然冷却，水中浸泡脱膜，得到透明聚酰亚胺薄膜。
此配方中联苯型四羧酸二酐采用3,3',4,4'-联苯四羧酸二酐，含氟芳香型四羧酸二酐采用4,4'-(六氟异丙烯)二酞酸酐，脂环族四羧酸二酐采用环丁烷四甲酸二酐。
按照实施例1中测定薄膜的紫外可见光透过光谱的方法,结果得到薄膜的截止波长为386nm，在450nm-780nm平均透过率为90％以上。紫外光区380nm以下透过率为0。薄膜具备很好的紫外屏蔽效果，同时具备优异的无色透明度。
按照实施例1中测定薄膜热性能的方法。测定得到结果是玻璃化转变温度是400℃。热重分析测定薄膜样品的热分解温度T5％为540℃，T10％为590℃。薄膜具备优异的耐热性能。
实施例6
在反应容器内，将4.924g3,5-二氨基三氟甲苯、11.533g 9,9’-双(3-氟-4-氨基苯基)芴共混溶解于150g N,N-二甲基甲酰胺中，溶解完毕后，加入15.993g 4,4'-(六氟异丙烯)二酞酸酐，反应完全后缓慢加入2.353g1,2,4,5-环丁烷四甲酸二酐，最后加入3.531g2,2',3,3'-联苯四羧酸二酐，反应15小时后停止搅拌。
过滤后真空脱泡5小时，进行钢板上流延涂膜。阶梯升温，80℃/150℃/250℃/350℃，每个阶梯停留1小时。之后自然冷却，水中浸泡脱膜，得到透明聚酰亚胺薄膜。
此配方中联苯型四羧酸二酐采用3,3',4,4'-联苯四羧酸二酐，含氟芳香型四羧酸二酐采用4,4'-(六氟异丙烯)二酞酸酐，脂环族四羧酸二酐采用1,2,4,5-环己烷四甲酸二酐。
按照实施例1中测定薄膜的紫外可见光透过光谱的方法,结果得到薄膜的截止波长为390nm，在450nm-780nm平均透过率为89％以上。紫外光区380nm以下透过率为0。薄膜具备很好的紫外屏蔽效果，同时具备优异的无色透明度。
按照实施例1中测定薄膜热性能的方法。测定得到结果是玻璃化转变温度是396℃。热重分析测定薄膜样品的热分解温度T5％为530℃，T10％为586℃。薄膜具备优异的耐热性能。
实施例7
在反应容器内，将16.012g4,4’-二氨基-2,2’-双三氟甲基联苯、4.844g 9,9’-双(3-三氟甲基-4-氨基苯基)芴共混溶解于150g N,N-二甲基乙酰胺中，溶解完毕后，加入7.996g 4,4'-(六氟异丙烯)二酞酸酐，反应完全后缓慢加入2.690g 1,2,4,5-环己烷四甲酸二酐，最后加入8.826g3,3',4,4'-联苯四羧酸二酐，反应20小时后停止搅拌。
过滤后真空脱泡5小时，进行钢板上流延涂膜。阶梯升温， 80℃/150℃/250℃/350℃，每个阶梯停留1小时。之后自然冷却，水中浸泡脱膜，得到透明聚酰亚胺薄膜。
此配方中联苯型四羧酸二酐采用3,3',4,4'-联苯四羧酸二酐，含氟芳香型四羧酸二酐采用4,4'-(六氟异丙烯)二酞酸酐，脂环族四羧酸二酐采用1,2,4,5-环己烷四甲酸二酐。
按照实施例1中测定薄膜的紫外可见光透过光谱的方法,结果得到薄膜的截止波长为384nm，在450nm-780nm平均透过率为89％以上。紫外光区380nm以下透过率为0。薄膜具备很好的紫外屏蔽效果，同时具备优异的无色透明度。
按照实施例1中测定薄膜热性能的方法。测定得到结果是玻璃化转变温度是372℃。热重分析测定薄膜样品的热分解温度T5％为520℃，T10％为560℃。薄膜具备优异的耐热性能。
实施例8
按照实施1中配方制备得到聚酰胺酸溶液，采用双向拉伸聚酰亚胺薄膜生产线生产得到薄膜，热处理基本工艺参数：流延段上温150℃，下温180℃，亚胺化最高温度380℃，拉伸比：横向1:1，纵向1:1.2。
制备得到的薄膜紫外截止波长为385nm，在450nm-780nm平均透过率为87％以上。阻隔紫外线效果优异。热性能测试得到玻璃化转变温度为375℃。T5％为515℃，T10％为557℃。薄膜的耐热性能优异。
实施例9
按照实施1中配方制备得到聚酰胺酸溶液，采用双向拉伸聚酰亚胺薄膜生产线生产得到薄膜，热处理基本工艺参数：流延段上温120℃，下温220℃，亚胺化最高温度400℃，拉伸比：横向1:0.8，纵向1:1.1。
制备得到的薄膜紫外截止波长为387nm，在450nm-780nm平均透过率为85％以上。阻隔紫外线效果优异。热性能测试得到玻璃化转变温度为375℃。T5％为519℃，T10％为567℃。薄膜的耐热性能优异。
实施例10
按照实施1中配方制备得到聚酰胺酸溶液，采用双向拉伸聚酰亚胺薄膜生产线生产得到薄膜，热处理基本工艺参数：流延段上温140℃，下温190℃，亚胺化最高温度360℃，拉伸比：横向1:1.2，纵向1:1.6。
制备得到的薄膜紫外截止波长为389nm，在450nm-780nm平均透过率为83％以上。阻隔紫外线效果优异。热性能测试得到玻璃化转变温度为379℃。T5％为525℃，T10％为571℃。薄膜的耐热性能优异。
实施例11
按照实施1中配方制备得到聚酰胺酸溶液，采用双向拉伸聚酰亚胺薄膜生产线生产得到薄膜，热处理基本工艺参数：流延段上温160℃，下温210℃，亚胺化最高温度350℃，拉伸比：横向1:0.9，纵向1:1.4。
制备得到的薄膜紫外截止波长为381nm，在450nm-780nm平均透过率为86％以上。阻隔紫外线效果优异。热性能测试得到玻璃化转变温度为371℃。T5％为505℃，T10％为565℃。薄膜的耐热性能优异。
对比实例1
在室温下，将30g4,4’-二氨基二苯醚溶解于313gN-甲基吡咯烷酮中，机械搅拌，完全溶解后分批加入32.66g3,3',4,4'-联苯四羧酸二酐，继续搅拌反应8小时，得到的透明、粘稠状聚酰胺酸溶液。
第二步：将所得的聚酰胺酸溶液静置24小时待其中气泡消除后，在清洁的玻璃上涂膜，放入高温烘箱。在80℃下烘2小时，阶梯升温到100℃、140℃、180℃、220℃、260℃每一阶梯各维持30分钟,再到300℃烘1小时，然后自然冷却到室温，将玻璃板放入水中脱膜，得到聚酰亚胺薄膜。
测定薄膜的紫外可见光透过光谱，测试扫描波长范围是200nm-850nm,结果得到薄膜的截止波长为398nm，在450nm处透过率为40％，在550nm处透过率为62％。实施例1与对比实例1的透过率如图3所示。虽然截止波长差别不大，但与实施例1比较，该对比实例得到的薄膜为深黄色，在可见光 波段吸收强，不是无色透明薄膜。
对比实例2
在室温下，称取2.00g二氨基二苯醚、2.48g二氨基二苯砜加入到反应瓶，氮气保护下加入40gN-甲基吡咯烷酮，搅拌溶解后，加入1.4g环己二酐反应，再加入2.67g4,4'-(六氟异丙烯)二酞酸酐，完全反应溶解后，加入0.5mL乙酸酐，升温至170℃，反应12小时。冷却至室温后将反应液倒入乙醇析出，乙醇煮洗，过滤烘干得到聚酰亚胺树脂粉末。
称取1g聚酰亚胺树脂粉末，用9g N,N-二甲基甲酰胺溶解后得到聚酰亚胺溶液，在玻璃板上涂膜，在80℃下烘2小时，阶梯升温到100℃、120℃、140℃、160℃、180℃，每一阶梯各维持30分钟,再到200℃烘1小时，冷却，放入水中脱膜，得到聚酰亚胺薄膜。
测定薄膜的紫外可见光透过光谱，测试扫描波长范围是200nm-850nm,结果得到薄膜的截止波长为297nm，在310nm处透过率为30％，在350nm处透过率为80％，在400nm处透过率为96％。对比实例2与实施例1的透过率情况如图4所示，该对比实例中，在波长380nm以下波段的平均透过率超过60％，对紫外线不具备阻隔效果。
对比实例3
在反应容器内，将3.212g间苯二胺、1.475g二氨基二苯砜、11.510g9,9-双(3-三氟甲基-4-氨基苯基)芴共混溶解于150g N,N-二甲基乙酰胺溶剂中，溶解完毕后，加入13.212g 4,4'-(六氟异丙烯)二酞酸酐，加入9.247g3,3',4,4'-联苯四羧酸二酐。反应18小时后停止搅拌。
过滤后真空脱泡5小时，进行玻璃基板涂膜。阶梯升温，80℃/150℃/250℃/350℃，每个阶梯停留1小时。之后自然冷却，水中浸泡脱膜，得到透明聚酰亚胺薄膜。
此配方中联苯型四羧酸二酐采用3,3',4,4'-联苯四羧酸二酐，含氟芳香型四羧酸二酐采用4,4'-(六氟异丙烯)二酞酸酐，与实施例1比较，未加入 脂环族二酐。
测定薄膜的紫外可见光透过光谱，测试扫描波长范围是200nm-850nm,结果得到薄膜的截止波长为400nm，在450nm-780nm平均透过率为70％。与实施例1中薄膜作对比，在可见光区透过率下降，为黄色薄膜。
对比实例4
在反应容器内，将6.484g 4,4’-二苯醚二胺、14.407g 9,9’-双(3-三氟甲基-4-氨基苯基)芴共混溶解于150g N-甲基吡咯烷酮中，溶解完毕后，缓慢加入3.125g环戊烷四甲酸二酐，最后加入13.125g2,3,3',4'-联苯四羧酸二酐，反应13小时后停止搅拌。
过滤后真空脱泡5小时，进行钢板上流延涂膜。阶梯升温，80℃/150℃/250℃/350℃，每个阶梯停留1小时。之后自然冷却，水中浸泡脱膜，得到透明聚酰亚胺薄膜。
此配方中联苯型四羧酸二酐采用2,3,3',4'-联苯四羧酸二酐，脂环族四羧酸二酐采用环戊烷四甲酸二酐，与实施例3比较，未加入含氟芳香型二酐。测定薄膜的紫外可见光透过光谱，测试扫描波长范围是200nm-850nm,结果得到薄膜的截止波长为400nm，在450nm-780nm平均透过率为74％。结果显示，此薄膜在可见光范围内的透过率低于实施例3，是淡黄色薄膜。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (15)

  1. 具有阻隔紫外线作用的透明聚酰亚胺薄膜，其特征在于：薄膜紫外截止波长范围是380nm-400nm，在波长380nm以下短波波段透过率为0，完全阻隔。
  2. 根据权利要求1所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜，其特征在于：薄膜包括以二胺类化合物与二酐类化合物为原料制备的均聚物和/或共聚物聚酰亚胺高分子，具有如下化学结构简式，
    Figure PCTCN2016103781-appb-100001
  3. 根据权利要求2所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜，其特征在于：在均聚物或者共聚物中具有重复单元-D-A-，D表示二胺类化合物残基，A表示二酐类化合物残基，D结构单元属于电子给体，A结构单元属于电子受体，-D-A-结构之间存在电荷能量转移吸收作用，吸收峰在380-400nm以下短波范围，通过在高分子链中引入的-D-A-结构，达到吸收紫 外线目的。
  4. 根据权利要求2所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜，其特征在于：所述的二胺类化合物为以下化合物中的一种或二种以上组成：对苯二胺、间苯二胺、1,4-二氨基三氟甲苯、3,5-二氨基三氟甲苯，氟代对苯二胺、2,5-二氟对苯二胺、4,4’-二氨基二苯醚、3,3’-二氨基二苯醚、4,4’-二氨基二苯硫醚、9,9-双(4-氨基苯基)芴、9,9-双(3-取代基-4-氨基苯基)芴、9,9-双(3，5-二取代基-4-氨基苯基)芴、二氨基二苯砜、4,4’-二氨基联苯、m,m’-二氨基联苯、4,4’-二氨基-3,3’-二甲基联苯、4,4’-二氨基-3,3’-二(三氟甲基)联苯、4,4’-二氨基-2,2’-二(三氟甲基)联苯、2,2’-二氟联苯二胺、2,2’-二氯联苯二胺、2,2’-二溴联苯二胺、八氟联苯胺、3,5,3’,5’-四甲基联苯二胺、2,6,2’,6’-四甲基联苯二胺、2,2’-双三氟甲基-4,4’-二苯醚二胺、2,2’-双三氟甲基-4,4’-二苯硫醚二胺、2,2’-双三氟甲基-4,4’-二苯砜二胺、4,4’-二氨基二苯甲烷、3,4’-二氨基二苯甲烷或3,3’-二甲基-4,4’-二氨基二苯甲烷。
  5. 根据权利要求2所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜，其特征在于，所述的二酐类化合物包含以下三类化合物：联苯型四羧酸二酐、含氟芳香型四羧酸二酐、脂环族四羧酸二酐；其中，含氟芳香型四羧酸二酐占二酐类化合物总量的1-80mol％；联苯型四羧酸二酐占二酐类化合物总量的1-80mol％；脂环族四羧酸二酐占二酐类化合物总量的1-50mol％。
  6. 根据权利要求5所述的具有阻隔紫外线作用的透明二酐类化合物，其特征在于，联苯型四羧酸二酐为对称桥联型二酐、不对称桥联型二酐、对称桥联型为3,3位桥联、4,4位桥联和不对称桥联型为3,4位桥联中的一种或多种；含氟芳香型四羧酸二酐含氟原子数为1-8、苯环数为1-4；脂环族四羧酸二酐中脂环结构含碳数为4-8。
  7. 根据权利要求2所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜，其特征在于：其它共聚基团R基团表示不含有-D-A-重复单元的骨架基团，由 以下基团中的一种或多种组成：碳原子数为1-8的烷基、乙烯基、乙炔基、苯乙烯基、醚基、砜基、苯环数为1-4的芳香苯基、吡啶基、喹啉基和异喹啉基。
  8. 根据权利要求2至7任一项所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜，其特征在于，二胺类化合物和二酐类化合物的摩尔比例为1:0.98-1.02。
  9. 一种如权利要求1至8中任意一项所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜的制备方法，其特征在于，包括如下步骤：
    第一步：在反应容器中将二胺类化合物完全溶解于有机溶剂中，将二酐类化合物按照其所分的三个类别分批加入反应容器，反应温度控制-5℃-50℃，搅拌反应5-48小时，得到透明、粘稠状的聚酰胺酸溶液；将所得的聚酰胺酸溶液抽真空1-48小时消除气泡；
    第二步：在玻璃上涂覆薄膜，烘箱内进行热处理，从室温逐渐升温至350℃-450℃，保温0.5-4小时，升温速率为1℃/分钟-8℃/分钟；自然冷却至25℃-50℃后得到薄膜。
  10. 一种如权利要求1至8中任意一项所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜的制备方法，其特征在于，包括如下步骤：
    第一步：在反应容器中将二胺类化合物完全溶解于有机溶剂中，将二酐类化合物分批加入反应容器，反应温度控制-5℃-50℃，搅拌反应5-48小时，得到透明、粘稠状的聚酰胺酸溶液；将所得的聚酰胺酸溶液抽真空1-48小时消除气泡；
    第二步：将聚酰胺酸溶液在双向拉伸聚酰亚胺薄膜生产线上制备薄膜。
  11. 根据权利要求10所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜的制备方法，其特征在于，双向拉伸聚酰亚胺薄膜生产线流延机流延段温度控制范围120℃-220℃。
  12. 根据权利要求10所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜的制备方法，其特征在于，双向拉伸聚酰亚胺薄膜生产线流延机亚胺炉最高温度控制范围300℃-400℃，亚胺化温度升温阶梯10℃-100℃。
  13. 根据权利要求10所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜的制备方法，其特征在于，控制薄膜横向拉伸比1:0.8-1.2,纵向拉伸比1:1.1-1.6。
  14. 根据权利要求9至13任一项所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜的制备方法，其特征在于，所用的有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮或γ-丁内酯，或者以上溶剂中两种以上的混合溶剂。
  15. 一种如权利要求1至8任一项所述的具有阻隔紫外线作用的透明聚酰亚胺薄膜的应用，其特征在于，应用于防紫外线辐射的人体保护服饰、灯具、窗膜，玻璃贴膜，车膜或遮阳用具。
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