WO2021051258A1 - 一种使用偶氮染料的薄膜偏光片的制备方法 - Google Patents

一种使用偶氮染料的薄膜偏光片的制备方法 Download PDF

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WO2021051258A1
WO2021051258A1 PCT/CN2019/106099 CN2019106099W WO2021051258A1 WO 2021051258 A1 WO2021051258 A1 WO 2021051258A1 CN 2019106099 W CN2019106099 W CN 2019106099W WO 2021051258 A1 WO2021051258 A1 WO 2021051258A1
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acid
film
azo
iii
azo dye
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PCT/CN2019/106099
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English (en)
French (fr)
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瓦什琴科·V
郭海成
瓦什琴科·O
蒙翠玲
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香港科技大学
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Priority to CN201980004382.6A priority Critical patent/CN112823297B/zh
Priority to PCT/CN2019/106099 priority patent/WO2021051258A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/02—Disazo dyes
    • C09B33/16—Disazo dyes from other coupling components
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • C09K19/601—Azoic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers

Definitions

  • the invention relates to the technical field of thin film polarizers, in particular to a method for preparing thin film polarizers using azo dyes.
  • polarizer The full name of polarizer is polarizer. It has been used in many optical technologies and instruments and is an important part of various display devices, such as liquid crystal displays (LCD) and organic light emitting diode (OLED) displays. In order to produce thin flexible displays, suitable thin film polarizers are required.
  • LCD liquid crystal displays
  • OLED organic light emitting diode
  • Thin film polarizers can be divided into different types.
  • One is a polymer film polarizer doped with iodine and/or dichroic dyes, which can achieve optical alignment by stretching the film.
  • H-polarizers are widely used.
  • the H-polarizers are made of iodine-containing polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • Such polarizers have the advantages of absorption bandwidth, high dichroism, and relatively low cost.
  • the heat resistance and moisture resistance of iodine are very poor, and the mechanical strength of the film itself is also weak. For this reason, the PVA film must be additionally protected, and triacetyl cellulose is often used as a protective layer. Therefore, the manufacturing process of the polarizer is complicated.
  • PVA-based polarizers may include several dichroic dyes with complementary absorption spectra in the entire visible spectrum instead of iodine. Although the dye material is more heat-resistant and moisture-resistant than iodine, the application of PVA/dichroic dye polarizing film is limited due to its poor polarization.
  • polar PVA film For non-polar dichroic dyes, some people propose to replace polar PVA film with hydrophobic polyolefin film, such as polypropylene or polyethylene-polypropylene copolymer film.
  • hydrophobic polyolefin film such as polypropylene or polyethylene-polypropylene copolymer film.
  • the resulting polarizer is thinner, but its optical properties are not as good as H -Polarizer.
  • coated polarizers which are more stable and thinner than stretched film polarizers.
  • One of the preparation methods of coated polarizers is to use a guest-host system, which is composed of a dichroic dye (guest) and a thermotropic liquid crystal (LC) monomer (host).
  • guest-host nematic liquid crystals
  • LC thermotropic liquid crystal
  • guest-host nematic liquid crystals
  • the polarizer uses a highly ordered smectic-B liquid crystal monomer. However, since it involves the production of liquid crystal cells, the manufacturing process is complicated.
  • LLC lyotropic liquid crystal
  • the most promising method for preparing thin-film polarizers is photo-aligned azo dye film.
  • a photosensitive dichroic dye layer is coated on the substrate, and the dye molecules can be aligned and arranged in an orderly manner under the irradiation of polarized light.
  • Optical alignment technology has been researched and developed in the past 30 years, and is widely used in liquid crystal displays and photonics applications.
  • the present invention is based on the photo-alignment of azo dye molecules, through chemical modification after photo-alignment operation, it solves the problems of narrow absorption band and unstable alignment in the prior art.
  • the method of the present invention prepares The absorption band and stability of the obtained polarizer have been significantly improved.
  • the present invention is realized by adopting the following technical solutions.
  • the present invention provides a method for preparing a thin film polarizer using azo dyes, the method comprising the following steps:
  • At least one azo dye is deposited on the substrate to form an azo film
  • step (ii) photo-aligning the azo film prepared in step (i) to obtain a photo-aligned azo film
  • step (iii) Chemically modify the photo-aligned azo film prepared in step (ii) to obtain.
  • the azo dye is more than one kind.
  • the azo dye is selected from one or more of the compounds of the following molecular formulas:
  • a and C are independently selected from the following rings:
  • X, Y, and Z are independently selected from H, halogen, alkyl (for example, C 1-6 alkyl) and OH;
  • n and n are independently integers between 0 and 2. In the same compound, m and n are not equal to 0 or 2 at the same time.
  • step (i) the azo dye is
  • the azo dye is disclosed in US Pat. No. 8,576,485 B2 as an example of a preferred embodiment.
  • the alkyl end chain of the azo dye is C 4 H 9 , which is called AD-1.
  • other azo dyes can also be used.
  • the substrate is a polymer flexible substrate or glass.
  • the deposition is performed by spin coating, vacuum deposition, printing, spraying or other techniques.
  • the optical alignment is obtained by using linearly polarized light irradiation, wherein the choice of the wavelength of the linearly polarized light depends on the azo dye material.
  • step (ii) the linearly polarized light passes through a shadow mask to form patterned polarized light.
  • step (iii) the chemical modification is modified by chemical vapor deposition technology.
  • step (iii) the chemical modification is carried out in a solution containing a chemical modifier or a derivative thereof.
  • the chemical modifier is an acid or an acid derivative, and the acid or acid derivative can protonate the molecule of the azo dye.
  • the chemical modifier is an acid or a mixture of acid derivatives.
  • the acid is selected from hydrogen halide acid, nitric acid, sulfuric acid, phosphoric acid, aryl sulfonic acid, alkyl sulfonic acid, halogenated sulfonic acid, and halogen-containing carboxylic acid.
  • the concentration of the acid is 10v/v% to 40v/v%;
  • the temperature of the acid is 30°C to 80°C;
  • the modification time of the chemical modification is 15 to 40 minutes, preferably 25 to 37 minutes.
  • the acid derivative is an acid anhydride, including but not limited to trifluoroacid anhydride (1 v/v% trifluoromethanesulfonic anhydride).
  • the chemical modifier is an acid halide.
  • the chemical modifier is an ester.
  • the chemical modifier is acid trimethylsilyl ester, preferably, the acid trimethylsilyl ester is trimethylsilyl trifluoromethanesulfonate.
  • the chemical modifier is an acidic oxide; preferably, the acidic oxide is NO 2 , N 2 O 4 or SO 3 .
  • the chemical modifier is one or more of the derivatives of the general formula R t EX 4-t , wherein R is an alkyl group (for example, a C 1-6 alkyl group) or an alkoxy group ( For example, C 1-6 alkoxy group), E is selected from Si, Sn, Ti, X is a halogen atom, and t is an integer from 0 to 4.
  • the chemical modifier is Me 2 SiCl 2 .
  • the chemical modifier is MeSiCl 3 .
  • the chemical modifier is (C 2 H 5 O) 4 Si.
  • the thin film polarizer is a multilayer film.
  • the multilayer film is realized by repeating steps (i)-(iii) after completing steps (i)-(iii) (being a layer of film).
  • the multilayer film is realized by repeating step (i) after completing steps (i)-(iii).
  • the multilayer film is realized by repeating steps (i) and (iii) (that is, further depositing an azo dye and performing chemical modification) after completing steps (i)-(iii).
  • the method further comprises: (iv) depositing a polymer on the product obtained after step (iii) chemical modification; and, optionally, (v) after step (iv), polymerizing the polymer Things.
  • the polymer is a liquid crystal polymer, such as an acrylic polymer.
  • the invention discloses a method for preparing a broadband film polarizer from a high dichroic azo dye (which is resistant to further irradiation).
  • the first two steps of the three main steps of the present invention i.e. steps (i), (ii) and (iii)
  • steps (i), (ii) and (iii)) are photo-alignment by using polarized light irradiation after depositing the azo dye.
  • steps (i), (ii) and (iii) are photo-alignment by using polarized light irradiation after depositing the azo dye.
  • the present invention uses a protonating agent (an acid or a derivative capable of generating an acid on the surface of the film) to treat the membrane.
  • the starting azo dyes are also called neutral dyes.
  • the azo dye has the following general structure:
  • a and C are independently selected from the following rings:
  • X, Y, and Z are independently selected from H, halogen, alkyl and OH;
  • n and n are independently integers between 0 and 2. In the same compound, m and n are not equal to 0 or 2 at the same time.
  • the alkyl end chain is C 4 H 9 , which is referred to as AD-1 herein.
  • Other azo dyes can also be aligned with polarized light.
  • the concept of light stabilization is based on the following hypothesis: the photo-induced process of EZ-isomerization of azo dyes (also called cis-trans) is the main reason for the rotation of azo dye molecules (or aggregates), which leads to the final Preferably, the alignment is perpendicular to the light polarization plane. This is the process of light-induced rotation (PR). When the absorbing dipole is perpendicular to the direction of light polarization, the molecular rotation will stop. According to the present invention, preventing (or severely hindering) any chemical modification of the E-Z-isomerized azo dye molecules will also prevent any further rotation of the azo dye, thereby stabilizing the already aligned layer. This is the process of chemical modification and stabilization.
  • FIG. 2 A preferred device for chemical modification of the polarizing film for photo-alignment is schematically shown in FIG. 2.
  • the film polarizer sample is placed in a chamber for chemical modification and processing, the humidity, temperature, and pressure of the chamber are controlled.
  • the temperature of the azo dye-containing substrate is determined by the properties of the azo dye and should not exceed the limit of its dichroic stability. Therefore, when using AD1 (see Figure 1), the temperature should not be higher than 150°C, preferably 80°C.
  • auxiliary chemical reagents should be used to release free acid.
  • water preferably in the gas phase
  • auxiliary chemical agent is such an auxiliary chemical agent.
  • the concentration of the acid or its derivative is determined by weighing the film thickness and the film quality (defects, crack formation, etc.), which depends on the diffusion rate of the acid through the film and the properties of the azo dye.
  • the preferred chemical modification rate is determined by experiment, such as Example 11.
  • step (e) Since the chemical modifier is an acid or acid derivative, and the working material is a protonated azo dye, in step (iii), the unprotected membrane, and in optional steps (iv, v), must Avoid alkaline reagents that can neutralize protonated azo dyes.
  • alkaline reagents are: alkyl groups of arylamines, inorganic bases, dimethylformamide, dimethylsulfoxide.
  • chemical modification refers to treatment with an acid or its derivative (which can generate an acid, such as an acid anhydride, under an appropriate reaction, and simultaneously or sequentially treated with water, preferably but not limited to in the gas phase) to obtain protonation
  • an acid or its derivative which can generate an acid, such as an acid anhydride, under an appropriate reaction, and simultaneously or sequentially treated with water, preferably but not limited to in the gas phase
  • the form of azo dyes has expanded absorption in the VIS and NIR-1 regions and cannot be rearranged by further optical alignment.
  • the acid should be strong enough to be able to protonate the azo dye; the pKa value of the acid is determined by the alkalinity of the azo dye, see Heinrich Zollinger, Color Chemistry Synthesis, Properties, and Applications of Organic Dyes and Pigments, Third, revised edition WILEY-VCH, 2003, pp.637.
  • the chemical modification When an acid is used as a chemical modifier, it is called protonation.
  • the chemical modification also has the following advantages: the azo dyes usually used for thin film preparation show relatively narrow absorption in the blue spectral region, while in the protonated form they show broad absorption and red-shifted absorption in the visible spectral region. , See Heinrich Zollinger, Color Chemistry Synthesis, Properties, and Applications of Organic Dyes and Pigments, Third, revised editionWILEY-VCH, 2003, pp. 637 and PFGordon and P. Gregory, Organic and Chemistry business in colour, Spring 2012, pp.322.
  • the following substances or their mixtures can be used, including but not limited to: halogenated hydrogen acid, nitric acid, sulfuric acid, phosphoric acid, aryl sulfonic acid, alkyl sulfonic acid, halogenated sulfonic acid, and halogen-containing carboxylic acid.
  • a chemical modifier in the gas phase for chemical development, but it is not limited to this.
  • an appropriate solvent to dissolve the acid or its derivative for further azo dye film treatment. Basically, the solvent should neither dissolve the starting azo dye nor its modified form.
  • these solvents include saturated hydrocarbons such as hexane, heptane, octane or mixtures thereof.
  • the modified membrane with an additional layer of polymer material.
  • a non-limiting list of the polymer materials is: polyacrylate, epoxy, silicone.
  • the polymer is used as an already polymerized material or is prepared according to step (iv-v).
  • the polymer material it may be a liquid crystal polymer, such as an acrylic polymer.
  • the substrate of the azo dye film is used as the protective layer: any suitable polymer described above is used to bond the two films, see Example 14.
  • acid derivatives can also be used instead of free acids, which can react with the azo dye or water adsorbed on the surface to generate the protonated form of the azo dye.
  • acid derivatives are: acid anhydrides (e.g., trifluoro acid anhydride, sulfuric anhydride), acid halides (e.g., p-toluenesulfonyl chloride), esters (e.g., dialkyl sulfate, trisilyl trifluoromethanesulfonate ), nitrite sulfate, acidic oxides, such as NO 2 , N 2 O 4 and SO 3 .
  • acid anhydrides e.g., trifluoro acid anhydride, sulfuric anhydride
  • acid halides e.g., p-toluenesulfonyl chloride
  • esters e.g., dialkyl sulfate, trisilyl trifluoromethanesulfonate
  • nitrite sulfate acidic oxides, such as NO 2 , N 2 O 4 and SO 3 .
  • the acid or its derivative can be used in the form of a solution at an optimal concentration in an appropriate solvent.
  • the chemical solution can flow through the thin polarizer sample, or the thin polarizer sample can be immersed in a chemical bath.
  • a sufficiently thick initial azo dye film should be used.
  • the film thickness can be achieved at one time when the azo dye film is deposited, or can be achieved by multi-layer deposition, as in Example 16.
  • the chemical modification can be applied to the final deposited azo dye film with the desired thickness using the following general schemes, and can also be applied to each intermediate azo dye layer:
  • a mixture of azo dyes that absorb in different spectral regions can be used, which can be neutral or protonated.
  • the mixed dyes can be deposited as a mixture in a common layer, or can be deposited sequentially layer by layer. In the latter case, sequential chemical treatment is very beneficial because the protonated azo dyes have higher polarity, so their solubility in low-polar solvents is reduced compared to neutral azo dyes. Therefore, every subsequent deposition of the neutral azo dye will basically not dissolve the protonated azo dye in the previous layer.
  • each previous chemically modified layer can be used as the alignment layer of the neutral azo dye in the next layer.
  • the amount of acidic reagent absorbed by the former layer is sufficient to partially protonate the neutral azo dyes of the latter layer. Therefore, in the above case, an additional alignment step can be omitted.
  • ⁇ // and ⁇ ⁇ are the absorption coefficients in parallel and perpendicular directions, respectively.
  • T // and T ⁇ are the transmittances in parallel and perpendicular directions, respectively.
  • the anti-light stability of the polarizer was tested by laser irradiation.
  • the optical quality of the film was evaluated by surface roughness, uniformity and blur.
  • the width of the transmission peak is characterized by the full width at half maximum (FWHM), and the unit is nm.
  • the manufacturing method of this polarizer includes the following steps:
  • a substrate such as a polymer flexible substrate or glass.
  • the deposition method can be spin coating or vacuum deposition or printing or spraying or other techniques.
  • a protective layer is deposited on the surface of the chemically modified photo-alignment film.
  • An example of a protective layer is that reactive monomers are then polymerized.
  • the photo-alignment of the deposited film and subsequent chemical modification and final packaging protection can be carried out in the same room or in different rooms as required.
  • the present invention discloses a thin film absorbing polarizer (including a patterned film) using azo dyes for visible light and near-infrared -1 zone and a preparation method thereof.
  • the dichroic ratio (DR) of the film of the present invention is greater than 30.
  • the thickness of the film can vary from tens to thousands of nanometers, depending on the optical density required by the film.
  • the DR of the film is resistant to random polarized light irradiation.
  • the chemical modification of the present invention includes treatment with an acid or its derivative (which can generate an acid through a suitable reaction, such as preferably but not limited to simultaneous or sequential treatment of anhydride with water in the gas phase) to obtain a protonated form of the azo dye, It has expanded absorption in the visible and near-infrared-1 regions and will not be reorientated by further optical alignment.
  • a suitable reaction such as preferably but not limited to simultaneous or sequential treatment of anhydride with water in the gas phase
  • Figure 1 shows the AD-1 molecule
  • Figure 2 Air cell for chemically modified polarizer film
  • Figure 3 Air chamber for chemically modifying polarizer film with control of temperature and pressure of chemical modifier
  • Figure 4 shows the spectrum of AD-1 film before and after the light stability test
  • FIG. 5 The spectrum of AD-1 film before (A) and after (B) treatment with trifluoromethanesulfonic anhydride
  • Figure 6 The spectrum of AD-1 film treated with trifluoromethanesulfonic anhydride before (A) and after (B) the stability test against sunlight and polarized light radiation;
  • Figure 7 Cracks shown on samples treated with nitric acid (aqueous nitric acid solution above 69v/v%) in the gas phase;
  • Figure 8 Spectra of AD-1 film before (A) and after (B) treatment with nitric acid
  • Figure 10 Spectral evolution of AD-1 film during development in a gas chamber containing Tf 2 O vapor, and A
  • Figure 11 Spectra of the incompletely modified AD-1 film before the light stability test (A) and after the test (B);
  • Figure 12 The spectrum of AD-1 film after treatment with sulfuric acid
  • Figure 13 Spectra of AD-1 film treated with sulfuric acid before and after the light irradiation test.
  • Figure 14 Spectra of AD-1 film with protective layer (A) and without protective layer (B) after 10 days under environmental conditions.
  • AD-1 used in the following examples is
  • alkyl end chain is C 4 H 9 .
  • Example 1 Preparation of neutral azo film by spin coating technology
  • the glass substrate was washed with water and surfactant, dried and activated in an ozone chamber for 20 minutes.
  • One drop of 1-8% AD-1 toluene solution was spin-coated onto the substrate at a speed of 3000 rpm, and then rotated for 30 seconds. After that, the film was soft baked at 70°C for 5 minutes.
  • the AD will be obtained -1
  • the film is subjected to optical alignment treatment with linearly polarized light.
  • the wavelength of the light source is 450nm.
  • Example 2 Preparation of neutral azo film by vapor vacuum deposition technology
  • the dye is deposited on clean bare glass or other substrates (20mm ⁇ 20mm) under a base pressure of 1 ⁇ 10 -6 mbar in a high vacuum.
  • AD-1 starts to evaporate at about 140°C, and the deposition rate is controlled to A constant value within the range of, which is monitored by the quartz membrane. Verify the final thickness of the film with a profiler.
  • the light intensity of linearly polarized light is fixed at 30 mW/cm 2 .
  • the deposition and in-situ optical alignment start simultaneously, and both stop when the thickness reaches 200nm.
  • the film was chemically modified by treatment with a chemical modifier.
  • Example 4 Chemical modification of membranes in the vapor phase of trifluoromethanesulfonic anhydride in a closed container
  • the membrane was processed by treating the aligned AD-1 sample (obtained according to Example 1) with trifluoromethanesulfonic anhydride (1v/v% trifluoromethanesulfonic anhydride in n-octane solution) in the gas phase Chemical modification, samples are taken regularly under environmental conditions to monitor the spectrum and dichroic ratio. When the maximum dichroic ratio is reached, the total exposure time is approximately 5 minutes. The evolution of the absorption spectrum is shown in Figure 5.
  • Example 6 Chemical modification of membranes in the gas phase of nitric acid (concentrated acid, high chemical modification rate)
  • Example 1 an aligned AD-1 film sample was prepared.
  • the film is chemically modified by treatment in the gas phase of nitric acid (69v/v% nitric acid aqueous solution), and the spectrum and dichroic ratio are regularly monitored.
  • nitric acid 69v/v% nitric acid aqueous solution
  • the spectrum and dichroic ratio are regularly monitored.
  • Figure 7 after the sampler was exposed for 30 seconds, the sample had cracks due to the excessively high chemical modification rate.
  • Example 7 Chemical modification of membrane in the gas phase of nitric acid (dilute acid, slower chemical modification rate)
  • Example 1 an aligned AD-1 film sample was prepared.
  • the membrane is chemically modified by treatment with an aqueous nitric acid solution in the gas phase.
  • HNO 3 is further diluted to a lower concentration of 40 v/v% to 10 v/v%.
  • the total exposure time depends on the acid concentration and is approximately 1.7 minutes for 40 v/v% and approximately 15 minutes for 10 v/v%.
  • the change of the absorption spectrum after chemical modification is shown in Figure 8. It can be seen that after protonation, the absorption spectrum extends to the red region again while maintaining the dichroic ratio. In addition, no cracks were shown on the film.
  • a protective layer ie, acrylic polymer
  • cover the sample with acrylic UV glue, and then polymerize under UV light ( ⁇ 365nm, 20mW/cm 2 ) for 3 minutes to form a strong film. This shows that the film covered with the protective layer is quite stable for at least two weeks.
  • Example 8 Chemical modification of AD-1 film by treatment in the gas phase of trifluoroacetic acid (TFA); test of volatile acid.
  • TFA trifluoroacetic acid
  • a sample of the aligned AD-1 film was prepared according to Example 1.
  • the chemical modification procedure is basically the same as that used in Example 7.
  • the maximum dichroic ratio is reached, the total exposure time to trifluoroacetic acid vapor is approximately 1 minute.
  • the spectrum of the modified AD-1 gradually changed back, and after about 30 minutes, the original spectrum was completely restored, DR ⁇ 15-16.
  • the protective layer ie, acrylic polymer
  • the film covered with the protective layer is stable for at least two weeks.
  • Example 9 Chemical modification of AD-1 membrane by in the gas phase of acetic acid (AcOH): weak acid test
  • Example 1 an aligned AD-1 film sample was prepared.
  • the chemical modification procedure is basically the same as that used in Example 7.
  • the total exposure time of AcOH vapor is about 20 minutes. No substantial change in the color of the film during this period was observed.
  • Example 10 The chemical modification of the membrane was carried out by treating with trifluoromethanesulfonic anhydride in a special gas chamber, and continuously monitoring the modification process through UV-Vis spectroscopy and DR detection
  • Example 11 As shown in Example 10, the membrane was chemically modified by treatment with trifluoromethanesulfonic anhydride in a special air chamber, and the time required to complete the protonation of the membrane was tested.
  • Example 10 Except for the total duration of the process (modification is terminated after 4 cycles), a method similar to that described in Example 10 was used to form an AD-1 oriented film sample.
  • the dichroic ratio of the film is 42.
  • Example 12 Chemical modification of membranes in sulfuric acid gas phase at atmospheric pressure (low volatile acid test)
  • the aligned AD-1 film sample was prepared according to Example 1, and the DR was 63.
  • the chemical modification of the membrane is carried out in a chamber ( Figure 3) at atmospheric pressure. At ambient temperature, nothing happens. After heating the acid to 180°C, the red color of the azo dye turns to dark blue, and the azo dye is collected in the form of separated small droplets.
  • the DR in the membrane area is changing, and the maximum DR value is less than 6.
  • Example 13 The membrane was chemically modified in the sulfuric acid gas phase under low pressure (low volatile acid test, high chemical modification rate).
  • the aligned AD-1 film sample was prepared according to Example 1, and the DR was 60.
  • the chemical modification of the membrane is carried out in a chamber ( Figure 3) at a pressure of 0.25 mbar.
  • the temperature of the acid is 100°C.
  • the azo dye film was exposed for 1 minute, the color changed to dark blue, and the film had many defects and cracks.
  • the DR in the membrane area is changing, and the maximum DR value is less than 5.
  • Example 14 Chemical modification of the membrane in the sulfuric acid gas phase at low pressure (low volatile acid test, reduced chemical modification rate).
  • the aligned AD-1 film sample was prepared according to Example 1, and the DR was 25.
  • the chemical modification of the membrane is carried out in a chamber ( Figure 3) at a pressure of 0.25 mbar.
  • the exposure time of the azo dye film depends on the temperature of the acid, so it ranges from 6 minutes at 80°C to 30 minutes at 30°C. After the azo dye film was exposed for 8 minutes, the color changed to gray blue, and no defects or cracks were observed on the film (as shown in Figure 12).
  • DR is 14.
  • the AD-1 membrane samples treated with sulfuric acid were stored under ambient conditions in sunlight for 7 days.
  • the sample was irradiated with unpolarized light (including 405 nm and 365 nm, with a total intensity of 67 mW/cm 2 ), and the amount of light was 200 J/cm 2 .
  • the angle between the light polarization and the initial orientation of AD-1 is 45°.
  • the spectral evolution is shown in Figure 13. The results showed that no significant changes were observed.
  • the photo-alignment sample of AD-1 is stable to strong light irradiation, and it is also stable to environmental conditions.
  • Example 15 Reliability test of modified film without protective layer and protective layer.
  • Two AD-1 membrane samples treated with trifluoromethanesulfonic anhydride were prepared as described in Example 4.
  • One of the modified films is bare and not covered with any protective layer.
  • the two samples were stored under ambient conditions for 10 days.
  • Figure 14 (A) and (B) the samples covered with the protective layer are much stronger than the bare samples.
  • the spectrum of the protected sample after 10 days showed no change, however, the sample without any protective layer was significantly degraded, that is, the contrast became worse.
  • Example 16 A multilayer polarizer (polarizing film) prepared by sequentially depositing/chemically modifying AD1 with trifluoromethanesulfonic anhydride/water in a special airflow chamber
  • the first layer of the chemically modified AD-1 alignment film was prepared substantially as described in Example 10.
  • the average DR from 450 nm to 700 nm is 24, and the CR is 217, as shown in FIG. 15.
  • the second layer of AD-1 was deposited by spin-coating a 4% w/w solution of AD-1 in toluene similar to that described in Example 1.
  • the absorption spectrum of the formed film is shown in FIG. 15.
  • the increase in absorbance in the range of 400-520 nm clearly confirms that part of the AD-1 material in the second layer is oriented and some parts are not.
  • the film was additionally oriented with linearly polarized light so that the remaining unoriented AD-1 was completely oriented, as shown in FIG. 16.

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Abstract

提供一种使用偶氮染料的薄膜偏光片的制备方法，该方法包括如下步骤：(i)将至少一种偶氮染料沉积到基底上，形成偶氮膜；(ii)使步骤(i)制备得到的偶氮膜光配向，以得到光配向的偶氮膜；以及(iii)对步骤(ii)制备得到的光配向的偶氮膜进行化学改性，即得。薄膜偏光片在强烈的非偏振光照射和各种环境条件下保持稳定。

Description

一种使用偶氮染料的薄膜偏光片的制备方法 技术领域
本发明涉及薄膜偏光片技术领域，具体涉及一种使用偶氮染料的薄膜偏光片的制备方法。
背景技术
偏光片的全称是偏振光片，目前已经被应用于许多光学技术和仪器中，是各种显示设备，如液晶显示器(LCD)和有机发光二极管(OLED)显示器中重要的组成部分。为了生产薄的柔性显示器，需要适宜的薄膜偏光片。
薄膜偏光片可以分为不同的类型。一种是掺杂有碘和/或二色性染料的聚合物膜偏光片，该偏光片通过拉伸薄膜可以实现光配向。目前，广泛使用的是H-偏光片，该H-偏光片由含碘聚乙烯醇(PVA)制成，这种偏光片具有吸收带宽、二向色性高和成本相对低廉的优点。然而，碘的耐热性和抗湿性都很差，该薄膜本身的机械强度也很弱，为此，该PVA膜必须另外进行保护，常常使用三乙酰纤维素作为保护层。因此，该偏光片的制造工艺复杂，更重要的是，这种偏光片相当厚，厚度通常在200μm左右，该厚度无法满足薄和超薄显示器应用的要求。此外，这种偏光片不适用于高分辨率制图。这种偏光片的另一个缺点与拉伸偏光膜的高收缩力有关，这会导致诸如面板弯曲、面板变形和尺寸变化以及不均匀性等许多问题。为了实现中性灰色，基于PVA的偏光片可以包括在整个可见光谱区域内具有互补吸收光谱的若干二色性染料来替代碘。尽管染料材料比碘更耐热、更耐潮，但是由于偏光性差的特点使得PVA/二色性染料偏光膜的应用受到限制。对于非极性二色性染料，有人提议以疏水性聚烯烃膜，如聚丙烯或聚乙烯-聚丙烯共聚物膜替代极性PVA膜，这样得到的偏光片较薄，但其光学性能不如H-偏光片。
另一种基于二色性染料的偏光片技术是涂覆式偏光片，这样的偏光片比拉伸膜偏光片更稳定、更薄。涂覆式偏光片的制备方法之一是采用客体-主体系统，该系统由二色性染料(客体)和热致液晶(LC)单体(主体)组成。 具体而言，在向列型液晶(LC)中“客-主”效应使其可能获得高达14的二向色性比，但这对于实际应用来说还不够高。另外，由于主体中染料含量不超过2-3％，导致薄膜过厚。已经显示一种5μm厚的高对比度的偏光片，该偏光片中使用了高有序的近晶型-B液晶单体，然而，由于涉及液晶盒的制作，因此，制造工艺复杂。
另一种制造涂覆式偏光片的方法是基于使用溶致液晶(LLC)系统。已经报道了一种以溶致液晶为主体、厚度小于1μm的偏光片，然而，这些偏光片的二向色性比不是很高，通常不超过30。溶致液晶的水溶性对偏光片的稳定性也提出了挑战。
制备薄膜偏光片(包括带有图案的偏光片)最有希望的方法是光配向偶氮染料膜。在该方法中，基底上涂覆有光敏二色性染料层，该染料分子在偏振光照射下可以配向并有序排列。光配向技术在过去30年中得到了研究和发展，并广泛用于液晶显示器和光子学应用。
现有技术(ACS Appl.Mater.Interfaces,2016,8,762-771；Photoalignment of liquid crystalline materials:physics and applications；和WO2011045959 A1)已经报道基于偶氮染料和溶致或热致液晶开发了带有图案的偏光片的光配向方法，然而，该方法制备的偏光片的二向色性比不超过20，通过高纯度的AD-1偶氮染料的光配向获得高二向色性(DR＝50及更高)和极薄(厚度在100-300nm范围内，高达500nm)的偏光片膜。但是这种染料只在蓝色区域有吸收，因此该偏光片不是宽谱带的，这种光配向薄膜偏光片的另一个问题是，即使使用聚合物保护，暴露在非偏振光下时仍然不稳定，且染料分子会重新取向。
发明内容
为了克服现有技术的缺陷，本发明基于偶氮染料分子的光配向，通过光配向操作后的化学改性，解决了现有技术吸收谱带窄及配向不稳定的问题，本发明的方法制备得到的偏光片的吸收谱带和稳定性都得到了明显的改善。
本发明是采用如下技术方案来实现的。
本发明提供一种使用偶氮染料的薄膜偏光片的制备方法，该方法包括如 下步骤：
(i)将至少一种偶氮染料沉积到基底上，形成偶氮膜；
(ii)使步骤(i)制备得到的偶氮膜光配向，以得到光配向的偶氮膜；以及
(iii)对步骤(ii)制备得到的光配向的偶氮膜进行化学改性，即得。
优选地，在步骤(i)中，所述偶氮染料为一种以上。
优选地，在步骤(i)中，所述偶氮染料选自以下分子式的化合物中的一种或多种：
Figure PCTCN2019106099-appb-000001
其中，R 1和R 2独立地选自H、烷基(例如C 1-6的烷基)、烯基(例如C 2-6的烯基)、-C kH 2k-OC(O)C＝CH 2和-C lH 2l-OC(O)C(CH 3)＝CH 2，其中k和l独立地为1至12的整数，优选为1至6的整数；
A、C相互独立地选自以下所列的环：
Figure PCTCN2019106099-appb-000002
其中，X、Y、Z独立地选自H、卤素、烷基(例如C 1-6的烷基)和OH；
B选自：单键、-C＝C-双键、-COO-、-OCO-、-N＝N-和-CH 2O-；
m、n独立地为0到2之间的整数，在相同的化合物中，m和n不同时等于0或2。
优选地，在步骤(i)中，所述偶氮染料为
Figure PCTCN2019106099-appb-000003
该偶氮染料在美国专利US8,576,485B2公开了，用作优选实施方案的例子，该偶氮染料中烷基端链为C 4H 9，称为AD-1。在本申请中，也可以使用 其他的偶氮染料。
优选地，在步骤(i)中，所述基底为聚合物柔性基底或玻璃。
优选地，在步骤(i)中，所述沉积通过旋涂、真空沉积、印刷、喷涂或其他技术来进行。
优选地，在步骤(ii)中，所述光配向通过使用线偏振光照射来获得，其中线偏振光的波长的选择取决于偶氮染料材料。
优选地，在步骤(ii)中，所述线偏振光通过阴影遮罩形成带有图案的偏振光。
优选地，在步骤(iii)中，所述化学改性是通过化学气相沉积技术进行改性。
优选地，在步骤(iii)中，所述化学改性是在含有化学改性剂或其衍生物的溶液中进行的。
优选地，所述化学改性剂为酸或酸衍生物，所述酸或酸衍生物能够使所述偶氮染料的分子质子化。
优选地，所述化学改性剂为酸或酸衍生物的混合物。
优选地，所述酸选自卤化氢酸、硝酸、硫酸、磷酸、芳基磺酸、烷基磺酸、卤代磺酸和含卤羧酸。
优选地，所述酸的浓度为10v/v％至40v/v％；
优选地，所述酸的温度为30℃至80℃；
优选地，在步骤(iii)中，所述化学改性的改性时间为15至40分钟，优选为25至37分钟。
优选地，所述酸衍生物是酸酐，包括但不限于三氟酸酐(1v/v％三氟甲磺酸酐)。
优选地，所述化学改性剂为酰卤。
优选地，所述化学改性剂为酯。
优选地，所述化学改性剂为酸的三甲基硅烷酯，优选地，所述酸的三甲基硅烷酯为三氟甲磺酸三甲基硅酯。
优选地，所述化学改性剂为酸性氧化物；优选地，所述酸性氧化物是NO 2、N 2O 4或SO 3。
优选地，所述化学改性剂是通式为R tEX 4-t的衍生物中的一种或多种，其中R是烷基(例如C 1-6的烷基)或烷氧基(例如C 1-6的烷氧基)，E选自Si、Sn、Ti，X是卤素原子，并且t是0到4的整数。
优选地，所述化学改性剂是Me 2SiCl 2。
优选地，所述化学改性剂是MeSiCl 3。
优选地，所述化学改性剂是(C 2H 5O) 4Si。
优选地，所述薄膜偏光片为多层膜。
优选地，所述多层膜通过在完成步骤(i)-(iii)后(为一层膜)，重复步骤(i)-(iii)来实现。
优选地，所述多层膜通过在完成步骤(i)-(iii)后，重复步骤(i)来实现。
优选地，所述多层膜通过在完成步骤(i)-(iii)后，重复步骤(i)和(iii)(即进一步沉积偶氮染料，并且进行化学改性)来实现。
优选地，所述方法还包括：(iv)将聚合物沉积在步骤(iii)化学改性后获得的产品上；以及，任选地，(v)在步骤(iv)后，聚合所述聚合物。
优选地，所述聚合物为液晶聚合物，例如丙烯酸聚合物。
以下将对本发明进行详细的描述。
本发明公开一种由高二色性偶氮染料(其耐进一步的照射)来制备宽带薄膜偏振片的方法。本发明的三个主要步骤(即步骤(i)、(ii)和(iii))中的前两个步骤是通过沉积偶氮染料后，使用偏振光照射进行光配向。为了稳定光配向的偶氮染料层，避免其例如，在环境光照射下发生任何进一步的光促再配向，本发明采用质子化剂(酸或能够在膜表面产生酸的衍生物)处理所述膜。起始偶氮染料也称为中性染料。
在本发明中，所述的偶氮染料具有以下通式结构：
Figure PCTCN2019106099-appb-000004
其中R 1和R 2独立地选自H、烷基、烯基、-C kH 2k-OC(O)C＝CH 2和–C lH 2l-OC(O)C(CH 3)＝CH 2，其中k和l均为1至12的整数，优选为1至6 的整数；
A、C相互独立地选自以下所列的环：
Figure PCTCN2019106099-appb-000005
其中，X、Y、Z独立地选自H、卤素、烷基和OH；
B选自：单键、-C＝C-双键、-COO-、-OCO-、-N＝N-和-CH 2O-；
m、n独立地为0到2之间的整数，在相同的化合物中，m和n不同时等于0或2。
更具体地，可以采用美国专利号US8576485B2中公开的偶氮染料，其分子式为：
Figure PCTCN2019106099-appb-000006
其中烷基末端链是C 4H 9，本文称为AD-1。其他的偶氮染料也可以用偏振光进行光配向。
光稳定化的构思是基于以下假设：偶氮染料的EZ-异构化(也称为顺-反)的光诱导过程是偶氮染料分子(或其聚集体)旋转的主要原因，这导致最终优选垂直于光偏振面进行配向。这是光诱导旋转(PR)的过程。当吸收偶极子垂直于光偏振方向时，分子旋转将停止。根据本发明，防止(或严重阻碍)所述E-Z-异构化的偶氮染料分子的任何化学改性也将阻止偶氮染料的任何进一步旋转，从而稳定已经配向的层。这是化学改性和稳定化的过程。
用于光配向的偏振膜的化学改性的优选装置示意性地显示在图2中。在沉积步骤(步骤(i))和光配向步骤(步骤(ii))之后，将膜偏振片样品放置在用于化学改性和处理的室内，该室的湿度、温度和压力受到控制。
在化学改性期间，需要控制如下条件：
(a)含偶氮染料的基底的温度由偶氮染料的性质决定，不应超过其二 色性稳定性的限度。因此，在使用AD1(参见图1)时，温度不应高于150℃，优选为80℃。
(b)在使用单个酸作为化学改性剂的情况下，气室(见图2)内酸的温度和压力由酸的挥发性和所需的化学改性率决定。
(c)在应用酸衍生物的情况下，应使用辅助化学试剂来释放游离酸。在使用酸酐的情况下，水(优选在气相中)是这样的辅助化学试剂。
(d)酸或其衍生物的浓度通过权衡膜厚度和膜质量(缺陷，裂缝的形成等)来确定，这依赖于酸穿过膜的扩散速率和偶氮染料的性质。对于基底与其厚度的特定组合，优选的化学改性率由实验确定，例如实施例11。
(e)由于化学改性剂是酸或酸衍生物，工作材料是质子化偶氮染料，在步骤(iii)中，未受保护的膜，以及在任选步骤(iv，v)中，必须避免能够中和质子化的偶氮染料的碱性试剂。这些碱性试剂的非限制性实例是：芳基胺的烷基，无机碱，二甲基甲酰胺，二甲基亚砜。
在本发明中，化学改性是指以酸或其衍生物(其能够在适当的反应下产生酸，例如酸酐，同时或依次用水处理，优选但不限于在气相中)进行处理以得到质子化的偶氮染料的形式，在VIS和NIR-1区域具有扩大的吸收，并且不能通过进一步的光配向重新排列。酸应该足够强以便能够质子化偶氮染料；酸的pKa值由偶氮染料的碱度决定，合适的常数参见Heinrich Zollinger,Color Chemistry Syntheses,Properties,and Applications of Organic Dyes and Pigments,Third,revised edition WILEY-VCH,2003,pp.637。
当酸用作化学改性剂时，称为质子化。该化学改性还具有如下优点：通常用于薄膜制备的偶氮染料在蓝色光谱区域中显示相对窄的吸收，而以质子化形式存在时在可见光谱区域中显示宽的吸收和红移吸收，参见Heinrich Zollinger,Color Chemistry Syntheses,Properties,and Applications of Organic Dyes and Pigments,Third,revised editionWILEY-VCH,2003,pp.637和P.F.Gordon and P.Gregory,Organic Chemistry in colour,Springer science and business media,2012,pp.322。对于酸，可以使用以下物质或它们的混合物，包括但不限于：卤化氢酸、硝酸、硫酸、磷酸、芳基磺酸、烷基磺酸、卤代磺酸，含卤素羧酸。
进行这样的改性是重要的，以至于不会严重破坏在步骤(i)-(ii)中获得的已经配向的偶氮染料的顺序。为了满足上述条件，优选在气相中使用化学改性剂进行化学显影，但不限于此。在某些情况下，还可能使用适当的溶剂溶解酸或其衍生物，用于进一步的偶氮染料的膜处理。溶剂基本上既不应该溶解起始偶氮染料，又不应该溶解其改性形式。这些溶剂的非限制性实例包括饱和烃，如己烷、庚烷、辛烷或其混合物。
为了避免化学改性过程的逆反应，或为了防止化学改性剂蒸发，可以应用以下措施(或其组合)：
-使用低挥发性(低蒸气压)的酸，以减慢逆反应或蒸发，参见实施例4、10、13和7、8。
-使用强酸以确保偶氮染料分子的完全质子化，参见实施例7、8、10、13和19。
-用额外的聚合物材料层覆盖改性膜。所述聚合物材料的非限制性列表是：聚丙烯酸酯、环氧树脂、硅树脂。聚合物作为已经聚合的材料来使用，或者根据步骤(iv-v)来制备。对于聚合物材料，可以为液晶聚合物，例如丙烯酸聚合物。在一个具体情况下，偶氮染料膜的基底被用作保护层：使用上述任何合适的聚合物粘合两个薄膜，参见实施例14。
最后一个操作，由于酸的低挥发性，自然也会严重地减慢直接反应(质子化)。为了加速化学改性，还可以使用酸的衍生物来替代游离酸，其能够与吸附在其表面上的偶氮染料或水发生反应，生成偶氮染料的质子化形式。这种酸衍生物的例子为：酸酐(例如，三氟酸酐、硫酸酐)、酰卤(例如，对甲苯磺酰氯)、酯(例如，二烷基硫酸酯、三氟甲磺酸三甲硅烷酯)、硫酸亚硝酸酯、酸性氧化物，例如NO 2、N 2O 4和SO 3。
为了精细调节化学改性率，所述酸或其衍生物可以以溶液形式、在适当溶剂中以最佳浓度使用。化学溶液能够流动穿过薄偏光片样品，或者薄偏光片样品能够浸入化学浴中。
为了获得高光密度的偏光片，应该使用足够厚的初始偶氮染料膜。所述膜厚度可以在偶氮染料膜沉积时一次性达到，或者通过多层沉积达到，如实施例16。化学改性可以使用以下通用方案应用于具有所需厚度的最终沉积的 偶氮染料膜上，也可以应用于每个中间偶氮染料层上：
-第一偶氮染料层沉积
-所述第一偶氮染料层的化学改性
-第二偶氮染料层沉积
-如果需要，光配向第二偶氮染料层
-所述第二偶氮染料层的化学改性……等，直到达到期望光密度的膜。
为了覆盖整个可见光谱范围，可以采用在不同光谱区域有吸收的偶氮染料混合物，可以是中性的，也可以是质子化的。所述混合染料可以作为混合物沉积在一个共同的层中，也可以分别顺序逐层沉积。对于后一种情况，顺序化学处理很有益处，因为质子化偶氮染料具有更高的极性，于是与中性偶氮染料相比其在低极性溶剂中的溶解度降低。因此，每一次后续中性偶氮染料的沉积，基本上不会溶解上一层的质子化偶氮染料。在某些情况下，每一在前的化学改性层都可以作为下一层的中性偶氮染料的配向层。另外，前一层吸收的酸性试剂的量足够使后一层中性偶氮染料部分质子化。因此，在上述情况下，可省略额外的配向步骤。
采用以下参数及其对波长的依赖性，对偏振片的效率进行评估和表征：
根据下式计算二向色性比：
Figure PCTCN2019106099-appb-000007
其中α //和α ⊥分别是平行和垂直方向的吸收系数。
根据下式计算偏振率：
Figure PCTCN2019106099-appb-000008
其中Τ //和T ⊥分别是平行和垂直方向的透射率。
用激光照射检测偏光片的抗光稳定性。
用表面粗糙度、均匀性和模糊性评价薄膜的光学质量。透射峰的宽度用半峰宽(FWHM)来表征，单位为nm。
这种偏光片的制造方法包括以下步骤：
(i)在基底，诸如聚合物柔性基底或玻璃上沉积高质量的偶氮染料薄膜。沉积方法可以是旋涂或真空沉积或印刷或喷涂或其他技术。
(ii)然后使用线偏振光辐照对染料分子膜进行光配向
(iii)然后在溶液或气相中用酸或酸前体对定向排列的染料膜进行化学改性。
(iv)任选地，在化学改性的光配向薄膜表面沉积保护层。保护层的一个例子是反应性单体然后聚合。
沉积薄膜的光配向以及随后的化学改性和最终封装保护可根据需要在同一室或不同的室中进行。
本发明公开了用于可见光和近红外-1区的使用偶氮染料的薄膜吸收偏光片(包括带有图案的薄膜)及其制备方法，本发明的薄膜的二向色性比(DR)大于30，该薄膜的厚度可以从几十到数千纳米变化，这取决于薄膜所需的光密度，该薄膜的DR耐随机偏振光的照射。本发明的化学改性包括用酸或其衍生物(其经合适的反应能够产生酸，例如优选但不限于在气相中同时或依次以水处理酸酐)处理以获得质子化形式的偶氮染料，其在可见光和近红外-1区域中具有扩大的吸收，且不会被进一步的光配向再取向。
附图的简要说明
图1为AD-1分子；
图2：用于化学改性偏光片薄膜的气室；
图3：具有控制化学改性剂温度和压力的用于化学改性偏光片薄膜的气室；
图4为光稳定性试验前后AD-1膜的光谱图；
图5以三氟甲磺酸酐处理前(A)和处理后(B)AD-1膜的光谱图；
图6：抗日光和偏振光辐射的稳定性测试前(A)和测试后(B)以三氟甲磺酸酐处理AD-1膜的光谱图；
图7：在气相中以硝酸(69v/v％以上的硝酸水溶液)处理的样品上显示的裂缝；
图8：以硝酸处理前(A)和处理后(B)AD-1膜的光谱图；
图9：以硝酸处理的AD-1薄膜在环境条件下储存3天后的光谱图；
图10：在含有Tf 2O蒸汽的气室中AD-1薄膜在显影时的光谱演变， 每个周期结束时记录光谱的A ||；
图11：光稳定性测试前(A)和测试后(B)未完全改性的AD-1薄膜的光谱图；
图12：用硫酸处理后AD-1薄膜的光谱图；
图13：在光照射测试前后用硫酸处理的AD-1膜的光谱图；以及
图14：有保护层(A)和没有保护层(B)的AD-1膜在环境条件下10天后的光谱图。
具体实施方式
以下实施例中使用的AD-1为
Figure PCTCN2019106099-appb-000009
其中烷基末端链是C 4H 9。
实施例1：通过旋涂技术制备中性偶氮膜
用水和表面活性剂洗涤玻璃基底，干燥并在臭氧室中活化20分钟。将1滴1-8％的AD-1甲苯溶液以3000rpm的速度旋涂到基底上，进一步旋转30秒。之后，将薄膜在70℃下软烘烤5分钟。当冷却到室温时，基本上如现有技术Displays 2001,22,pp 27-32-Photo-patterned e-wave polarizer,W.C.Yip,H.S.Kwok,V.M.Kozenkov,V.G.Chigrinov和US008576485B2所述，将获得的AD-1膜用线性偏振光进行光配向处理。光源波长为450nm。
实施例2：通过蒸气真空沉积技术制备中性偶氮膜
使用热蒸发体系，在1×10 -6mbar的基础压力下、在高真空中，将染料沉积在干净的裸玻璃或其他基底上(20mm×20mm)。AD-1在140℃左右开始蒸发，将沉积速率控制为
Figure PCTCN2019106099-appb-000010
至
Figure PCTCN2019106099-appb-000011
的范围内的一个恒定值，其由石英膜监控。通过轮廓仪验证薄膜的最终厚度。线性偏振光的光强度固定在30mW/cm 2。沉积和原位光配向同步开始，当厚度达到200nm时二者停止。如 实施例4所述，通过用化学改性剂进行处理来对薄膜进行化学改性。
实施例3:AD-1膜的稳定性试验
根据实施例1制备配向的AD-1膜样品，从400nm至550nm的平均DR为36。然后将样品暴露于线偏振光(λ＝405nm(30mW/cm 2)，总光量为36J/cm 2)。光偏振与AD-1的初始取向之间的夹角为45°。光谱演化如图4所示。可以看出，发生了非常显著的变化。AD-1膜从400nm至550nm的平均DR为1.08。AD-1膜的光配向样品对其激活光(例如405nm)显示相当弱的稳定性。
实施例4：在封闭容器中在三氟甲磺酸酐的蒸气相中进行膜的化学改性
在封闭容器中，通过将配向的AD-1样品(根据实施例1获得)用三氟甲磺酸酐(1v/v％三氟甲磺酸酐的正辛烷溶液)在气相中处理来进行膜的化学改性，在环境条件下定期提取样品以监控光谱和二向色性比。当达到最大二向色性比时，总暴露时间约为5分钟。吸收光谱的演化如图5所示。
实施例5:改性膜的稳定性测试
如实施例4所述，用1v/v％三氟甲磺酸酐处理AD-1膜样品，在日光环境条件下储存10天。然后用线偏振光(λ＝632nm(50mW/cm 2)照射样品，总光量为400J/cm 2。接着用线偏振光(λ＝442nm(20mW/cm 2)照射样品，总光量为150J/cm 2。两种情况下，光偏振与AD-1的初始取向的夹角均为45°。图6示出光谱的演化。可以看出，没有观察到明显的变化。用三氟甲磺酸酐进行化学改性后的光配向AD-1样品在强光照射下是稳定的，其在使用环境下也很稳定。
实施例6:在硝酸气相中进行膜的化学改性(浓酸、高化学改性率)
根据实施例1制备配向的AD-1膜样品。通过在硝酸气相(69v/v％硝酸水溶液)中处理来进行膜的化学改性，定期监控光谱和二向色性比。如图7所示，采样器暴露30秒后，由于过高的化学改性率，样品有裂缝。
实施例7:硝酸气相中(稀酸，较慢的化学改性率)膜的化学改性
根据实施例1制备配向的AD-1膜样品。通过在气相中用硝酸水溶液处 理来进行膜的化学改性，为了避免裂缝，将HNO 3进一步稀释至40v/v％至10v/v％的更低的浓度。当达到最大二向色性比时，总暴露时间取决于酸浓度，对于40v/v％约为1.7分钟，对于10v/v％约为15分钟。化学改性后吸收光谱的变化如图8所示。可以看出，质子化后吸收光谱再次延伸到红色区域，同时保持二色性比。此外，膜上没有显示裂缝。
然而，由于硝酸是挥发性的，这样改性的AD-1的光谱在环境条件下约3天会逐渐从灰色变为红色，如图9所示。
为了防止颜色随时间衰减，保护层(即丙烯酸聚合物)被覆盖在化学改性的AD-1膜上方。例如，用丙烯酸UV胶覆盖样品，然后在UV光(λ＝365nm，20mW/cm 2)下聚合3分钟以形成坚固的膜。这表明，覆盖有保护层的薄膜至少在两周内相当稳定。
实施例8:通过在三氟乙酸(TFA)的气相中处理来进行AD-1膜的化学改性；挥发性酸的试验。
根据实施例1制备配向的AD-1膜样品，在490nm下DR为22，λ max＝490nm,半峰宽(FWHM)＝173。化学改性的程序与实施例7使用的基本一致。当达到最大二向色性比时，三氟乙酸蒸气总暴露时间约为1分钟。改性AD1-TFA的光谱红移，λ max＝560nm，半峰宽(FWHM)＝254nm，DR＝19。在环境条件下，如此改性的AD-1的光谱逐渐变回来，大约30分钟后，完全恢复起始光谱，DR≈15-16。
为了防止颜色随时间衰减，保护层(即丙烯酸聚合物)基本上以与实施例7中所述相同的方式覆盖在化学改性的AD-1膜上。覆盖有保护层的膜至少稳定两周。
实施例9:通过在乙酸(AcOH)气相中来进行AD-1膜的化学改性：弱酸测试
根据实施例1制备配向的AD-1膜样品。化学改性的程序与实施例7使用的基本一致。AcOH蒸气的总暴露时间为约20分钟。没有观察到此期间膜颜色发生任何实质的变化。
实施例10:通过在特殊气室中用三氟甲磺酸酐处理，并通过紫外-可见 光谱和DR检测连续监控改性过程来进行膜的化学改性
根据实施例1制备配向的AD-1膜样品(490nm下DR为82)，将该膜样品放置于气室内(图2)，并且如下所述以湿氮气、干氮气和化学蒸汽依次进行吹扫。每个吹扫步骤的流速和持续时间取决于腔室容积；例如，对于80ml室容积，使用以下条件：
(i)切换至湿管线，并用湿氮气(90％RH)以150毫升/分钟的流速吹扫2分钟。
(ii)切换至干管线，并用干氮气以500毫升/分钟的流速吹扫30秒。
(iii)切换至化学品管线(使用的化学改性剂为三氟甲磺酸酐)，并以50毫升/分钟的流速吹扫1分钟。
(iv)切换至干管线，并用干燥氮气以500ml/min的流速吹扫30秒。
根据程序(i)-(iv)的方法重复几次(几个周期)，通常5-8个周期，直至达到所需的二色性比。利用紫外可见光谱仪在线监控化学改性的进展。正交偏振片(A //)的吸收逐渐红移，强度略微增加。平行偏振片(A ⊥)的吸收在改性开始时增大，3-4个周期后开始下降，见图10。一旦A ⊥达到最小值，用流速为150ml/min的湿氮气吹扫气室5分钟。
这样改性的膜的光谱几乎覆盖整个可见光谱范围；改性后的膜显示λmax＝650nm，FWHM＝309nm，DR＝32。在实施例5中描述的条件下，改性膜可稳定至少10天。
实施例11:如实施例10所示，在特殊的气室中通过用三氟甲磺酸酐处理来进行膜的化学改性，测试完成膜质子化所需的时间。
除该过程的总时长(4个周期后终止改性)外，采用与实施例10描述的类似的方法形成AD-1定向的膜样品。在650nm处，膜的二色性比为42。然而，在暴露于总光量为100J/cm 2的线偏振光(λ＝442nm，20mW/cm 2)后，蓝光区的DR变差，即在442nm处，DR＝8，如图11所示。这是由于改性时间不足，导致未改性的AD-1留在薄膜中。
实施例12:大气压下在硫酸气相中对膜进行化学改性(低挥发性酸的测试)
根据实施例1制备配向的AD-1膜样品，DR为63。膜的化学改性在大 气压下在室(图3)中进行。在环境温度下，没有任何反应。将酸加热至180℃后，偶氮染料的红色变为深蓝色，以分离的小液滴的形式收集偶氮染料。膜区域内的DR在变化，最大DR值小于6。
实施例13:低气压下在硫酸气相中对膜进行化学改性(低挥发性酸的测试，高化学改性率)。
根据实施例1制备配向的AD-1膜样品，DR为60。膜的化学改性在0.25毫巴的压力下在室(图3)中进行。酸的温度为100℃。在偶氮染料膜暴露1分钟后，颜色变为深蓝色，膜有许多缺陷和裂缝。膜区域内的DR在变化，最大DR值小于5。
实施例14:低气压下在硫酸气相中对膜进行化学改性(低挥发性酸的测试，降低的化学改性率)。
根据实施例1制备配向的AD-1膜样品，DR为25。膜的化学改性在0.25毫巴的压力下在室(图3)中进行。偶氮染料的膜的暴露时间取决于酸的温度，因此，从80℃下的6分钟到30℃时30分钟不等。偶氮染料膜暴露8分钟后，颜色变为灰蓝色，在膜上未观察到任何缺陷或裂缝(如图12所示)。DR是14。将用硫酸处理的AD-1膜样品在环境条件下在日光下储存7天。然后用非偏振光(包括405nm和365nm，总强度67mW/cm 2)照射样品，光量为200J/cm 2。光偏振与AD-1的初始取向之间的夹角为45°。光谱演化在图13中示出。结果显示没有观察到明显变化。用硫酸进行化学修饰后，AD-1的光配向样品对强光照射是稳定的，其对环境条件也是稳定的。
实施例15:没有保护层和有保护层的改性膜的可靠性测试。
如实施例4所述制备用三氟甲磺酸酐处理的两个AD-1膜样品。其中一个改性膜是裸露的，没有覆盖任何保护层。而另一个改性膜涂有聚合物膜(即丙烯酸聚合物)，然后在紫外光(λ＝365nm，20mW/cm 2)下聚合3分钟，形成坚固的膜。将两个样品在环境条件下储存10天。如图14(A)和(B)所示，覆盖有保护层的样品比裸露样品结实得多。如图14可以看出，在平行方向的吸收中，10天后保护的样品光谱显示没有变化，然而，没有任何保护层的样品明显降解，即，对比度变得更差。
实施例16:在特殊气流室中通过以三氟甲磺酸酐/水顺序沉积/化学改性AD1制备的多层偏光片(偏光膜)
化学改性的AD-1取向膜的第一层基本上如实施例10中所述来制备。450nm至700nm的平均DR为24，CR为217，如图15所示。以类似于实施例1中所述的，通过旋涂4％w/w的AD-1的甲苯溶液来沉积AD-1的第二层。形成的膜的吸收光谱如图15所示。在400-520nm范围内吸光度的增加清楚地证实第二层中AD-1材料的一部分被取向，而一些部分是未被取向的。如实施例1所述的，用线性偏振光对膜进行额外取向使得残留的未取向AD-1完全取向，如图16所示。通过用以下处理对样品残留的AD-1分子进行额外的化学修饰。如实施例10中所述(4个循环)，通过在气流室中，以“Tf 2O/湿气”处理，在残留的AD-1分子上额外的化学改性基本上形成了膜。如图17所示，与单个改性层(CR＝217)相比，最终的膜显示了两倍的对比度，即CR＝443。

Claims (10)

  1. 一种使用偶氮染料的薄膜偏光片的制备方法，该方法包括如下步骤：
    (i)将至少一种偶氮染料沉积到基底上，形成偶氮膜；
    (ii)使步骤(i)制备得到的偶氮膜光配向，以得到光配向的偶氮膜；以及
    (iii)对步骤(ii)制备得到的光配向的偶氮膜进行化学改性，即得。
  2. 根据权利要求1所述的制备方法，其中，在步骤(i)中，所述偶氮染料为一种以上；
    优选地，在步骤(i)中，所述偶氮染料选自以下分子式的化合物中的一种或多种：
    Figure PCTCN2019106099-appb-100001
    其中，R 1和R 2独立地选自H、烷基(例如C 1-6的烷基)、烯基(例如C 2-6的烯基)、-C kH 2k-OC(O)C＝CH 2和-C lH 2l-OC(O)C(CH 3)＝CH 2，其中k和l独立地为1至12的整数，优选为1至6的整数；
    A、C相互独立地选自以下所列的环：
    Figure PCTCN2019106099-appb-100002
    其中，X、Y、Z独立地选自H、卤素、烷基(例如C 1-6的烷基)和OH；
    B选自：单键、-C＝C-双键、-COO-、-OCO-、-N＝N-和-CH 2O-；
    m、n独立地为0到2之间的整数，在相同的化合物中，m和n不同时等于0或2；
    优选地，在步骤(i)中，所述偶氮染料为
    Figure PCTCN2019106099-appb-100003
    优选地，在步骤(i)中，所述基底为聚合物柔性基底或玻璃。
    优选地，在步骤(i)中，所述沉积通过旋涂、真空沉积、印刷、喷涂或其他技术来进行。
  3. 根据权利要求1或2所述的制备方法，其中，在步骤(ii)中，所述光配向通过使用线偏振光照射来获得；
    优选地，在步骤(ii)中，所述线偏振光通过阴影遮罩形成带有图案的偏振光。
  4. 根据权利要求1至3中任一项所述的制备方法，其中，在步骤(iii)中，所述化学改性是通过化学气相沉积技术进行改性。
  5. 根据权利要求1至4中任一项所述的制备方法，其中，在步骤(iii)中，所述化学改性是在含有化学改性剂或其衍生物的溶液中进行的。
  6. 根据权利要求5所述的制备方法，其中，所述化学改性剂为酸或酸衍生物，所述酸或酸衍生物能够使所述偶氮染料的分子质子化；
    优选地，所述化学改性剂为酸或酸衍生物的混合物；
    优选地，所述酸选自卤化氢酸、硝酸、硫酸、磷酸、芳基磺酸、烷基磺酸、卤代磺酸和含卤羧酸；
    优选地，所述酸的浓度为10v/v％至40v/v％；
    优选地，所述酸的温度为30℃至80℃；
    优选地，在步骤(iii)中，所述化学改性的改性时间为15至40分钟，优选为25至37分钟。
  7. 根据权利要求1至6中任一项所述的制备方法，其中，所述酸衍生物是酸酐，包括但不限于三氟酸酐，例如三氟甲磺酸酐(1v/v％三氟甲磺酸酐)；
    优选地，所述化学改性剂为酰卤；
    优选地，所述化学改性剂为酯；
    优选地，所述化学改性剂为酸的三甲基硅烷酯，优选地，所述酸的三甲基硅烷酯为三氟甲磺酸三甲基硅酯；
    优选地，所述化学改性剂为酸性氧化物；优选地，所述酸性氧化物是NO 2、N 2O 4、或SO 3。
  8. 根据权利要求1至7中任一项所述的制备方法，其中，所述化学改性剂是通式为R tEX 4-t的衍生物中的一种或多种，其中R是烷基(例如C 1-6的烷基)或烷氧基(例如C 1-6的烷氧基)，E选自Si、Sn、Ti，X是卤素原子，并且t是0到4的整数；
    优选地，所述化学改性剂是Me 2SiCl 2；
    优选地，所述化学改性剂是MeSiCl 3；
    优选地，所述化学改性剂是(C 2H 5O) 4Si。
  9. 根据权利要求1至8中任一项所述的制备方法，其中，所述薄膜偏光片为多层膜；
    优选地，所述多层膜通过在完成步骤(i)-(iii)后，重复步骤(i)-(iii)来实现；
    优选地，所述多层膜通过在完成步骤(i)-(iii)后，重复步骤(i)来实现；
    优选地，所述多层膜通过在完成步骤(i)-(iii)后，重复步骤(i)和(iii)来实现。
  10. 根据权利要求1至9中任一项所述的制备方法，其中，所述方法还包括：(iv)将聚合物沉积在步骤(iii)化学改性后获得的产品上；以及，任选地，(v)在步骤(iv)后，聚合所述聚合物；
    优选地，所述聚合物为液晶聚合物，例如丙烯酸聚合物。
PCT/CN2019/106099 2019-09-17 2019-09-17 一种使用偶氮染料的薄膜偏光片的制备方法 WO2021051258A1 (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023148173A1 (en) 2022-02-01 2023-08-10 Nchain Licensing Ag Method and system for permission management

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201114847A (en) * 2009-10-15 2011-05-01 Nitto Denko Corp Coating fluid, process for producing same, and polarizing film
CN102171592A (zh) * 2008-09-30 2011-08-31 富士胶片株式会社 二色性染料组合物、光吸收各向异性膜和偏振元件
US20120307363A1 (en) * 2001-05-14 2012-12-06 The Hong Kong University Of Science And Technology Photo-induced dichroic polarizers and fabrication methods thereof
CN107144911A (zh) * 2017-06-30 2017-09-08 深圳市华星光电技术有限公司 染料偏光片的制备方法及显示面板
CN107532009A (zh) * 2015-04-20 2018-01-02 日本化药株式会社 含有二色性色素的组合物、使用该组合物制作的色素膜以及具有该色素膜的偏振元件

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4547946B2 (ja) * 2004-03-11 2010-09-22 三菱化学株式会社 アゾ色素、異方性色素膜用二色性アゾ色素並びにこれを用いた異方性色素膜形成用組成物、異方性色素膜および偏光素子
JP4876549B2 (ja) * 2004-12-16 2012-02-15 三菱化学株式会社 アゾ色素、これを用いた異方性色素膜用組成物、異方性色素膜および偏光素子
JP2008031454A (ja) * 2006-06-30 2008-02-14 Mitsubishi Chemicals Corp 異方性色素膜用アゾ色素
JP6111193B2 (ja) * 2011-05-31 2017-04-05 日本化薬株式会社 染料系偏光素子及び偏光板
CN108073001B (zh) * 2016-10-17 2021-03-30 香港科技大学 在合适相对湿度范围的光配向层的加工方法
CN107916017B (zh) * 2017-11-30 2019-11-15 深圳市华星光电技术有限公司 耐uv染料的制作方法及对应的涂布型染料偏光片

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120307363A1 (en) * 2001-05-14 2012-12-06 The Hong Kong University Of Science And Technology Photo-induced dichroic polarizers and fabrication methods thereof
CN102171592A (zh) * 2008-09-30 2011-08-31 富士胶片株式会社 二色性染料组合物、光吸收各向异性膜和偏振元件
TW201114847A (en) * 2009-10-15 2011-05-01 Nitto Denko Corp Coating fluid, process for producing same, and polarizing film
CN107532009A (zh) * 2015-04-20 2018-01-02 日本化药株式会社 含有二色性色素的组合物、使用该组合物制作的色素膜以及具有该色素膜的偏振元件
CN107144911A (zh) * 2017-06-30 2017-09-08 深圳市华星光电技术有限公司 染料偏光片的制备方法及显示面板

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023148173A1 (en) 2022-02-01 2023-08-10 Nchain Licensing Ag Method and system for permission management
WO2023148176A1 (en) 2022-02-01 2023-08-10 Nchain Licensing Ag Method and system for permission management

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