US20130045390A1 - Base Film of Modified Polyvinyl Alcohol and Its Preparation Method and Polarizer - Google Patents
Base Film of Modified Polyvinyl Alcohol and Its Preparation Method and Polarizer Download PDFInfo
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- US20130045390A1 US20130045390A1 US13/377,537 US201113377537A US2013045390A1 US 20130045390 A1 US20130045390 A1 US 20130045390A1 US 201113377537 A US201113377537 A US 201113377537A US 2013045390 A1 US2013045390 A1 US 2013045390A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to a base film, of polyvinyl alcohol and more particularly to a base film of modified polyvinyl alcohol as well as its preparation method and a polarizer prepared from the base film of modified polyvinyl alcohol.
- Polarizer is one of the essential important components in a liquid crystal display (LCD), and its function is to convert natural light into polarized light, in order to cooperate with liquid crystal molecules twisted to control light passing and presentation of color signals.
- An existing polarizer used in a LCD is mostly made of a highly oriented high polymer such as a base film of polyvinyl alcohol (PVA) as its substrate, dyed with various types of dichroic dyes, extended under a certain humidity and temperature, and then a layer of triacetate cellulose (TAC) film with high light transmission rate, excellent waterproof characteristic and a certain degree of mechanical strength is composited on each of two sides of the PVA base film, so as to prepare the polarizer.
- PVA polyvinyl alcohol
- TAC triacetate cellulose
- iodine polarizers In comparing to polarizers dyed with organic dichroic dyes, iodine polarizers have become the mainstream polarizers for LCDs because of their polarization characteristic of wider range of wavelengths, higher light transmission rates and better price-performance ratios. Nevertheless, iodine polarizers are comparatively less resistant to heat and water. As liquid crystal displays are commonly applied to many products, higher durability for polarizers is also demanded. Therefore, modification of PVA base films for development of polarizers with excellent optical and durability performances for LCDs is a technical difficulty encountered currently.
- a PVA base film is swelled, soaked and dyed in iodine, and extended uniaxially; then a layer of triacetate cellulose (TAC) film is composited on each of two sides of the PVA base film, so as to prepare an iodine polarizer.
- PVA is a linear high molecular polymer with a plurality of —OH groups of strong polarity evenly distributed in a long molecular chain as shown in FIG. 1 , therefore it has relatively strong hydrophilic property, and is less water resistant and less stable.
- iodine molecular structure is easily damaged under high temperatures and humidity, so that iodine polarizers are less humidity and heat resistant with poor mechanical performance. Generally, they may only meet testing conditions of 80° C. ⁇ 500 hrs or 60° C. ⁇ 90% RH ⁇ 500 hrs, and may easily become warped and peeled off, resulting in limiting their application range.
- FIG. 1 shows a diagram of a molecular structure of a PVA base film of an existing iodine polarizer, wherein a TAC protection film of the iodine polarizer is not shown.
- a plurality of OH groups with strong polarity and hydrophilic property is evenly distributed on a surface of a polyvinyl alcohol polymer 3 of the PVA base film.
- a structure of iodine molecules 2 may be easily damaged under high temperatures and humidity. Therefore, the PVA base film of the iodine polarizer is relatively less stable under high temperatures and humidity.
- the PVA base film In order to improve the heat and humidity resistances of the PVA base film of the iodine polarizer, the PVA base film needed to be modified or cross-linked.
- a method for improving the heat and humidity resistances of the PVA base film is to add a second constituent which is a material to be cross-linked with the hydrophilic —OH groups in PVA.
- both China patents published No. 1979231A and 101281267A employ dicarboxylic acids and boric acids to have the PVA base film cross-linked. Nevertheless, boric acids increase the toughness of the PVA base film which will limit its extension percentage during a stretching process.
- a first object of the present invention is to provide a method for preparing a base film of modified polyvinyl alcohol.
- the present invention provides a method for preparing a base film of modified polyvinyl alcohol, comprising preparation steps of:
- dodecafluoro-heptyl-propyl-trimethoxy-silane dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane, tetramethyl-(perfluoro-hexyl-ethyl)propyl-trimethoxy-silane and tridecafluoro-octyl-trimethoxy-silane, and the weight of the added fluorinated silane is 33% to 40% of that of the nano-silicon dioxide; and
- a molecular formula of the anionic carboxylate fluorocarbonic surfactant in the step (2) is RF—CH 2 —COOH, wherein R represents a carbon chain of C 6 to C 10 , and the weight of the added modified silicon dioxide powders is 4% to 8% of that of the polyvinyl alcohol polymer.
- particle diameter of the nano-silicon dioxides in the step (1) is between 35 and 45 nm.
- the weight of the surfactant added in the step (2) is 0.2% to 0.3% of that of the polyvinyl alcohol polymer.
- the present invention further provides a method for preparing a base film of modified polyvinyl alcohol, comprising preparation steps of:
- the fluorinated silane in the step (1) are selected from one or any mixture of dodecafluoro-heptyl-propyl-trimethoxy-silane, dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane, tetramethyl-(perfluoro-hexyl-ethyl)propyl-trimethoxy-silane and tridecafluoro-octyl-trimethoxy-silane.
- the purity specification of nano-silicon dioxides in the step (1) is analytical degree pure reagent, and particle diameter thereof is between 35 and 45 nm.
- the weight of the fluorinated silane added in the step (1) is 33% to 40% of that of the nano-silicon dioxide.
- the degree of polymerization of the polyvinyl alcohol polymer in the step (2) is 4000 and its degree of alcoholysis is 98%.
- the weight of the modified silicon dioxide powder added in the step (2) is 4% to 8% of that of the polyvinyl alcohol polymer.
- an anionic carboxylate fluorocarbonic surfactant is further added in the step (2), and a molecular formula thereof is RF—CH 2 —COOH, wherein R represents a carbon chain of C 6 to C 10 .
- the weight of the surfactant added in the step (2) is 0.2% to 0.3% of that of the polyvinyl alcohol polymer.
- a second object of the present invention is to provide a base film of modified polyvinyl alcohol prepared from the abovementioned preparation method.
- the present invention discloses a technical solution, as follows:
- a base film of modified polyvinyl alcohol comprises polyvinyl alcohol polymers, nano-silicon dioxide groups and fluorinated silane groups, the base film of modified polyvinyl alcohol has a general formula shown as below:
- (A) groups represent the fluorinated silane groups
- the fluorinated silane groups are selected from one or any mixture of dodecafluoro-heptyl-propyl-trimethoxy-silane, dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane,tetramethyl-(perfluoro-hexyl-ethyl)propyl-tri methoxy-silane and tridecafluoro-octyl-trimethoxy-silane; and
- (B) group represents nano-silicon dioxide group.
- iodine molecules are bonded in the polyvinyl alcohol polymers, wherein the nano-silicon dioxide group connected with the fluorinated silane groups is coated on and outside the polyvinyl alcohol polymers and the iodine molecules.
- a third object of the present invention is to provide a polarizer made of the abovementioned base film of modified polyvinyl alcohol.
- a polarizer comprising: the abovementioned base film of modified polyvinyl alcohol; and a protection film adhered on one surface or two surfaces of the polarizing film, the protection film for example is a triacetate cellulose (TAC) film.
- TAC triacetate cellulose
- Low surface energy fluorinated groups migrate and aggregate toward a surface of the PVA base film, so that the PVA base film will feature excellent water, oil and corrosion resistances. Furthermore, the bond energy of C—F bonds is strong, and the bonds are very closely arranged on an outer layer of a carbon skeleton, so that fluoride polymers have excellent stability against heat.
- Nano-silicon dioxide has high rigidity, and has characteristics of high strength, high toughness, and high stability under high temperatures, and a 3-dimensional network is formed when combined with a high polymer chain of PVA, so that the mechanical strength, elasticity and abrasion resistance of the PVA base film are substantially enhanced.
- easily damaged iodine molecules are protected when they are coated with nano-silicon dioxides grafted with long-chain fluorinated silicon groups, so as to enhance the mechanical stability of the PVA polarizing film.
- the acting force between polymer molecules of C—F bonds of fluorinated materials is weak and therefore has excellent sticking-resistance and surface self-cleaning performance.
- later-staged adhering process of the PVA base film and other membrane layers it can effectively prevent foreign substances from entering, as a result, the defective percentage of polarizers can be reduced.
- a protective film of triacetate cellulose (TAC) with high light transmission rate, excellent waterproof characteristic and a certain degree of mechanical strength is composited on each of two sides of the PVA base film.
- TAC triacetate cellulose
- the present invention can substantially enhance the heat and humidity resistances as well as the mechanical strength of the PVA base film, even that the TAC film can be omitted (i.e. the PVA base film can be directly used as a polarizer).
- a certain degree of roughness can be formed on the surface of the PVA base film by controlling the sizes of nano-silicon dioxides, and thus images are diffused and reflected by the concave and convex shapes thereof, in order to prevent the light from being overly-concentrated to cause discomfort in viewing, as a result, an anti-glare function is achieved.
- FIG. 1 is an illustration of a molecular structure of a PVA base film of an existing iodine polarizer
- FIG. 2 is an illustration of a molecular structure of a PVA base film of a polarizer of a preferred embodiment of the present invention.
- numeral 1 is nano-silicon dioxide group
- numeral 2 is iodine molecule
- numeral 3 is polyvinyl alcohol (PVA) polymer
- numeral 4 is fluorinated silane group.
- the present invention provides a base film of modified polyvinyl alcohol (PVA) and its preparation method, wherein its specific preparation steps include:
- modified nano-silicon dioxide powders obtained from the step (1) and an anionic carboxylate fluorocarbonic surfactant (RF—CH 2 —COOH) are added to an aqueous solution of polyvinyl alcohol (PVA) polymers, and dispersed by ultrasonic at room temperature for 1 hour; then stirring in high speed for 5 hours under 40° C., in order to prepare a composite solution of polyvinyl alcohol (PVA) polymers.
- PVA polyvinyl alcohol
- modified nano-silicon dioxides which thus can be evenly distributed in a system; on the other hand, there are still some —OH on the surface of the hydrolytic fluorinated silane and the surface of the modified nano-silicon dioxides, which can be further cross-linked and condensed with the —OH in the long molecular chain of PVA.
- the fluorinated silane is selected from dodecafluoro-heptyl-propyl-trimethoxy-silane, but not limited thereto, the fluorinated silane may be selected from one or any mixture of dodecafluoro-heptyl-propyl-trimethoxy-silane, dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane, tetramethyl-(perfluoro-hexyl-ethyl)propyl-trimethoxy-silane and tridecafluoro-octyl-trimethoxy-silane.
- the purity specification of nano-silicon dioxides is analytical degree pure reagent, and the particle diameter is between 35 and 45 nm; the degree of polymerization of polyvinyl alcohol polymer is 4000 and its degree of alcoholysis is 98%.
- the weight of the fluorinated silane is 33% to 40% of that of the nano-silicon dioxide.
- the weight of the modified silicon dioxide powder added in the step (2) is 4% to 8% of that of the polyvinyl alcohol polymer; the molecular formula of the anionic carboxylate fluorocarbonic surfactant added in the step (2) is RF—CH 2 —COOH, wherein R represents a carbon chain of C 6 to C 10 .
- the weight of the added surfactant is 0.2% to 0.3% of that of the polyvinyl alcohol polymer.
- modified PVA base film is used as a substrate material.
- a modified PVA base film of a polarizer is prepared as shown in a molecular structure in FIG. 2 , and it comprises polyvinyl alcohol (PVA) polymers 3 , iodine molecules 2 , a nano-silicon dioxide group 1 and fluorinated silane groups 4 .
- PVA polyvinyl alcohol
- the nano-silicon dioxide group 1 is grafted and modified by dodecafluoro-heptyl-propyl-trimethoxy-silane; after treated with a certain dispersing means, the grafted and modified nano-silicon dioxide group 1 is evenly dispersed in the PVA base film and combined with a high polymer chain of the polyvinyl alcohol (PVA) polymers 3 to form a three-dimensional network structure, and organic and inorganic nano-composite materials are obtained.
- PVA polyvinyl alcohol
- Fluorinated materials are materials with the lowest surface energy discovered so far, low surface energy fluorinated groups migrate and aggregate towards a surface of the PVA base film, with only a very little amount, the surface of the PVA base film will feature excellent hydrophobic, oleophobic, sticking-resistant and self-cleaning performances. Furthermore, rigid nano-silicon dioxides allow the PVA base film to have excellent capabilities of heat resistance and mechanical stability. Better compatibility of organic and inorganic can be achieved from organic and inorganic nano-composite materials prepared from silicon dioxides modified by organic fluorinated silane.
- low surface energy fluorinated groups migrate and aggregate towards a surface of the PVA base film, so that the PVA base film will feature excellent water, oil and corrosion resistances. Furthermore, the bond energy of C—F bonds is strong, and the bonds are very closely arranged on an outer layer of a carbon skeleton, so that fluoride polymers have excellent stability against heat.
- the nano-silicon dioxide group has high rigidity, and has characteristics of high strength, high toughness, and high stability under high temperatures, and a 3-dimensional network is formed when combined with a high polymer chain of PVA, so that the mechanical strength, elasticity and abrasion resistance of the PVA base film are substantially enhanced.
- easily damaged iodine molecules are protected when they are coated with nano-silicon dioxides grafted with long-chain fluorinated silicon groups, which enhances the mechanical strength and stability of the PVA base film.
- the acting force between the polymer molecules of C—F bonds of fluorinated materials is weak and therefore has excellent sticking-resistance and surface self-cleaning performance.
- the PVA base film and other membrane (e.g. TAC film) layers it may effectively prevent foreign substances from entering, as a result, the defective percentage of polarizers can be reduced.
- a certain degree of roughness can be formed on the surface of the polarizer by controlling the sizes of nano-silicon dioxides, and thus images are diffused and reflected by the concave and convex shapes, in order to prevent the light from being overly-concentrated to cause discomfort in viewing, as a result, an anti-glare function is achieved.
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Abstract
The present invention provides a base film of modified polyvinyl alcohol as well as a method for preparing the base film of modified polyvinyl alcohol and a polarizer made from the base film. The method includes steps of: (1) executing surface graft modification of nano-silicon dioxides with fluorinated silane to obtain modified nano-silicon dioxide powders; (2) adding the modified nano-silicon dioxide powders obtained from the step (1) to an aqueous solution of polyvinyl alcohol polymers, in order to prepare a composite solution of polyvinyl alcohol polymers; and (3) pouring the composite solution of polyvinyl alcohol polymers prepared from the step (2) onto a surface of a casting substrate to obtain a base film of modified polyvinyl alcohol (PVA). The present invention enhances the heat and humidity resistances and the stability of the PVA base film, and improves its mechanical performance and sticking-resistance.
Description
- 1. Field of Invention
- The present invention relates to a base film, of polyvinyl alcohol and more particularly to a base film of modified polyvinyl alcohol as well as its preparation method and a polarizer prepared from the base film of modified polyvinyl alcohol.
- 2. Related Art
- Polarizer is one of the essential important components in a liquid crystal display (LCD), and its function is to convert natural light into polarized light, in order to cooperate with liquid crystal molecules twisted to control light passing and presentation of color signals. An existing polarizer used in a LCD is mostly made of a highly oriented high polymer such as a base film of polyvinyl alcohol (PVA) as its substrate, dyed with various types of dichroic dyes, extended under a certain humidity and temperature, and then a layer of triacetate cellulose (TAC) film with high light transmission rate, excellent waterproof characteristic and a certain degree of mechanical strength is composited on each of two sides of the PVA base film, so as to prepare the polarizer. In comparing to polarizers dyed with organic dichroic dyes, iodine polarizers have become the mainstream polarizers for LCDs because of their polarization characteristic of wider range of wavelengths, higher light transmission rates and better price-performance ratios. Nevertheless, iodine polarizers are comparatively less resistant to heat and water. As liquid crystal displays are commonly applied to many products, higher durability for polarizers is also demanded. Therefore, modification of PVA base films for development of polarizers with excellent optical and durability performances for LCDs is a technical difficulty encountered currently.
- Firstly, a PVA base film is swelled, soaked and dyed in iodine, and extended uniaxially; then a layer of triacetate cellulose (TAC) film is composited on each of two sides of the PVA base film, so as to prepare an iodine polarizer. PVA is a linear high molecular polymer with a plurality of —OH groups of strong polarity evenly distributed in a long molecular chain as shown in
FIG. 1 , therefore it has relatively strong hydrophilic property, and is less water resistant and less stable. Furthermore, iodine molecular structure is easily damaged under high temperatures and humidity, so that iodine polarizers are less humidity and heat resistant with poor mechanical performance. Generally, they may only meet testing conditions of 80° C.×500 hrs or 60° C.×90% RH×500 hrs, and may easily become warped and peeled off, resulting in limiting their application range. - Referring to
FIG. 1 which shows a diagram of a molecular structure of a PVA base film of an existing iodine polarizer, wherein a TAC protection film of the iodine polarizer is not shown. A plurality of OH groups with strong polarity and hydrophilic property is evenly distributed on a surface of apolyvinyl alcohol polymer 3 of the PVA base film. And a structure ofiodine molecules 2 may be easily damaged under high temperatures and humidity. Therefore, the PVA base film of the iodine polarizer is relatively less stable under high temperatures and humidity. - In order to improve the heat and humidity resistances of the PVA base film of the iodine polarizer, the PVA base film needed to be modified or cross-linked. Currently, a method for improving the heat and humidity resistances of the PVA base film is to add a second constituent which is a material to be cross-linked with the hydrophilic —OH groups in PVA. For example, both China patents published No. 1979231A and 101281267A employ dicarboxylic acids and boric acids to have the PVA base film cross-linked. Nevertheless, boric acids increase the toughness of the PVA base film which will limit its extension percentage during a stretching process. Others use vacuum coating or ion sputtering method to have silicon dioxides (SiO2) plated on the PVA base film in order to improve its heat and humidity resistances, but costs for both coating methods of silicon dioxide film are relatively high, and a problem with compatibility between silicon dioxides and the PVA base film also arises.
- Therefore, a new PVA base film is required in the hope that it features relatively higher heat and humidity resistances, stability and mechanical performance, and at the same time with lower defective percentage of polarizers and have anti-glare function.
- A first object of the present invention is to provide a method for preparing a base film of modified polyvinyl alcohol.
- To achieve the above object, the present invention provides a method for preparing a base film of modified polyvinyl alcohol, comprising preparation steps of:
- (1) executing surface graft modification of nano-silicon dioxides with fluorinated silane to obtain modified nano-silicon dioxide powders;
- (2) adding the modified nano-silicon dioxide powders obtained from the step (1) and an anionic carboxylate fluorocarbonic surfactant to an aqueous solution of polyvinyl alcohol polymers, in order to prepare a composite solution of polyvinyl alcohol polymers; and
- (3) pouring the composite solution of polyvinyl alcohol polymers prepared from the step (2) onto a surface of a casting substrate, in order to obtain a base film of modified polyvinyl alcohol; wherein the fluorinated silane in the step (1) are selected from one or any mixture of
- dodecafluoro-heptyl-propyl-trimethoxy-silane,
dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane,
tetramethyl-(perfluoro-hexyl-ethyl)propyl-trimethoxy-silane and
tridecafluoro-octyl-trimethoxy-silane, and the weight of the added fluorinated silane is 33% to 40% of that of the nano-silicon dioxide; and - wherein a molecular formula of the anionic carboxylate fluorocarbonic surfactant in the step (2) is RF—CH2—COOH, wherein R represents a carbon chain of C6 to C10, and the weight of the added modified silicon dioxide powders is 4% to 8% of that of the polyvinyl alcohol polymer.
- In an embodiment of the present invention, particle diameter of the nano-silicon dioxides in the step (1) is between 35 and 45 nm.
- In an embodiment of the present invention, the weight of the surfactant added in the step (2) is 0.2% to 0.3% of that of the polyvinyl alcohol polymer.
- A first object of the present invention, the present invention further provides a method for preparing a base film of modified polyvinyl alcohol, comprising preparation steps of:
- (1) executing surface graft modification of nano-silicon dioxides with fluorinated silane to obtain modified nano-silicon dioxide powders;
- (2) adding the modified nano-silicon dioxide powders obtained from the step (1) to an aqueous solution of polyvinyl alcohol polymers, in order to have a composite solution of polyvinyl alcohol polymers prepared; and
- (3) pouring the composite solution of polyvinyl alcohol polymers prepared from the step (2) onto a surface of a casting substrate, and then vacuum drying it to a constant weight to obtain a base film of modified polyvinyl alcohol (PVA).
- In an embodiment of the present invention, specific steps of the method for preparing a base film of modified polyvinyl alcohol include:
- (1) executing surface graft modification of nano-silicon dioxides with fluorinated silane: adding dried nano-silicon dioxide particles, anhydrous ethanol, deionized water, ammonia and fluorinated silane into a round-bottom flask in turn; after ultrasonic dispersion and then stirring in high speed; executing filtration and deposition, washing with anhydrous ethanol repeatedly; then extracting with toluene to remove unreacted fluorinated silane; finally vacuum drying to a constant weight, and grinding to obtain modified nano-silicon dioxide powders;
- (2) adding the modified silicon dioxide powders obtained from the step (1) and a surfactant to an aqueous solution of polyvinyl alcohol polymers, and dispersing by ultrasonic at room temperature; and then stirring in high speed, in order to prepare a composite solution of polyvinyl alcohol polymers;
- (3) pouring the composite solution of polyvinyl alcohol polymers prepared from the step (2) onto a surface of a cast substrate, and vacuum drying under 80° C.˜90° C. to a constant weight, so as to obtain a base film of modified polyvinyl alcohol (PVA).
- In an embodiment of the present invention, the fluorinated silane in the step (1) are selected from one or any mixture of dodecafluoro-heptyl-propyl-trimethoxy-silane, dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane, tetramethyl-(perfluoro-hexyl-ethyl)propyl-trimethoxy-silane and tridecafluoro-octyl-trimethoxy-silane.
- In an embodiment of the present invention, the purity specification of nano-silicon dioxides in the step (1) is analytical degree pure reagent, and particle diameter thereof is between 35 and 45 nm.
- In an embodiment of the present invention, the weight of the fluorinated silane added in the step (1) is 33% to 40% of that of the nano-silicon dioxide.
- In an embodiment of the present invention, the degree of polymerization of the polyvinyl alcohol polymer in the step (2) is 4000 and its degree of alcoholysis is 98%.
- In an embodiment of the present invention, the weight of the modified silicon dioxide powder added in the step (2) is 4% to 8% of that of the polyvinyl alcohol polymer.
- In an embodiment of the present invention, an anionic carboxylate fluorocarbonic surfactant is further added in the step (2), and a molecular formula thereof is RF—CH2—COOH, wherein R represents a carbon chain of C6 to C10.
- In an embodiment of the present invention, the weight of the surfactant added in the step (2) is 0.2% to 0.3% of that of the polyvinyl alcohol polymer.
- A second object of the present invention is to provide a base film of modified polyvinyl alcohol prepared from the abovementioned preparation method.
- In order to achieve the abovementioned object, the present invention discloses a technical solution, as follows:
- A base film of modified polyvinyl alcohol, the base film of modified polyvinyl alcohol comprises polyvinyl alcohol polymers, nano-silicon dioxide groups and fluorinated silane groups, the base film of modified polyvinyl alcohol has a general formula shown as below:
- wherein:
- (A) groups represent the fluorinated silane groups, the fluorinated silane groups are selected from one or any mixture of dodecafluoro-heptyl-propyl-trimethoxy-silane, dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane,tetramethyl-(perfluoro-hexyl-ethyl)propyl-tri methoxy-silane and tridecafluoro-octyl-trimethoxy-silane; and
- (B) group represents nano-silicon dioxide group.
- In an embodiment of the present invention, by dyeing with an iodine solution, iodine molecules are bonded in the polyvinyl alcohol polymers, wherein the nano-silicon dioxide group connected with the fluorinated silane groups is coated on and outside the polyvinyl alcohol polymers and the iodine molecules.
- A third object of the present invention is to provide a polarizer made of the abovementioned base film of modified polyvinyl alcohol.
- In order to achieve the abovementioned object, the present invention discloses technical plans as follow: a polarizer, comprising: the abovementioned base film of modified polyvinyl alcohol; and a protection film adhered on one surface or two surfaces of the polarizing film, the protection film for example is a triacetate cellulose (TAC) film. The base film of modified polyvinyl alcohol and the protection film adhered on one surface or two surfaces of the base film of modified polyvinyl alcohol commonly form a polarizer of the base film of modified polyvinyl alcohol.
- The present invention has the following positive effects:
- 1) Heat and humidity resistances as well as stability of the base film of modified polyvinyl alcohol (PVA) are enhanced:
- Low surface energy fluorinated groups migrate and aggregate toward a surface of the PVA base film, so that the PVA base film will feature excellent water, oil and corrosion resistances. Furthermore, the bond energy of C—F bonds is strong, and the bonds are very closely arranged on an outer layer of a carbon skeleton, so that fluoride polymers have excellent stability against heat.
- 2) Mechanical performance of the PVA base film is enhanced:
- Nano-silicon dioxide has high rigidity, and has characteristics of high strength, high toughness, and high stability under high temperatures, and a 3-dimensional network is formed when combined with a high polymer chain of PVA, so that the mechanical strength, elasticity and abrasion resistance of the PVA base film are substantially enhanced. On the other hand, easily damaged iodine molecules are protected when they are coated with nano-silicon dioxides grafted with long-chain fluorinated silicon groups, so as to enhance the mechanical stability of the PVA polarizing film.
- 3) Defective percentage of polarizers is reduced:
- The acting force between polymer molecules of C—F bonds of fluorinated materials is weak and therefore has excellent sticking-resistance and surface self-cleaning performance. During later-staged adhering process of the PVA base film and other membrane layers, it can effectively prevent foreign substances from entering, as a result, the defective percentage of polarizers can be reduced.
- 4) Anti-Glare function is obtained:
- In existing processes, in order that the PVA base film is protected because of its hydrophilic property, a protective film of triacetate cellulose (TAC) with high light transmission rate, excellent waterproof characteristic and a certain degree of mechanical strength is composited on each of two sides of the PVA base film. However, the size of this type of protective film can easily be changed under high temperatures and humidity, and thus its mechanical performance is weakened and its protective performance is also affected. The present invention can substantially enhance the heat and humidity resistances as well as the mechanical strength of the PVA base film, even that the TAC film can be omitted (i.e. the PVA base film can be directly used as a polarizer). Furthermore, a certain degree of roughness can be formed on the surface of the PVA base film by controlling the sizes of nano-silicon dioxides, and thus images are diffused and reflected by the concave and convex shapes thereof, in order to prevent the light from being overly-concentrated to cause discomfort in viewing, as a result, an anti-glare function is achieved.
-
FIG. 1 is an illustration of a molecular structure of a PVA base film of an existing iodine polarizer; and -
FIG. 2 is an illustration of a molecular structure of a PVA base film of a polarizer of a preferred embodiment of the present invention. - Wherein: numeral 1 is nano-silicon dioxide group, numeral 2 is iodine molecule, numeral 3 is polyvinyl alcohol (PVA) polymer, and numeral 4 is fluorinated silane group.
- The structure and the technical means adopted by the present invention to achieve the above and other objects can be best understood by referring to the following detailed description of the preferred embodiment and the accompanying drawings, but should not be construed as limitations thereof.
- According to a preferred embodiment of the present invention, the present invention provides a base film of modified polyvinyl alcohol (PVA) and its preparation method, wherein its specific preparation steps include:
- (1) Surface graft modification of nano-silicon dioxides using fluorinated silane: 6 g of dried nano-silicon dioxide particles, 120 ml of anhydrous ethanol, 6.5 g of deionized water, 3.4 g of ammonia of 25% weight percentage and 2.0˜2.4 g of dodecafluoro-heptyl-propyl-trimethoxy-silane are added in a round-bottom flask in turn; after 1 hour of ultrasonic dispersion and then stirring in high speed for 5 hours under 40° C., processing with filtration and deposition, washing with anhydrous ethanol repeatedly; then extracting with toluene for 16 hours to remove unreacted dodecafluoro-heptyl-propyl-trimethoxy-silane; vacuum drying to a constant weight, and grinding to obtain white modified nano-silicon dioxide powders, wherein condensation polymerization occurred between hydroxyl groups (—OH) generated by hydrolysis of —OCH3 groups which are connected to Si in dodecafluoro-heptyl-propyl-trimethoxy-silane, and hydroxyl groups (—OH) on the surfaces of the nano-silicon dioxide particles, thus Si—O—Si bonds are formed. In the Si—O—Si bonds, the binding force between Si and O is stronger than that between silicon and oxygen in the connection of Si and —OH, therefore fluorinated silane can be reacted with nano-silicon dioxide particles.
- (2) The modified nano-silicon dioxide powders obtained from the step (1) and an anionic carboxylate fluorocarbonic surfactant (RF—CH2—COOH) are added to an aqueous solution of polyvinyl alcohol (PVA) polymers, and dispersed by ultrasonic at room temperature for 1 hour; then stirring in high speed for 5 hours under 40° C., in order to prepare a composite solution of polyvinyl alcohol (PVA) polymers. Steric hindering effect between particles is enhanced by the modified nano-silicon dioxides which thus can be evenly distributed in a system; on the other hand, there are still some —OH on the surface of the hydrolytic fluorinated silane and the surface of the modified nano-silicon dioxides, which can be further cross-linked and condensed with the —OH in the long molecular chain of PVA.
- (3) The composite solution of polyvinyl alcohol polymers prepared from the step (2) is poured on a surface of a casting substrate, and vacuum drying under 80° C.˜90° C. is kept until a constant weight is reached, so as to obtain a base film of modified polyvinyl alcohol (PVA).
- Wherein, the fluorinated silane is selected from dodecafluoro-heptyl-propyl-trimethoxy-silane, but not limited thereto, the fluorinated silane may be selected from one or any mixture of dodecafluoro-heptyl-propyl-trimethoxy-silane, dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane, tetramethyl-(perfluoro-hexyl-ethyl)propyl-trimethoxy-silane and tridecafluoro-octyl-trimethoxy-silane.
- Wherein, the purity specification of nano-silicon dioxides is analytical degree pure reagent, and the particle diameter is between 35 and 45 nm; the degree of polymerization of polyvinyl alcohol polymer is 4000 and its degree of alcoholysis is 98%.
- Wherein, the weight of the fluorinated silane is 33% to 40% of that of the nano-silicon dioxide.
- The weight of the modified silicon dioxide powder added in the step (2) is 4% to 8% of that of the polyvinyl alcohol polymer; the molecular formula of the anionic carboxylate fluorocarbonic surfactant added in the step (2) is RF—CH2—COOH, wherein R represents a carbon chain of C6 to C10. The weight of the added surfactant is 0.2% to 0.3% of that of the polyvinyl alcohol polymer.
- The obtained modified PVA base film is used as a substrate material. After being dyed in iodine and stretched uniaxially as conventionally used in prior arts, a modified PVA base film of a polarizer is prepared as shown in a molecular structure in
FIG. 2 , and it comprises polyvinyl alcohol (PVA)polymers 3,iodine molecules 2, a nano-silicon dioxide group 1 andfluorinated silane groups 4. - More specifically, as shown in
FIG. 2 , wherein the nano-silicon dioxide group 1 is grafted and modified by dodecafluoro-heptyl-propyl-trimethoxy-silane; after treated with a certain dispersing means, the grafted and modified nano-silicon dioxide group 1 is evenly dispersed in the PVA base film and combined with a high polymer chain of the polyvinyl alcohol (PVA)polymers 3 to form a three-dimensional network structure, and organic and inorganic nano-composite materials are obtained. The organic and inorganic nano-composite materials are incorporated with the excellent characteristics of the PVA base film and nano materials. Fluorinated materials are materials with the lowest surface energy discovered so far, low surface energy fluorinated groups migrate and aggregate towards a surface of the PVA base film, with only a very little amount, the surface of the PVA base film will feature excellent hydrophobic, oleophobic, sticking-resistant and self-cleaning performances. Furthermore, rigid nano-silicon dioxides allow the PVA base film to have excellent capabilities of heat resistance and mechanical stability. Better compatibility of organic and inorganic can be achieved from organic and inorganic nano-composite materials prepared from silicon dioxides modified by organic fluorinated silane. - More specifically, in the present invention, during a heating process, low surface energy fluorinated groups migrate and aggregate towards a surface of the PVA base film, so that the PVA base film will feature excellent water, oil and corrosion resistances. Furthermore, the bond energy of C—F bonds is strong, and the bonds are very closely arranged on an outer layer of a carbon skeleton, so that fluoride polymers have excellent stability against heat.
- The nano-silicon dioxide group has high rigidity, and has characteristics of high strength, high toughness, and high stability under high temperatures, and a 3-dimensional network is formed when combined with a high polymer chain of PVA, so that the mechanical strength, elasticity and abrasion resistance of the PVA base film are substantially enhanced. On the other hand, easily damaged iodine molecules are protected when they are coated with nano-silicon dioxides grafted with long-chain fluorinated silicon groups, which enhances the mechanical strength and stability of the PVA base film.
- The acting force between the polymer molecules of C—F bonds of fluorinated materials is weak and therefore has excellent sticking-resistance and surface self-cleaning performance. During later-staged adhering process of the PVA base film and other membrane (e.g. TAC film) layers, it may effectively prevent foreign substances from entering, as a result, the defective percentage of polarizers can be reduced.
- A certain degree of roughness can be formed on the surface of the polarizer by controlling the sizes of nano-silicon dioxides, and thus images are diffused and reflected by the concave and convex shapes, in order to prevent the light from being overly-concentrated to cause discomfort in viewing, as a result, an anti-glare function is achieved.
- The present invention has been described with a preferred embodiment thereof and it is understood that many changes and modifications to the described embodiment can be carried out without departing from the scope and the spirit of the invention that is intended to be limited only by the appended claims.
Claims (13)
1. A preparation method for a base film of modified polyvinyl alcohol, wherein comprising preparation steps of:
(1) executing surface graft modification of nano-silicon dioxides with fluorinated silane to obtain modified nano-silicon dioxide powders;
(2) adding the modified nano-silicon dioxide powders obtained from the step (1) and an anionic carboxylate fluorocarbonic surfactant to an aqueous solution of polyvinyl alcohol polymers, in order to prepare a composite solution of polyvinyl alcohol polymers; and
(3) pouring the composite solution of polyvinyl alcohol polymers prepared from the step (2) onto a surface of a casting substrate, in order to obtain a base film of modified polyvinyl alcohol;
wherein the fluorinated silane in the step (1) are selected from one or any mixture of dodecafluoro-heptyl-propyl-trimethoxy-silane, dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane, tetramethyl-(perfluoro-hexyl-ethyl)propyl-trimethoxy-silane and tridecafluoro-octyl-trimethoxy-silane, and the weight of the added fluorinated silane is 33% to 40% of that of the nano-silicon dioxide; and
wherein a molecular formula of the anionic carboxylate fluorocarbonic surfactant in the step (2) is RF—CH2—COOH, wherein R represents a carbon chain of C6 to C10, and the weight of the added modified silicon dioxide powders is 4% to 8% of that of the polyvinyl alcohol polymer.
2. The preparation method for a base film of modified polyvinyl alcohol as claimed in claim 1 , wherein the particle diameter of the nano-silicon dioxides in the step (1) is between 35 and 45 nm.
3. The preparation method for a base film of modified polyvinyl alcohol as claimed in claim 1 , wherein the weight of the surfactant added in the step (2) is 0.2% to 0.3% of that of the polyvinyl alcohol polymer.
4. A preparation method for a base film of modified polyvinyl alcohol, wherein comprising preparation steps of:
(1) executing surface graft modification of nano-silicon dioxides with fluorinated silane to obtain modified nano-silicon dioxide powders;
(2) adding the modified nano-silicon dioxide powders obtained from the step (1) to an aqueous solution of polyvinyl alcohol polymers, in order to prepare a composite solution of polyvinyl alcohol polymers; and
(3) pouring the composite solution of polyvinyl alcohol polymers prepared from the step (2) onto a surface of a casting substrate, in order to obtain a base film of modified polyvinyl alcohol.
5. The preparation method for a base film of modified polyvinyl alcohol as claimed in claim 4 , wherein the fluorinated silane in the step (1) are selected from one or the mixture of dodecafluoro-heptyl-propyl-trimethoxy-silane, dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane, tetramethyl-(perfluoro-hexyl-ethyl)propyl-trimethoxy-silane and tridecafluoro-octyl-trimethoxy-silane.
6. The preparation method for a base film of modified polyvinyl alcohol as claimed in claim 4 , wherein the particle diameter of the nano-silicon dioxides in the step (1) is between 35 and 45 nm.
7. The preparation method for a base film of modified polyvinyl alcohol as claimed in claim 4 , wherein the weight of the fluorinated silane added in the step (1) is 33% to 40% of that of the nano-silicon dioxide.
8. The preparation method for a base film of modified polyvinyl alcohol as claimed in claim 4 , wherein the weight of the modified silicon dioxide powder added in the step (2) is 4% to 8% of that of the polyvinyl alcohol polymer.
9. The preparation method for a base film of modified polyvinyl alcohol as claimed in claim 4 , wherein an anionic carboxylate fluorocarbonic surfactant is further added in the step (2), and the molecular formula thereof is RF—CH2—COOH, wherein R represents a carbon chain of C6 to C10.
10. The preparation method for a base film of modified polyvinyl alcohol as claimed in claim 9 , wherein the weight of the surfactant added in the step (2) is 0.2% to 0.3% of that of the polyvinyl alcohol polymer.
11. A base film of modified polyvinyl alcohol, wherein the base film of modified polyvinyl alcohol comprises polyvinyl alcohol polymers, nano-silicon dioxide groups and fluorinated silane groups, the base film of modified polyvinyl alcohol has the following general formula:
wherein A group is the fluorinated silane group; and B group is the nano-silicon dioxide group;
wherein the fluorinated silane group is selected from one or any mixture of dodecafluoro-heptyl-propyl-trimethoxy-silane, dodecafluoro-heptyl-propyl-methyl-dimethoxy-silane, tetramethyl-(perfluoro-hexyl-ethyl)propyl-trimethoxy-silane and tridecafluoro-octyl-trimethoxy-silane.
12. The base film of modified polyvinyl alcohol as claimed in claim 11 , wherein iodine molecules are bonded in the polyvinyl alcohol polymers, wherein the nano-silicon dioxide group connected with the fluorinated silane groups is coated on the polyvinyl alcohol polymers and the iodine molecules.
13. The base film of modified polyvinyl alcohol as claimed in claim 11 , wherein the base film of modified polyvinyl alcohol and a protection film adhered on one surface or two surfaces of the base film of modified polyvinyl alcohol commonly form a polarizer.
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US15/015,153 US20160145402A1 (en) | 2011-08-16 | 2016-02-04 | Base film of modified polyvinyl alcohol polymer |
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CN2011102340451A CN102432899A (en) | 2011-08-16 | 2011-08-16 | Modified polyvinyl alcohol base film, preparation method thereof and polaroid |
PCT/CN2011/080581 WO2013023403A1 (en) | 2011-08-16 | 2011-10-09 | Modified polyvinyl alcohol-based film and preparation method therefor and polarizer thereof |
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JP2018072818A (en) * | 2016-10-25 | 2018-05-10 | 日本合成化学工業株式会社 | Aqueous solution of polyvinyl alcohol-based resin, laminate, method for producing laminate, optical polyvinyl alcohol-based film, polarizing film with thermoplastic film, polarizing film and polarizing plate |
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Owner name: SHENZHEN CHINA STAR OPTOELECTRONICS TECHNOLOGY CO. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:XU, RUI;ZHANG, WEIWEI;HUANG, HONGQING;AND OTHERS;REEL/FRAME:027369/0689 Effective date: 20111024 |
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