WO2021066401A1 - 용융 압출식 편광필름 - Google Patents

용융 압출식 편광필름 Download PDF

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WO2021066401A1
WO2021066401A1 PCT/KR2020/013061 KR2020013061W WO2021066401A1 WO 2021066401 A1 WO2021066401 A1 WO 2021066401A1 KR 2020013061 W KR2020013061 W KR 2020013061W WO 2021066401 A1 WO2021066401 A1 WO 2021066401A1
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polarizing film
resin
dichroic dye
film
polarizing
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PCT/KR2020/013061
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English (en)
French (fr)
Korean (ko)
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조덕재
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조덕재
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Priority claimed from KR1020190121243A external-priority patent/KR102231814B1/ko
Priority claimed from KR1020190121248A external-priority patent/KR102215047B1/ko
Application filed by 조덕재 filed Critical 조덕재
Priority to CN202080068688.0A priority Critical patent/CN114555327A/zh
Publication of WO2021066401A1 publication Critical patent/WO2021066401A1/ko

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms

Definitions

  • the present invention relates to a resin composition of a melt extrusion type dispersed polarizing film, a polarizing filler using the same, and a method of manufacturing the polarizing film. More specifically, through the melt extrusion process, the resin (C) containing the dichroic dye (B) is dispersed inside the thermoplastic resin (A), and the dichroic dye (B) is oriented through the dry stretching process, and the orientation Melt extrusion as a polarizing film characterized in that the resin (C) containing the dichroic dye (B) is dispersed in a certain direction continuously or discontinuously in the interior of the thermoplastic resin (A) in a needle-shaped needle shape. And a resin composition of a polarizing film and a method of manufacturing a polarizing film made through a uniaxial or biaxial stretching process or simultaneous biaxial stretching.
  • liquid crystal displays must use two polarizing films in principle, and organic light emitting diodes also use one polarizing film to increase the contrast ratio.
  • Polarizing films can be largely divided into dye-type polarizing films and polarizing films using dichroic dyes.
  • polarizing films using dichroic dyes that is, iodine
  • the manufacturing method of a wet dichroic dye polarizing film is to prepare a non-stretched film using a polyvinyl alcohol resin, and iodine, potassium iodide, or zinc iodide is dissolved in a water bath at a temperature of 30 to 60°C. It is manufactured by making it act as a polarizer, and wastewater is also generated during this process.
  • a protective film and a retardation film are attached to protect the polarizer.
  • TAC film As a protective film, TAC film, PMMA film, COP film, PET film, etc. are typically used.
  • the protective film is manufactured through a separate process. Depending on the characteristics of the film, a separate adhesive or adhesive may be used. This multi-step manufacturing process requires not only high manufacturing costs, but also the quality of each film.
  • the inventors of the present invention are dispersing the resin (C) containing the dichroic dye (B) in the thermoplastic resin (A) through a melt extrusion process, and a dichroic dye through a dry stretching process.
  • (B) is oriented and the resin (C) containing the oriented dichroic dye (B) is dispersed in a certain direction continuously or discontinuously in the interior of the thermoplastic resin (A) in a needle-shaped needle shape.
  • the thermoplastic resin (A) not only serves as a carrier for the resin (C) containing the dichroic dye (B), but also protects it.
  • An integrated polarizing film could be invented by making the film's resin and component the same or similar.
  • the present invention is a protective film separate from dyeing of dichroic dyes by inventing a polarizing film having a form in which the resin (C) containing the dichroic dye (B) is continuously or discontinuously dispersed in the thermoplastic resin (A). It is to provide a polarizing film with excellent quality such as epoch-making cost reduction and stains through a single melt extrusion process and dry stretching process without the need for a manufacturing process.
  • thermoplastic resin (A) must have a transmittance and a refractive index suitable for a polarizing film.
  • Resins that can be used as materials for polarizing films include polymethyl methacrylate (PMMA), triacetyl cellulose (TAC), polypropylene (PP), cycloolefin polymer (COP), polyethylene terephthalate (PET), and polycarbonate ( PC), Amorphopolyethylene terephthalate (APET), Polypropylene terephthalate (PPT), Polybutylene terephthalate (PBT), Polyethylene naphthalate (PEN), Polyethylene terephthalate glycerol (PETG), Polycyclohexylene dimethylene Terephthalate (PCTG), cycloolefin copolymer (COC), polyacrylate (PA), polystyrene (PS), polyester sulfone (PES), polyethylene (PE), silicone resin, modified epoxy resin,
  • the component of the resin (C) containing the dichroic dye is preferably an olefin-based resin that can facilitate the orientation of the dichroic dye, and in particular, polyvinyl alcohol (PVA), which is used in conventional polarizing films, is the best.
  • PVA polyvinyl alcohol
  • the polarizing film it is necessary to minimize the refraction of light.
  • an interface is formed between the resin and the resin, and when the difference in refractive index of each resin is large, some light is reflected at the interface, which appears as a loss of light. In order to reduce this, it is good to eliminate or minimize the difference in refractive index of each resin.
  • the resin containing the dichroic dye is polyvinyl alcohol (PVA)
  • the refractive index of polyvinyl alcohol is about 1.50
  • triacetylcellulose TAC, refractive index 1.50
  • polymethyl methacrylate It is recommended to select one or more resins from PMMA, refractive index 1.49), polypropylene (PP, refractive index 1.47), and cycloolefin polymer (COP, refractive index 1.50).
  • a resin capable of melt extrusion at a temperature lower than the thermal decomposition temperature of polyvinyl alcohol 220°C is preferable.
  • these include polymethyl methacrylate (PMMA), polypropylene (PP), cycloolefin polymer (COP), and amorphous polyethylene terephthalate (APET).
  • PMMA polymethyl methacrylate
  • PP polypropylene
  • COP cycloolefin polymer
  • APET amorphous polyethylene terephthalate
  • polymethyl methacrylate (PMMA) is optimal as the thermoplastic resin (A), and as a dichroic dye, one or more of iodine, potassium iodide, and zinc iodide can be selected and used.
  • a dichroic dye When using a dichroic dye, it is recommended to dissolve it in glycerin, diglycerin, triglycerin, etc. When dissolving, it is necessary to adjust the mixing ratio of iodine, potassium iodide, and zinc iodide in order to increase the dissolved concentration.
  • PMMA resin used in the present invention is a representative resin, since polymethyl methacrylate (PMMA) is also a part of the acrylic resin, the acrylic resin will be described in detail.
  • the acrylic resin used in the present invention refers to a resin prepared by polymerizing an acrylate-based monomer, and is characterized in that it does not contain a ring structure in the main chain.
  • acrylate-based monomer there is no ring structure in the main chain, and it is composed of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and benzyl methacrylate. Any one or more selected from the group consisting of may be used.
  • the acrylic resin may further include a styrene-based monomer.
  • the glass transition temperature of the acrylic resin is 90 to 120°C. When the glass transition temperature is less than 90°C, the thermal stability of the film is deteriorated.
  • the weight average molecular weight of the acrylic resin is 90,000 to 160,000 g/mole. If the weight average molecular weight is less than 90,000 g/mole, fractures frequently occur during the film manufacturing process, resulting in a problem in establishing process conditions as well as poor mechanical properties. When the weight average molecular weight exceeds 160,000 g/mole, extrusion processing becomes difficult.
  • Polyvinyl alcohol (PVA) resins are used as raw materials for various moldings such as films and sheets, and various plasticizers are used in these moldings for the purpose of softening polyvinyl alcohol resins.
  • the plasticizer's performance is (1) to make PVA resin flexible and to prevent thermal decomposition by lowering the processing temperature during extrusion (2) to have low volatility and long-term function (3) to have similar compatibility with PVA and optical refractive index characteristics. And keeping the optical properties good.
  • the plasticizer of PVA glycerin satisfies the above functions relatively well, but diglycerin, triglycerin, etc. can also be used.
  • triacetin dibutyl sebacate (yoon), diethyl phthalate (DEP), di phthalate It consists of butyl (DBP), ethyl phthalate, methyl phthalate, dipropyl phthalate, triethyl citrate (TEC), and combinations thereof, and is present in the range of 5 to 20 parts by weight of the composition, more preferably 8 to 15 parts by weight. good.
  • glycerin As for the content of glycerin, it is preferable to contain 8 parts by weight or more of glycerin based on 100 parts by weight of the PVA resin. Glycerin and diglycerin can be used alone or in combination of two or more.
  • the degree of polymerization of PVA is not particularly limited, but a degree of polymerization of 100 or more and 10,000 or less is preferable. In particular, since it is used for dispersion, it is also possible to use a PVA resin having a lower polymerization degree than a general PVA film.
  • the degree of saponification is preferably 90 mole% or more, but 99.0 mole% or more is good for the degree of polarization, and more preferably 99.9 mole% or more.
  • a method of swelling and dyeing an unstretched film made of a PVA material in a hot water state in which dichroic dyes such as iodine and potassium iodine are dissolved Therefore, it is used by dissolving iodine and potassium iodide in water. Since water cannot be used in the melt extrusion method, it is used by dissolving in one or more substances such as glycerin, diglycerin, triglycerin, etc. instead of water.
  • the method of raising the temperature of the plasticizer and the mixing ratio of iodine, potassium iodide, and zinc iodide can be adjusted to be used.
  • the ratio (B/A) of iodine (A) and potassium iodine (B) is preferably 0.5 to 100 or less.
  • the layer structure of the polarizing film is composed of a core layer constituting the polarizer in the case of the lower polarizing plate of the liquid crystal, and a retardation film layer on the upper polarizer protective layer in the case of the lower polarizing plate, and the core layer in the case of the upper polarizing plate, and It consists of a protective film layer.
  • the upper and lower protective films and the retardation film may be made of the same material, or different types of films may be used. In the present invention, the design was made of PMMA material. In the case of coextrusion, when the core layer is present and the skin layer is present above and below the skin layer, production is stabilized when the thickness of the top and bottom of the skin layer is the same.
  • the thickness of the skin layer may be 1 ⁇ m or less in the case of coextrusion.
  • the thickness of the skin layer can be varied depending on the conditions of the LCD to be used. In other words, it is also possible to make the thickness thinner in mobiles and tablet PCs. For monitors and TVs, there are relatively few restrictions on the thickness.
  • the total thickness of the polarizing film is 7 to 300 ⁇ m.
  • Resin (C) containing dichroic dyes such as iodine, potassium iodide, and zinc iodide is a resin that has been tested for polyvinyl alcohol (PVA). Iodine or the like is impregnated in PVA and extruded through a melt extruder with PMMA resin. At this time, the PMMA resin of the skin layer is also coextruded, so if the content of the PVA resin is too high, peeling occurs at the interface due to the effect of heterogeneous resins between the core layer and the skin layer.
  • the content of the PVA resin is preferably 50% or less based on the volume of the total resin present in the core layer. In other words, if PMMA is used as the sea and PVA is present in the form of an island, the delamination phenomenon can be eliminated. That is, it should be less than 50% by volume, more preferably less than 45%.
  • the dichroic dye-containing resin PVA is blended like PMMA, its shape has an amorphous shape. As this is cooled and fixed after a dry uniaxial or biaxial stretching process or simultaneous biaxial stretching, it exists in the form of a needle-shaped needle inside the polarizing film.
  • the length varies depending on the conditions of the melt extruder and is also affected by the draw ratio. It is 2.0 ⁇ m or more as confirmed by the present inventors.
  • the polarizing film may be subjected to various surface treatment processes depending on the purpose of use.
  • the first is lamination with retardation film. Due to the difference in optical properties, the polarizing film may or may not be laminated with other retardation films.
  • Types of retardation film include PMMA film, TAC film, COP film, and PET film.
  • anti-reflection to prevent the reduction of the contrast ratio (CONTRAST RATIO) due to reflection (ANTI-REFLECTION)
  • ANTI-REFLECTION On the surface of the polarizing film, anti-reflection (ANTI-REFLECTION) to prevent the reduction of the contrast ratio (CONTRAST RATIO) due to reflection (ANTI-REFLECTION), low It can be treated such as LOW-REFLECTION treatment, ANTI-STASTIC treatment to prevent dust generation to protect the liquid crystal array, and hard coating to protect the surface of the polarizing film.
  • an ultraviolet (UV) curing agent may be used depending on the surface treatment conditions and may be subjected to an ultraviolet treatment process.
  • Amorphous inorganic particles are sometimes used when particles are mixed with a solvent and a binder for surface treatment of the film, but organic particles are preferably used for accurate refractive index control.
  • organic particles the more uniform the particle size distribution, the easier it is to design a binder and a solvent.
  • the spherical type of particles is good, and acrylic, silicone, and polystyrene are typical.
  • an acrylic series is more preferable.
  • the size of the particles varies depending on the required physical properties of the polarizing film, but the diameter is preferably 0.1 to 20 ⁇ m.
  • the polarizing film of the present invention can be used for LCD panels and OLED panels, and can be used for final products such as LCD products and OLED products.
  • the polarizing film manufactured through the present invention can achieve superior manufacturing cost reduction compared to the conventional manufacturing method by coextruding the core layer serving as a polarizing function and the skin layer serving as a polarizer protection function at the same time.
  • the thickness increases, so that the manufacturing processability is improved and the overall thickness of the polarizing film can be drastically reduced.
  • the representative drawing (Fig. 1) is a state in which a dichroic dye, especially three iodine molecules 3 or five 4, is oriented in a thermoplastic resin 1, and is contained in a separate resin 2, and a protective layer is arranged on the upper layer 5 lower layer 6. .
  • FIG. 2 shows that the dispersed polarizing film 7 and the retardation film 8 are laminated to be laminated up and down on a glass liquid crystal 9.
  • FIG. 3 is a result of laminating a dispersion-type polarizing film 7 and a reflective polarizing film 10 using an adhesive or adhesive 11.
  • FIG. 5 shows a non-penetrating coating 13 using particles 14 on a dispersed polarizing film 7.
  • iodine particles are dispersed in the PVA resin in the form of 3 atom continuous orientation (I3) or 5 atom continuous orientation (I5) for polarization.
  • iodine In order to achieve polarization, iodine must be uniformly oriented in one axis direction. As a method to achieve this, the polymer molecules and iodine molecules inside the PVA are oriented through the stretching process.
  • PVA resin is hydrophilic and easily swells in water and is also easy to draw.
  • iodine particles In the swollen state, iodine particles also enter the molecular chain; however, depending on the molecular weight of PVA, it may dissolve when swelling in water, and the density of iodine particles varies from site to site, causing stains in many cases.
  • thermoplastic resin is used as a method by a melt extrusion method.
  • resins that can be used for polarizing films are acrylic resins, polymethyl methacrylate (PMMA), triacetyl cellulose (TAC), polypropylene (PP), cycloolefin polymer (COP), and polyethylene terephthalate.
  • PET Polycarbonate
  • APET Amorphous Polyethylene terephthalate
  • PPT Polypropylene terephthalate
  • PBT Polybutylene terephthalate
  • PEN Polyethylene naphthalate
  • PCTG Polycyclohexylenedimethylene terephthalate
  • COC cycloolefin copolymer
  • PA polyacrylate
  • PS polystyrene
  • PS polyester sulfone
  • PE polyethylene
  • silicone resin modified epoxy Suzy and the like.
  • the polarizing function resin used in the present invention is a resin whose polyvinyl alcohol has been tested.
  • the refractive index difference of the resin used in the polarizing film is large, light reflection occurs at the interface between the resin and the resin, which leads to a decrease in transmittance and a decrease in polarization rate, thereby deteriorating the value as a polarizing film. In order to solve this problem, it is good to minimize the difference in refractive index of the resin used.
  • the refractive index of the PVA resin is 1.50
  • a resin having a refractive index of 1.50 or a similar refractive index is preferable.
  • the corresponding resin is TAC resin.
  • TAC resin has a refractive index of 1.50, which is excellent optically as it is consistent with PVA resin.
  • TAC resin has the disadvantage of being hydrophilic and very expensive, and is not suitable for melt extrusion process. not.
  • the resin that approaches this with another resin is an acrylic-based PMMA resin.
  • PMMA resin has a refractive index of 1.49, almost similar to PVA resin, and has a light transmittance of 94%, which is a very good material for optics. For this reason, PMMA resin is widely used as a material for light guide plates and diffusion plates.
  • PMMA resin is a thermoplastic resin and is very suitable for use in melt extrusion.
  • PMMA resin has a glass transition temperature of 99°C and is excellent in heat resistance.
  • PVA resin is a material that has been certified as a polarizer functional resin for a polarizing film.
  • resins with a degree of saponification of 99.9 mole% or more have excellent performance in polarization function.
  • a polymerization degree of 500 to 5000 is usually preferred.
  • the degree of polymerization is 1700 to 3000, more preferably 2100 to 2700.
  • PVA resin is not suitable for melt extrusion process because its melting temperature and pyrolysis temperature are similar. However, it is possible to lower the temperature of the melt extruder by using a plasticizer, and it is advantageous in terms of retention in the process by dispersing it inside the PMMA resin.
  • Polyhydric alcohol ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, sorbitol, ethylene oxide, glycerin, diglycerin, triglycerin, and the like are used as plasticizers of the PVA resin.
  • glycerin is the best.
  • One glycerin can be used, but more than two can be used.
  • Glycerin may be used in an amount of 2 to 100 parts by weight based on 100 parts by weight of the PVA resin, but 5 to 30 parts by weight, more preferably, 15 to 25 parts by weight.
  • plasticizers include triacetin, dibutyl sebacate (yoon), diethyl phthalate (DEP), dibutyl phthalate (DBP), ethyl phthalate, methyl phthalate, dipropyl phthalate, triethyl citrate (TEC), and combinations thereof.
  • the composition is preferably in the range of 5 to 20 parts by weight, and more preferably in the range of 8 to 15 parts by weight.
  • 100 parts by weight or more may be used in some cases. In this case, a dysfunction may appear in the post process.
  • the refractive index is 1.47, which is similar to that of PVA resin, so light loss is relatively small.
  • Glycerin has a boiling point of 290° C., and thus has a relatively small bubble problem during the extrusion process.
  • Glycerin is a substance having three -OH groups, which are hydrophilic groups, and plays a good role as a solvent that dissolves iodine, potassium iodine, and zinc iodide instead of water.
  • Iodine is the most important material that performs a polarizing function in a polarizing film using a dichroic dye.
  • Iodine is a trimolecular iodine (I3), a 5-molecular iodine (I5), etc., and is present between the PVA molecules. Since iodine is a single substance and has a limited concentration in water or glycerin, the dissolution rate of iodine can be increased by mixing iodine with potassium iodide or zinc iodide. The mixing ratio of iodine and potassium iodide is 0.5 to 100 or less of potassium iodide/iodine by weight. In order to improve the polarization function, it is most important to orient iodine molecules uniformly in one axis direction.
  • the weight of iodine is 1 to 3 parts by weight based on 100 parts by weight of glycerin.
  • potassium iodide is preferably 9 to 27 parts by weight, more preferably 10 to 20 parts by weight.
  • Boric acid is preferably 1.0 to 3.0 parts by weight, and even more preferably 1.5 to 2.5 parts by weight.
  • the temperature of the mixed solution is dispersed at 30 to 70°C.
  • glycerin For the plasticity of the PVA resin, 5 to 50 parts by weight of glycerin, more preferably 10 to 40 parts by weight and even more preferably 15 to 25 parts by weight of 100 parts by weight of the PVA resin.
  • Potassium iodide is preferably 2 to 4 parts by weight. 0.22 to 0.44 parts by weight is good
  • the boric acid is preferably 0.25 to 0.55 parts by weight.
  • the PMMA resin and PVA resin are melt-extruded at a high temperature of 170 to 180°C, if there is moisture, breakage due to bubbles may occur, and the quality of the polarizing film is also problematic. To eliminate this, the PMMA resin and PVA resin are dried and moisture is dried. It is better to set it below 50 ppm.
  • the drying temperature is preferably 15 hours or more at 80°C for PMMA resin and 20 hours or more at 70°C for PVA resin.
  • the core of the present invention is whether or not the iodine-containing PVA resin is uniformly dispersed inside the PMMA resin, depending on whether it is successful or not.
  • a method of dispersing it is very important to make the viscosity of the two types of resins similar.
  • the viscosity similarity with PMMA resin is important below 180°C, which is the thermal stability temperature of PVA resin. If the difference in polymer viscosity is large, the dispersibility of iodine-containing PVA in the PMMA may become uneven.
  • the content of the iodine-containing resin is preferably 45% or less based on the volume of the core layer. In order to increase the dispersibility, it is relatively advantageous to increase the viscosity of these polymers.
  • the weight average molecular weight of PMMA for melt extrusion is preferably 100,000 to 150,000.
  • the iodine-containing PVA polymer In melt extrusion, the iodine-containing PVA polymer is dispersed in an amorphous shape during the melting process. At this time, since the skin polymer is PMMA, the core layer must have PMMA as the sea and iodine-containing PVA in the form of islands to eliminate the peeling phenomenon from the skin layer.
  • the melting temperature of the PMMA resin used for skin may be melt-extruded at 180 to 190°C.
  • the core layer polymer and the skin layer polymer are combined.
  • the thickness of the core layer and the thickness of the skin layer can be adjusted.
  • the thickness of the core layer is about 5 to 20 ⁇ m, as it functions as a polarizing function.
  • the skin layer it may be 2 ⁇ m to 50 ⁇ m for mobile and tablic PCs, and 80 to 200 ⁇ m or more for large TVs.
  • a pinning wire, etc. should be used for the casting method, which has an advantage in controlling the thickness.
  • the calendar method controls the thickness of the unstretched film by the interval between the two rolls.
  • the thickness uniformity is lower than that of the casting method, but the optical properties are improved because there is no additional additive.
  • the iodine-containing PVA resin serving as a polarizer becomes an amorphous shape.
  • the temperature condition of the calendar roll is important.
  • it is operated at a glass transition temperature of 10 to 30°C.
  • PMMA In the case of PMMA, it is operated at 70 to 90°C, which is lower than the glass transition temperature of 99°C.
  • MDO (species) stretching is the most important process in which molecules such as iodine, a polarizing function, are aligned, and consists of a preheating roll, a drawing roll, and a cooling roll.
  • the temperature of the preheating roll can be increased from the glass transition temperature to +30°C.
  • the preheating roll temperature is maintained at about 99 to 140°C.
  • Stretching takes place between rolls and rolls, and it is preferable that the stretching rolls have a diameter of about 100 to 300 mm for uniformity of stretching.
  • the stretching ratio is generally 4 to 10 times, and more preferably 5 to 7 times.
  • Cooling is operated below the glass transition temperature. In the present invention, it is operated at 99 to 30°C.
  • TDO (transverse) stretching is one of the most important processes in which molecules such as iodine, a polarizing function, are aligned.
  • TDO transverse
  • MDO longitudinal
  • the stretching ratio is better as the degree of orientation of the polarizing function is increased.
  • the stretching is performed 4 to 10 times, and more preferably, 5 to 7 times stretching is preferable. It operates at a temperature of 30 to 160°C, and it is also possible to stretch using a simultaneous biaxial stretching machine instead of stretching MDO to TDO.
  • Heat setting is done using a tenter.
  • the temperature is set to 120 to 150°C, about 20°C higher than the glass transition temperature.
  • the thick part of the edge is removed by slitting and wound around a 6-inch plastic paper tube.
  • an acrylic resin is dissolved in a methyl ethyl ketone solvent, and amorphous silica gel having an average particle diameter of 5 ⁇ m or more is mixed and coated, dried, and UV cured.
  • amorphous silica gel with an average particle diameter of 5 ⁇ m or less is mixed, and in high-resolution products, spherical organic particles of 5.0 ⁇ m or less with excellent particle size distribution are used.
  • hard coating or non-infiltrating coating is applied on the top of the polarizing film of the present invention. If a multilayer coating of three or more layers of a high-refractive resin and a low-refractive resin is applied thereon, a reflectance of ⁇ 0.1 to 0.3% can be realized. Preferably, about 5 layers of high-refractive-index resin and low-refractive-index resin are recommended. If the multilayer coating is made into 6 or more layers, the reflectance is further lowered, but there is a problem that the coating cost is increased. Low-reflective anti-reflective or hard coating is applied to the top of the polarizing film of the present invention, and then a low-refractive mixed resin is coated and UV cured. The reflectance is generally 0.7 to 1.7%.
  • the polarizing film is located at the outermost part of the liquid crystal display. Therefore, high definition, abrasion resistance, and scratch resistance are required. For this, hard coating is performed.
  • the lower polarizing film of the liquid crystal panel comes into contact with the backlight unit. At this time, friction with the uppermost film of the backlight unit may occur, and scratches may occur on the polarizing film or the backlight unit film. To prevent this, apply a scratch-resistant coating.
  • an acrylic resin is dissolved in a solvent such as methyl ethyl ketone, coated with particles of 20 ⁇ m or less, dried, and cured with ultraviolet rays. Particles of 20 ⁇ m or less are good, but particles of 2.0 ⁇ m or less may be used. The particles have a spherical shape such as acrylic, polystyrene, or polysilicon.
  • FIGS. 4 and 5 The contents of the scratch-resistant coating are shown in FIGS. 4 and 5.
  • the reflective polarizing film may be multilayered or a distributed reflective polarizing film may be used.
  • the contents of the reflective polarizing film laminate are shown in FIG. 3.
  • the retardation film includes a PMMA film, a TAC film, a COP film, a PET film, and the like, and may be used in combination with the above film according to the intended use.
  • FIG. 5 shows a non-penetrating coating 13 using particles 14 on a dispersed polarizing film 7.
  • PMMA (LG MMA, IF850) resin was dried at a drying temperature of 80° C. for 15 hours to prepare a dry resin having a water transport rate of 50 ppm.
  • PVA Karl Fischer, JC-25, saponification degree 99.98 mol%, polymerization degree 2400 resin was dried at a drying temperature of 70° C. for 20 hours to prepare a dry resin having a moisture content of 50 ppm.
  • a mixed solution was prepared by dissolving 1.7 parts by weight of iodine, 15.0 parts by weight of potassium iodide, and 2.0 parts by weight of boric acid at 50°C in 100 parts by weight of glycerin.
  • the dried PMMA resin, the dried PVA resin, and the mixed solution were added to 70 parts by weight of the dry PVA resin and 20 parts by weight of the mixed solution based on 100 parts by weight of PMMA into a single melt extruder and melted at 170°C.
  • the dried PMMA resin was melted through a single melt extruder at a temperature of 180°C.
  • the core polymer and the skin polymer were extruded through a feed block and a T-Die so that the layer ratio was 30:40:30. At this time, the width of the T-Die was set to 2.0 meters.
  • the coextruded polymer was cooled on three horizontal calender rolls (2.3 meters in width, 450 mm in diameter). At this time, the temperature of the calendar roll was maintained at 80°C.
  • the thickness of the unrolled film in the calendering process was controlled to 360 ⁇ m.
  • the line speed of the calendaring process was controlled at 5.0 meters per minute.
  • the unstretched film was preheated while controlling 10 preheating rolls of 300 mm in diameter in the range of 120 to 125°C.
  • the preheated film was stretched through two stretching rolls having a diameter of 200 mm. The distance between the stretching rolls was 15 mm, and the film was passed from the top of the stretching front roll to the lower portion of the stretching rear end roll. At this time, stretching was performed 6 times while heating between the stretching rolls through an infrared heater. After that, the stretched film was cooled through eight cooling rolls. At this time, the temperature of the roll was controlled at 30 to 90°C.
  • the stretched film was heat-set through a tenter.
  • the temperature of the tenter was controlled at 30°C to 160°C.
  • the above film was edge-cut, wound on a 6-inch plastic paper tube, and sample was collected to evaluate the physical properties.
  • the thickness of the produced polarizing film was 60 ⁇ m. The results of the physical properties are shown in the table.
  • Example 1 the ratio of the skin layer to the core layer was 1:8:1 and the thickness of the unstretched film was 180 ⁇ m. The remaining conditions were the same, and the film thickness after stretching was 30 ⁇ m. I did it.
  • Example 2 the ratio of the skin layer and the core was 3:4:3, and the thickness of the unstretched film was 180 ⁇ m. The rest were the same as in Example 2, and the film thickness after stretching was 30 ⁇ m.
  • Example 3 the ratio of the skin layer and the core layer was 4:2:4, the thickness of the unstretched film was 150 ⁇ m, and the film thickness after stretching was 25 ⁇ m.
  • Example 1 a mixed solution was prepared in which 3.4 parts by weight of iodine, 30.0 parts by weight of potassium iodide, and 2.0 parts by weight of boric acid were dissolved at 50° C. in 100 parts by weight of glycerin. The rest were prepared in the same conditions.
  • Example 5 the thickness of the unstretched film was set to 180 ⁇ m and the film thickness after stretching was set to 30 ⁇ m.
  • Example 3 the ratio of the skin layer and the core layer was 11:3:11, the unstretched film thickness was 150 ⁇ m, and the film thickness after stretching was 25 ⁇ m.
  • Example 1 the thickness ratio of the skin layer and the core layer was 1:8:1, the unstretched film thickness was set to 360um, and the film thickness after stretching was set to 60 ⁇ m.
  • Example 1 60 3:4:3 1.7+15.0 99.9 43.1
  • Example 2 30 1:8:1 1.7+15.0 99.9 43.0
  • Example 3 30 3:4:3 1.7+15.0 99.7 44.1
  • Example 4 25 4:2:4 1.7+15.0 97.9 45.2
  • Example 5 60 3:4:3 3.4+30.0 99.9 40.3
  • Example 6 30 3:4:3 3.4+30.0 99.9 43.1 Comparative Example 1 25 11:3:11 1.7+15.0 96.9 47.4 Comparative Example 2 60 1:8:1 1.7+15.0 99.9 35.1
  • Polarization degree and transmittance measurement method Japan Spectroscopic Co., Ltd. (JASCO) product V-7100, model name; VAP-7070 (SP)
  • the polarization and transmittance used are based on the wavelength of light of 550 nm.
  • the polarizing film of the present invention Since the polarizing film of the present invention has excellent polarization function, it can be widely used in fields requiring a polarization function. Specifically, optical devices such as cameras, microscopes, glasses, automobile exterior materials, mobile phones, computer monitors, liquid crystal displays (LCDs), etc. It can be widely used in technologies such as liquid crystal display devices, projection displays, plasma displays, and organic light-emitting diodes (OLEDs), which require a degree of polarization.
  • optical devices such as cameras, microscopes, glasses, automobile exterior materials, mobile phones, computer monitors, liquid crystal displays (LCDs), etc. It can be widely used in technologies such as liquid crystal display devices, projection displays, plasma displays, and organic light-emitting diodes (OLEDs), which require a degree of polarization.
  • LCDs liquid crystal displays
  • OLEDs organic light-emitting diodes

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