WO2014024855A1 - 偏光子保護用ポリエステルフィルム、偏光板および液晶表示装置 - Google Patents
偏光子保護用ポリエステルフィルム、偏光板および液晶表示装置 Download PDFInfo
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- WO2014024855A1 WO2014024855A1 PCT/JP2013/071201 JP2013071201W WO2014024855A1 WO 2014024855 A1 WO2014024855 A1 WO 2014024855A1 JP 2013071201 W JP2013071201 W JP 2013071201W WO 2014024855 A1 WO2014024855 A1 WO 2014024855A1
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- polarizer
- resin
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- polyester film
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- 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
-
- 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
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives 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; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—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
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
Definitions
- the present invention relates to a polyester film for protecting a polarizer used for protecting a polarizer. Specifically, the present invention relates to a polyester film for protecting a polarizer having high transmittance and excellent adhesion to the polarizer.
- polarizing plates are arranged on both sides of a glass substrate that forms the surface of the liquid crystal panel due to the image forming method.
- the polarizing plate generally has a configuration in which a polarizer protective film is bonded to both surfaces of a polarizer made of a dichroic material such as a polyvinyl alcohol film and iodine via a hydrophilic adhesive such as a polyvinyl alcohol resin.
- a protective film used for protecting a polarizer a triacetyl cellulose film has been conventionally used from the viewpoint of optical properties and transparency.
- triacetyl cellulose is not sufficiently durable, and when a polarizing plate using a triacetyl cellulose film as a polarizer protective film is used at high temperature or high humidity, the performance of the polarizing plate such as the degree of polarization and hue deteriorates. There is a case. In recent years, there has been a demand for thinning the polarizing plate in order to cope with the thinning of the display. However, from the viewpoint of maintaining moisture barrier properties, there has been a limit to thinning the triacetyl cellulose film. Therefore, it has been proposed to use a polyester film as a polarizer protective film having durability and moisture barrier properties (see Patent Documents 1 to 5).
- the triacetyl cellulose film used as a polarizer protective film is subjected to alkali treatment on the surface, and has an extremely high affinity with a hydrophilic adhesive. Therefore, the protective film made of a triacetyl cellulose film has extremely high adhesiveness with a polarizer coated with a hydrophilic adhesive.
- the polyester film has insufficient adhesion to the hydrophilic adhesive, and this tendency becomes more prominent particularly in the case of a polyester film having orientation by a stretching treatment. Therefore, Patent Documents 1 to 3 and 5 propose providing a polyester film with an easy-adhesion layer in order to improve the adhesion to the polarizer or the hydrophilic adhesive applied to the polarizer.
- the polyester film has a low affinity for water, and this tendency is particularly remarkable in the polyester film having an aromatic dicarboxylic acid as a dicarboxylic acid component. Moreover, the polyester film which has crystal orientation by extending
- the polarizer and the adhesive applied on the polarizer are mainly composed of a polyvinyl alcohol-based resin and have high hydrophilicity. Due to the difference in properties, the polyester film, the polarizer, and the adhesive have low affinity, and it has been difficult to firmly bond the two. Therefore, even the polyester film having the easy-adhesion layer disclosed in Patent Documents 1 to 3 and 5 has not yet obtained sufficient adhesion as compared with the triacetyl cellulose film.
- the polarizing film using a polyester film as the polarizer protective film has a higher refractive index than the triacetyl cellulose film. There was a problem that the light was scattered by a large amount and the transmittance was lowered.
- an object of the present invention is to provide a means for firmly bonding a polyester film and a polarizer or a polyvinyl alcohol-based resin layer such as an adhesive applied on the polarizer, and further, a light transmittance. It is providing the polyester film for polarizer protection with high.
- the inventors of the present invention have made extensive studies and examinations to solve the above problems, and have a polyester resin having a high affinity with a polyester film and a polyvinyl alcohol resin having a high affinity with a polyvinyl alcohol resin layer and a crosslinking agent. It came to the idea of providing the layer to contain between a polyester film and a polyvinyl alcohol-type resin layer. However, the present inventors have found that the function of closely adhering the polyester film and the polyvinyl alcohol-based resin layer due to each component cannot be sufficiently exhibited by simply combining these components.
- the present inventors adopted a polyester resin having a certain acid value as the polyester resin in the above concept, and further, polyvinyl alcohol having a certain degree of saponification as the polyvinyl alcohol resin. It has been found that by using a system resin, it is possible to effectively exert the adhesive action of each component with a resin layer having high affinity.
- the present inventors have adopted a cross-linking agent having high reactivity with a hydroxyl group, so that a polyester film and a polyvinyl alcohol resin layer such as a polarizer and an adhesive are used. It has been found that it is possible to adhere to each other more firmly.
- the average reflectance of the absolute reflectance at a wavelength of 400 to 700 nm on the surface opposite to the surface provided with the easy adhesion layer with the polarizer is controlled to 6% or less, thereby protecting the polarizer with high transmittance. It has been found that a polyester film can be provided. Based on these findings, the present inventors have made further studies and considerations, and have invented the present invention.
- Item 1 A polyester film having an easy adhesion layer with a polarizer on one side, wherein the easy adhesion layer contains a polyester resin (A), a polyvinyl alcohol resin (B), and a crosslinking agent (C),
- the acid value of the resin (A) is 20 KOH mg / g or less
- the saponification degree of the polyvinyl alcohol resin (B) is 60 to 85 mol%
- a polyester film for protecting a polarizer having an average absolute reflectance of 700 nm light of 6% or less.
- the polyester film for protecting a polarizer according to Item 1 comprising a low refractive index layer having a refractive index lower than that of the polyester film on the opposite surface.
- Item 3. Item 3.
- Item 4. The polyester film for protecting a polarizer according to any one of Items 1 to 3, wherein the polyester resin (A) contains a 5-sulfoisophthalic acid component in an amount of 1 to 15 mol% in the dicarboxylic acid component.
- Item 5. Item 5.
- Item 6. Item 6.
- a polarizing plate having a polarizer protective film on both sides of a polarizer, wherein at least one of the polarizer protective films is the polyester film for protecting a polarizer according to any one of Items 1 to 6.
- An image display device having at least one polarizing plate according to Item 7.
- the polyester film for protecting a polarizer of the present invention is excellent in adhesion with a polarizer or a polyvinyl alcohol-based resin layer typified by an adhesive applied thereon. Moreover, the polyester film of the present invention has high light transmittance and can be suitably used as a protective film for a polarizer.
- a polyester film of the present invention as a protective film for a polarizer, it is possible to produce a polarizing plate having superior durability and water barrier properties at a lower cost than before.
- the polarizing plate of the present invention is excellent in durability, it can be made thinner than before. Therefore, it is possible to further reduce the thickness of the liquid crystal display by using the polarizing plate of the present invention.
- the polyester film used as a substrate in the present invention is a film mainly composed of a polyester resin.
- a film mainly composed of a polyester resin is a film formed from a resin composition containing 50% by mass or more of a polyester resin. When blended with another polymer, the polyester resin is 50% by mass. % When it is copolymerized with other monomers, it means that 50 mol% or more of the polyester structural unit is contained.
- the polyester film contains a polyester resin in an amount of 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass.
- the material of the polyester resin is not particularly limited, but a copolymer formed by polycondensation of a dicarboxylic acid component and a diol component or a blend resin thereof can be used.
- the dicarboxylic acid component include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyl Carboxylic acid, diphenoxyethanedicarboxylic acid, diphenylsulfonecarboxylic acid, anthracenedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydro Isophthalic
- diol component constituting the polyester resin examples include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decamethylene glycol, 1,3- Examples thereof include propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexadiol, 2,2-bis (4-hydroxyphenyl) propane, and bis (4-hydroxyphenyl) sulfone.
- the dicarboxylic acid component and the diol component constituting the polyester resin may be used alone or in combination of two or more. Further, other acid components such as trimellitic acid and other hydroxyl components such as trimethylolpropane may be appropriately added.
- polyester resin examples include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
- polyethylene terephthalate is preferable from the balance of physical properties and cost.
- other copolymer components or other polymers are included.
- Preferred copolymer components from the viewpoint of controlling the optical properties of the polyester film include diethylene glycol and copolymer components having norbornene in the side chain.
- the polyester film of the present invention is used as a film for protecting a polarizer, it is preferable to have high transparency.
- the transparency of the polyester film for protecting a polarizer of the present invention is preferably 90% or more, more preferably 91% or more, and still more preferably 92% or more.
- the haze is preferably 3% or less, more preferably 2.5% or less, further preferably 2% or less, and particularly preferably 1.5% or less.
- the total light transmittance of a polyester film can be measured according to the method described in the Example mentioned later, for example. However, the polyester film of the present invention having an antiglare layer to be described later is not limited thereto.
- inert particles may be included in the film.
- the inert particles in the film may be included.
- the content is preferably as low as possible. Therefore, a multilayer structure in which particles are included only in the surface layer of the film, or particles are substantially not included in the film, and particles are included only in the easy-adhesion layer laminated on at least one side of the polyester film. It is preferable.
- “Substantially no particles” means, for example, in the case of inorganic particles, when the element derived from the particles is quantitatively analyzed by fluorescent X-ray analysis, 50 ppm or less, preferably 10 ppm or less, most preferably detected The content is below the limit. This means that even if particles are not actively added to the base film, contaminants derived from foreign substances and raw material resin or dirt adhering to the line or equipment in the film manufacturing process will be peeled off and mixed into the film. It is because there is a case to do.
- the base film has a multi-layer structure
- the two-layer / three-layer structure that does not substantially contain inert particles in the inner layer and contains inert particles only in the outermost layer achieves both transparency and workability. It is possible and preferable.
- the thickness of the film is not particularly limited.
- the thickness of the film is preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less.
- the thickness of the film is preferably 10 ⁇ m or more, more preferably 12 ⁇ m or more, and further preferably 20 ⁇ m or more.
- the polyester film serving as the substrate may be a single layer or a laminate of two or more layers.
- various additives can be contained in a film as needed.
- the additive include an antioxidant, a light resistance agent, an antigelling agent, an organic wetting agent, an antistatic agent, an ultraviolet absorber, and a surfactant.
- an additive according to the function of each layer as needed.
- the polyester film can be obtained by, for example, a method in which the above polyester resin is melt-extruded into a film shape and cooled and solidified with a casting drum to form a film.
- a non-stretched film or a stretched film can be used, but a stretched film is preferable from the viewpoint of durability such as mechanical strength and chemical resistance.
- the stretching method is not particularly limited, and a longitudinal uniaxial stretching method, a transverse uniaxial stretching method, a longitudinal and transverse sequential biaxial stretching method, a longitudinal and transverse simultaneous biaxial stretching method, and the like can be employed.
- the polyester film of the present invention has an acid value of 20 KOHmg / g or less on at least one surface thereof in order to improve the adhesion between the polarizer and a polyvinyl alcohol resin layer such as a water-based adhesive provided on one surface or both surfaces thereof.
- An easy adhesion layer formed from a resin composition containing a certain polyester resin (A), a polyvinyl alcohol resin (B) having a saponification degree of 60 to 85 mol%, and a crosslinking agent (C) is laminated. Yes.
- the polyester-based resin and the polyvinyl alcohol-based resin form separate domain units in the easy-adhesion layer, and form a phase separation structure generally called a sea-island structure.
- the adhesiveness to the polyester film by the domain constituted by the polyester resin and the adhesiveness to the polyvinyl alcohol resin layer by the domain constituted by the polyvinyl alcohol resin are two.
- the crosslinking agent (C) is considered to promote and maintain the formation of the domain structure by crosslinking and aggregating the polyvinyl alcohol resin (B).
- B polyvinyl alcohol resin
- polyester resin (A) used in the easy-adhesion layer of the present invention is a copolymer obtained by polycondensation of a dicarboxylic acid component and a diol component, and the above-described materials can be used as the dicarboxylic acid component and the diol component. it can. From the viewpoint of improving the adhesion to the polyester film substrate, it is preferable to use a dicarboxylic acid component having the same or similar structure and properties as the dicarboxylic acid component in the polyester film as the dicarboxylic acid component of the polyester resin (A). .
- an aromatic dicarboxylic acid when employed as the dicarboxylic acid component of the polyester film, it is preferable to use the aromatic dicarboxylic acid as the dicarboxylic acid component of the polyester resin (A).
- aromatic dicarboxylic acid component terephthalic acid and isophthalic acid are most preferred.
- Other aromatic dicarboxylic acids may be added and copolymerized within a range of 10 mol% or less with respect to the total dicarboxylic acid component.
- glycol component of the polyester-based resin (A) it is preferable to use ethylene glycol and branched glycol as constituent components.
- ethylene glycol and branched glycol By having a branched structure, it is considered that it contributes to stress relaxation in the easy-adhesion layer, and it is possible to suitably exhibit adhesion.
- the branched glycol component include 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, and 2-methyl-2-butyl-1,3.
- the molar ratio of the branched glycol component is preferably 10 mol%, particularly preferably 20 mol%, based on the total glycol component.
- the upper limit is preferably 80 mol%, more preferably 70 mol%, and particularly preferably 60 mol%. If necessary, diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4-cyclohexanedimethanol or the like may be used in combination.
- the polyester resin (A) used in the present invention is preferably a water-soluble or water-dispersible resin from the viewpoint of compatibility with the polyvinyl alcohol resin (B).
- a compound containing a hydrophilic group such as a sulfonate group or a carboxylate group.
- a dicarboxylic acid component having a sulfonate group is preferable from the viewpoint of imparting hydrophilicity while keeping the acid value of the polyester-based resin (A) low and controlling the reactivity with the crosslinking agent.
- dicarboxylic acid component having a sulfonate group examples include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthaleneisophthalic acid-2,7-dicarboxylic acid, and 5- (4-sulfophenoxy) isophthalic acid or an alkali thereof.
- metal salt examples include 5-sulfoisophthalic acid.
- the dicarboxylic acid component having a sulfonic acid group is preferably 1 to 15 mol%, more preferably 1.5 to 12 mol%, still more preferably 2 to 10 mol% in the dicarboxylic acid component of the polyester resin (A).
- the dicarboxylic acid component having a sulfonate group is at least the above lower limit, it is suitable for water-solubilization or water-dispersion of the polyester resin. Moreover, when the dicarboxylic acid component which has a sulfonate group is below the said upper limit, it is suitable for adhesiveness with a polyester film base material.
- the polyester resin (A) preferably has fewer carboxylic acid groups which are reactive groups with the crosslinking agent (C).
- the crosslinking agent (C) By reducing the number of carboxyl groups that are reactive with the cross-linking agent, the reactivity with the cross-linking agent is reduced. As a result, the cross-linking polyvinyl alcohol-based resin does not completely mix with the polyvinyl alcohol-based resin. It is considered possible to maintain the domain structure that is formed.
- the acid value of the polyester resin (A) is 20 KOHmg / g or less, preferably 15 KOHmg / g or less, more preferably 10 KOHmg / g or less, further preferably 8 KOHmg / g or less, and still more preferably 5 KOHmg. / G or less.
- the acid value of the polyester resin (A) can be theoretically determined from the result of component analysis by titration method described later or NMR.
- the introduction amount of the carboxylic acid base for water solubilization or water dispersion is reduced, or hydrophilic groups other than the carboxylic acid base are employed.
- lowering the carboxylic acid terminal concentration of the polyester resin it is preferable to employ a polyester resin in which the carboxylic acid terminal group is modified, or a polyester resin having a large number average molecular weight of the polyester resin.
- the number average molecular weight of the polyester resin (A) is preferably 5000 or more, more preferably 6000 or more, and further preferably 10,000 or more.
- the glass transition temperature of the polyester resin (A) is not particularly limited, but is preferably 20 to 90 ° C, and more preferably 30 to 80 ° C. When the glass transition temperature is not less than the above lower limit, it is suitable for blocking resistance, and when the glass transition temperature is not more than the above upper limit, it is suitable for adhesiveness to a polyester film substrate.
- 40 mass% or more and 90 mass% or less are preferable, as for content of the polyester-type resin (A) in an easily bonding layer, 45 mass% or more and 85 mass% or less are more preferable, and 50 mass% or more and 80 mass% or less are more preferable.
- content of the polyester resin (A) is at least the above lower limit, it is suitable for adhesion to the polyester film substrate, and when it is at most the above upper limit, it is suitable for adhesion to the polarizer / aqueous resin.
- the polyvinyl alcohol-based resin is not particularly limited.
- polyvinyl alcohol obtained by saponifying polyvinyl acetate; a derivative thereof; and a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability; And modified polyvinyl alcohol obtained by converting polyvinyl alcohol into acetalized, urethanized, etherified, grafted, phosphoric acid ester or the like.
- Examples of the monomer include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; ⁇ -olefins such as ethylene and propylene; (meth) Examples include allyl sulfonic acid (soda), sulfonic acid soda (monoalkylmalate), disulfonic acid soda alkylmalate, N-methylolacrylamide, acrylamide alkylsulfonic acid alkali salt, N-vinylpyrrolidone, and N-vinylpyrrolidone derivatives. . These polyvinyl alcohol resins may be used alone or in combination of two or more.
- Examples of the polyvinyl alcohol resin (B) used in the present invention include vinyl alcohol-vinyl acetate copolymer, vinyl alcohol-vinyl butyral copolymer, and ethylene-vinyl alcohol copolymer. Among these, vinyl alcohol-vinyl acetate A copolymer and an ethylene-vinyl alcohol copolymer are preferred.
- the polymerization degree of the polyvinyl alcohol-based resin (B) is not particularly limited, but the polymerization degree is preferably 3000 or less from the viewpoint of the coating solution viscosity.
- the copolymerization ratio of vinyl alcohol is represented by the degree of saponification.
- the saponification degree of the polyvinyl alcohol resin (B) of the present invention is preferably 60 mol% or more and 85 mol% or less, more preferably 65 mol% or more and 83 mol% or less, further preferably 68 mol% or more and 80 mol% or less, and 70 More preferably, it is more than mol% and less than 80 mol%, still more preferably 71 mol% or more and 78 mol% or less, and particularly preferably 73 mol% or more and 75 mol% or less.
- the degree of saponification of the polyvinyl alcohol resin (B) is not less than the above lower limit, a crosslinked structure can be more suitably formed with the crosslinking agent (C). Further, when the degree of saponification of the polyvinyl alcohol-based resin (B) is not more than the above upper limit (or less), compatibility with the polyester-based resin (A) can be more suitably achieved.
- the degree of saponification of the vinyl alcohol-based resin can be determined by the amount of alkali consumption required for hydrolysis of copolymer units such as vinyl acetate or the composition analysis by NMR.
- the content of the polyvinyl alcohol resin (B) is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 55% by mass or less, and more preferably 20% by mass or more and 50% by mass or less in the easy-adhesion layer. Further preferred.
- the content of the polyvinyl alcohol resin (B) is not less than the above lower limit, it is suitable for adhesion to a polarizer / water-based resin, and when it is not more than the above upper limit, it is suitable for adhesion to a polyester film substrate.
- the crosslinking agent (C) is not particularly limited as long as it has crosslinkability with a hydroxyl group, and examples thereof include melamine-based, isocyanate-based, carbodiimide-based, oxazoline-based, and epoxy-based compounds. Melamine-based, isocyanate-based, carbodiimide-based, and oxazoline-based compounds are preferable from the viewpoint of the temporal stability of the coating solution.
- the crosslinking agent is preferably a melamine compound or an isocyanate compound that suitably cross-links with the hydroxyl group of the polyvinyl alcohol resin (B).
- a carbodiimide-based cross-linking agent reacts with a carboxyl group
- a melamine-based compound or an isocyanate-based compound reacts with a hydroxyl group
- a polyvinyl alcohol resin (B) having a hydroxyl group as a functional group is more preferably a crosslinked structure.
- an isocyanate type compound from a viewpoint that it forms a crosslinking reaction suitably with the hydroxyl group of polyvinyl alcohol-type resin, and is excellent in transparency.
- you may use a catalyst etc. suitably as needed.
- isocyanate compound a low molecular or high molecular diisocyanate or a trivalent or higher polyisocyanate can be used.
- isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,5 -Naphthylene diisocyanate, 1,4-naphthylene diisocyanate, phenylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane- 4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4
- aliphatic diisocyanates such as alicyclic diisocyanates, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, and trimers of these isocyanate compounds.
- an excess amount of these isocyanate compounds and low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or polyester polyols, poly Mention may be made of a polymer containing a terminal isocyanate group of a polymer obtained by reacting a polymer active hydrogen compound such as ether polyols and polyamides.
- a blocked isocyanate compound is also preferable. By adding the blocked isocyanate compound, it is possible to more suitably improve the temporal stability of the coating solution.
- the blocked isocyanate compound can be prepared by subjecting the above isocyanate compound and blocking agent to an addition reaction by a conventionally known method.
- the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; thiophenols such as thiophenol and methylthiophenol; oximes such as acetoxime, methyl etiketooxime, and cyclohexanone oxime.
- Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol Pyrazole compounds such as 3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole; Triazole compounds such as 4-triazole; lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propyllactam; aromatic amines; imides; acetylacetone, acetoacetate, malonic acid ethyl ester, Active methylene compounds such as malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate,
- a crosslinking agent (C) As content of a crosslinking agent (C), 2 to 50 mass% is preferable in an easily bonding layer, 5 to 40 mass% is more preferable, 8 to 30 mass% is further more preferable. .
- the content of the crosslinking agent (C) is not less than the above lower limit, it is suitable for forming a crosslinked polyvinyl alcohol resin, and when it is not more than the above upper limit, it is suitable for expression of an adhesive effect by the binder resin.
- the blending ratio (A) / (B) of the polyester resin (A) and the polyvinyl alcohol resin (B) is preferably 0.8 to 5, more preferably 1 to 4, more preferably 2 Is more preferably 4 and particularly preferably 2.5 to 3.5.
- (A) / (B) is not less than the above lower limit, it is suitable for adhesion to a polyester film substrate, and when it is not more than the above upper limit, it is suitable for adhesion to a polarizer / water-based resin.
- the blending ratio ((A) + (B)) / (C) of the polyester resin (A) and polyvinyl alcohol resin (B) to the crosslinking agent (C) is preferably 2 to 50 in terms of mass ratio. More preferably, it is ⁇ 40, and more preferably 8-30.
- ((A) + (B)) / (C) is not less than the above lower limit, it is suitable for expression of the adhesive effect by the binder resin component, and when it is not more than the above upper limit, it is suitable for the adhesive effect by phase separation. .
- the easy-adhesion layer of the present invention adopts the above composition, and exhibits high adhesiveness equivalent to that of triacetyl cellulose to polarizers and aqueous adhesives, particularly polyvinyl alcohol-based polarizers and aqueous adhesives.
- the remaining area after peeling once is preferably 90% or more, more preferably 95% or more, and further preferably 100% with respect to the water-based adhesive according to the adhesive test described later.
- the remaining area after is preferably 75% or more, more preferably 85% or more, further preferably 95% or more, and the remaining area after 10 continuous peelings is preferably 50% or more, more preferably 80% or more, Preferably it is 90% or more, More preferably, it is 93% or more, Most preferably, it is 95% or more.
- additives such as surfactants, antioxidants, catalysts, heat stabilizers, weathering stabilizers, UV absorbers, organic absorbers, and the like within a range that does not inhibit the effects of the present invention.
- Lubricants, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, and the like may be added.
- the particles contained in the easy-adhesion layer in the present invention include titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay and the like, or a mixture thereof.
- Inorganic particles such as calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride and other inorganic particles, styrene-based, acrylic-based, melamine-based, benzoguanamine-based, silicone-based Examples include organic polymer particles.
- the average particle diameter of the particles in the easy-adhesion layer is preferably 0.04 to 2.0 ⁇ m, more preferably 0.1 to 1.0 ⁇ m. If the average particle size of the inert particles is less than 0.04 ⁇ m, the formation of irregularities on the film surface becomes insufficient, so that the handling properties such as the slipping property and the winding property of the film are deteriorated and the film is stuck. The workability at the time of alignment may deteriorate. On the other hand, if it exceeds 2.0 ⁇ m, the particles are likely to fall off, which is not preferable.
- the particle concentration in the easy-adhesion layer is preferably 1 to 20% by mass, more preferably 5 to 15% by mass in the solid component.
- the thickness of the easy-adhesion layer can be appropriately set in the range of 0.001 to 2 ⁇ m.
- the range of 0.01 to 1 ⁇ m is preferable, and more preferable.
- Adhesiveness will become inadequate that the thickness of an easily bonding layer is less than 0.01 micrometer.
- the thickness of the easy-adhesion layer exceeds 2 ⁇ m, blocking may occur.
- the average absolute reflectance of light having a wavelength of 400 to 700 nm on the surface opposite to the surface on which the easy adhesion layer is provided is 6% or less. Is preferred.
- the average absolute reflectance is more preferably 5% or less, and further preferably 4.5% or less.
- the average absolute reflectance is larger than 6%, the reflection of visible light to be transmitted on the film surface increases, and the transmittance decreases.
- it is 6% or less reflection on the film surface is suppressed, and a polyester film for protecting a polarizer having high transmittance can be provided.
- the means for controlling the average absolute reflectance within the above range is not particularly limited, but it is preferable to laminate a low refractive index layer on the surface opposite to the surface on which the easy adhesion layer of the polyester film of the present invention is provided.
- a low refractive index layer means a layer lower than the refractive index of the polyester film which is a base material. More specifically, it is a layer whose refractive index is 1.60 or less. More preferably, the refractive index is 1.55 or less.
- the lower limit of the refractive index is not particularly limited, but is preferably 1.20 or more in practice, and more preferably 1.25 or more.
- the material used for the low refractive index layer is not particularly limited, but polyester resins, polyurethane resins, acrylic resins, polyvinyl alcohol resins, polycarbonate resins, fluorine-containing resins, silicone resins, and the like are suitable. Used for. These resins may be resin compounds which are polymerized and / or reacted by drying, heat, chemical reaction, or irradiation with any of electron beam, radiation, and ultraviolet rays, and known materials may be used. it can. Among these, polyurethane resins, acrylic resins, and fluorine-containing resins have a relatively low refractive index and can be suitably used.
- the urethane resin used for the low refractive index layer preferably contains at least a polyol component and a polyisocyanate component as constituent components, and further contains a chain extender as necessary.
- the urethane resin is a polymer compound in which these constituent components are mainly copolymerized by urethane bonds.
- polystyrene resin examples include polyvalent carboxylic acids (for example, malonic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or acid anhydrides thereof and polyhydric alcohols (for example, Reaction of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, neopentylglycol, 1,6-hexanediol, etc.) Polyester polyols obtained from polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and other polyether polyols, polycarbonate Polyols and polyolefin polyols, and the like acrylic polyols.
- the aliphatic polycarbonate polyol which is excellent in heat resistance and hydrolysis resistance in the polyol component which is a structural component of a urethane resin.
- polyester resin examples include the following.
- the number average molecular weight of the polyester resin is preferably 15000 or more. When the number average molecular weight is low, the terminal carboxylic acid group increases, so that hydrolysis is promoted and adhesion at high temperature and high humidity cannot be obtained, but also adhesion to the substrate film is lowered. . Further, the number average molecular weight is more preferably 20000 or more, and it is preferably higher as long as it can be produced. However, the number average molecular weight is preferably 60000 or less because the solubility in the coating solution may be reduced as the number average molecular weight increases.
- Polyester resin has acid components such as terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, Examples include dimer acid, 5-sodium sulfoisophthalic acid, 4-sodium sulfonaphthalene-2,7-dicarboxylic acid, and the like.
- Diol components include ethylene glycol, propane glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylene glycol, ethylene oxide adducts of bisphenol A, etc. Is mentioned.
- the polyester resin is based on water or a water-soluble organic solvent (for example, an aqueous solution containing less than 50% by weight of alcohol, alkyl cellosolve, ketone, or ether) or an organic solvent (for example, toluene, ethyl acetate, etc.). Those dissolved or dispersed can be used.
- a water-soluble organic solvent for example, an aqueous solution containing less than 50% by weight of alcohol, alkyl cellosolve, ketone, or ether
- an organic solvent for example, toluene, ethyl acetate, etc.
- a water-soluble or water-dispersible polyester resin is used.
- a compound containing a sulfonate group or a carboxyl group is used. It is preferable to copolymerize a compound containing an acid base. Therefore, in addition to the dicarboxylic acid component described above, in order to impart water dispersibility to the polyester, it is preferable to use 5-sulfoisophthalic acid or an alkali metal salt thereof in the range of 1 to 10 mol%.
- the molar ratio of the third component having 3 or more carboxyl groups / one molecule or 3 or more hydroxyl groups / 1 molecule is preferably 5.0 mol% or less in the total dicarboxylic acid component. Preferably it is 1.0 mol% or less.
- the acrylic resin used for the low refractive index layer is not particularly limited, but a polymer composed of a polymerizable monomer having a carbon-carbon double bond, such as an acrylic or methacrylic monomer, can be used. . These may be either a homopolymer or a copolymer. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer.
- a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion is also included.
- a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or polyurethane dispersion is also included.
- a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion is also included.
- a fluorine atom-containing compound having a low refractive index it is also possible to use a fluorine atom-containing compound having a low refractive index.
- the polymerizable monomer having a carbon-carbon double bond is not particularly limited, but particularly representative compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citracone.
- Various carboxyl group-containing monomers such as acids, and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, Various hydroxyl group-containing monomers such as monobutylhydroxy itaconate; various monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate ( (Meth) acrylic acid ester
- Various nitrogen-containing compounds such as (meth) acrylamide, diacetoneacrylamide, N-methylo
- an acrylic resin that is cured by an electron beam or ultraviolet rays it is preferable to use an acrylic resin that is cured by an electron beam or ultraviolet rays.
- An acrylic resin that is cured by an electron beam or ultraviolet ray has an acrylate-based functional group.
- an electron beam or ultraviolet curable resin as a photopolymerization initiator in the above-mentioned resin, acetophenones, benzophenones, Michler benzoylbenzoate, ⁇ -amyloxime ester, tetramethyltyramium monosulfide, thioxanthones, As a photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used.
- the addition amount of the photopolymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the electron beam or ultraviolet curable resin.
- the method for curing the coating film is not particularly limited, but is preferably performed by ultraviolet irradiation.
- ultraviolet rays it is preferable to use ultraviolet rays having a wavelength range of 190 to 380 nm. Curing with ultraviolet rays can be performed, for example, with a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or the like.
- the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type.
- electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type.
- fluorine-containing resin Although it does not specifically limit as fluorine-containing resin used for a low refractive index layer, The following are used suitably.
- the fluorine-containing resin include 1- (meth) acryloyloxy-1-perfluoroalkylmethane, 1- (meth) acryloyloxy-2-perfluoroalkylethane, 1,10-bisacryloyloxy-1,1,10,10.
- Polyvinyl alcohol resin Although it does not specifically limit as polyvinyl alcohol resin used for a low-refractive-index layer, The same thing as what is used for the easily bonding layer of this specification can be used.
- organic or inorganic fine particles can be used. Examples thereof include silicon oxide fine particles and organic resin fine particles. It is also preferable to use hollow silica fine particles.
- the hollow silica fine particles are fine particles in which silica (silicon dioxide, SiO 2 ) is formed in a substantially spherical shape and has a hollow portion in the outer shell.
- the average particle diameter of the hollow silica fine particles is preferably 10 to 100 nm, more preferably 20 to 60 nm. When the average particle diameter of the hollow silica fine particles is smaller than 10 nm, it is not preferable because the production of the hollow silica fine particles becomes difficult. On the other hand, when the average particle diameter is larger than 100 nm, light scattering is increased, the reflection is increased in the thin film, and the surface reflectance is increased.
- the film thickness of the low refractive index layer preferably satisfies 400 ⁇ 4 n ⁇ d (nm) ⁇ 700.
- n represents the refractive index of the low refractive index layer
- d represents the film thickness.
- another layer may be provided between the low refractive index layer and the polyester film, and that there is an anchor coat layer that adheres the polyester film and the low refractive index layer.
- the low refractive index layer may be a functional layer having at least one function such as hard coat property, antiglare property, antireflection property, and antistatic property. In this case, you may have another layer between the functional layer and the polyester film.
- the low-refractive index layer which is a functional layer, is provided with another layer between the polyester film and the low-refractive index layer, and the other layer and the low-refractive index layer are integrated into a hard coat property, antiglare property, and antireflection property.
- a functional layer having at least one function of antistatic property may be configured. In any configuration, it is preferable that the low refractive index layer is disposed in the outermost layer in order to increase the transmittance of the film.
- a functional layer is demonstrated, it cannot be overemphasized that it is not limited to the structure shown below.
- the hard coating property of the low refractive index layer is as described above.
- resin used for a hard-coat layer it is preferable to use the above-mentioned resin hardened
- Anti-glare layer As a method for imparting antiglare properties to the low refractive index layer, a known technique can be used. For example, an uneven shape can be formed on a polyester film, and external light can be scattered to prevent a decrease in visibility due to reflection of external light or reflection of an image. As a method for forming the unevenness, a resin containing a large particle size or cohesive particles is applied to form an uneven shape on the film surface, or a film having unevenness on the layer surface is laminated to make unevenness There are a method of forming an antiglare layer by transferring the shape, a method of forming irregularities by nanoimprinting without containing the particles, and one type or a combination of two or more types can be used.
- the same electron beam or ultraviolet curable resin as described above can be used.
- One or two or more of the above-mentioned resins can be mixed and used.
- a resin that is not cured by an electron beam or ultraviolet rays can be mixed.
- resins that are not cured by electron beams or ultraviolet rays include polyurethane, cellulose derivatives, polyesters, acrylic resins, polyvinyl butyral, polyvinyl alcohol, polyvinyl chloride, polyvinyl acetate, polycarbonate, and polyamide.
- particles used in the antiglare layer include, for example, particles of inorganic compounds such as silica particles, alumina particles, TiO 2 particles, or polymethyl methacrylate particles, acrylic-styrene copolymer particles, crosslinked acrylic particles, melamine particles.
- resin particles such as crosslinked melamine particles, polycarbonate particles, polyvinyl chloride particles, benzoguanamine particles, crosslinked benzoguanamine particles, polystyrene particles, and crosslinked polystyrene particles.
- shape spherical particles having a uniform surface protrusion shape are preferably used, but indefinite shapes such as layered inorganic compounds such as talc and bentonite can also be used. Two or more different kinds of particles may be used in combination. Even if there are two or more kinds of material and two or more kinds of particle sizes, there is no limitation.
- the particle size of the particles used in the antiglare layer is, for example, 0.5 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m, still more preferably 0.5 to 3 ⁇ m, and even more preferably 0.5 to 1.5 ⁇ m. preferable.
- the content of the particles is 1 to 50% by weight with respect to the resin, and more preferably 2 to 30% by weight.
- the film thickness of the antiglare layer is preferably 0.5 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 20 ⁇ m, and further preferably 1 ⁇ m to 10 ⁇ m.
- the haze of the polyester film for protecting a polarizer having an antiglare layer of the present invention is preferably 1 to 50%. It is more preferably 1 to 30%, and further preferably 1 to 10%.
- JP-A-6-18706, JP-A-10-20103, JP-A-2009-227735, JP-A-2009-86361, JP-A-2009-80256, JP-A-2011-81217, JP-A-20102010. -204479, JP-A 2010-181898, JP-A 2011-197329, JP-A 2011-197330, JP-A 2011-215393, and the like can also be suitably used.
- An antiglare layer can be laminated between the low refractive index layer of the present invention and the polyester film to form an antiglare antireflection layer.
- a known technique can be used for laminating the antiglare antireflection layer. At this time, the effect of the present invention can be maintained by making the refractive index of the antiglare layer higher than that of the low refractive index layer.
- the antiglare antireflection layer used in the present invention is the antiglare antireflection layer disclosed in JP2001-281405, JP2004125958, JP4225675, JP2009-47938, JP2009-157234, and the like. It is also preferable to use it.
- Antireflection layer Between the low refractive index layer and the polyester film, only the middle refractive index layer, the high refractive index layer, or the high refractive index layer can be laminated in order from the polyester film side to form an antireflection layer. As an antireflection layer, it can also laminate
- the high refractive index layer and middle refractive index layer of the antireflection layer of the polyester film of the present invention are configured by combining inorganic materials, organic materials, and the like.
- the refractive index of the high refractive index layer is higher than that of the low refractive index layer, preferably 1.60 or more, and preferably 1.60 to 1.90. If it is less than 1.60, sufficient antireflection effect cannot be obtained, and it becomes difficult to form a resin layer exceeding 1.90 by wet coating.
- the refractive index of the middle refractive index layer is preferably lower than that of the high refractive index layer and higher than that of the low refractive index layer, and is preferably in the range of 1.50 to 1.65.
- the material constituting the high refractive index layer and the medium refractive index layer is not particularly limited, and inorganic materials and organic materials can be used.
- the high refractive index layer and the medium refractive index layer are formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD), particularly by vacuum vapor deposition or sputtering, which is a kind of physical vapor deposition, to form a transparent thin film of inorganic oxide. Although it can be used, an all wet coating method is preferred.
- the high refractive index layer is composed of inorganic fine particles containing at least one metal oxide selected from Ti, Zr, In, Zn, Sn, Al and Sb.
- a curable resin having a polymerizable group (which can also be used in the hard coat layer of the present invention), a coating composition containing a solvent and a polymerization initiator is applied, and after drying the solvent, heating, ionizing radiation It is preferably formed by curing by irradiation or a combination of both means.
- a high refractive index layer can be formed by curing the curable resin by a polymerization reaction by heat and / or ionizing radiation after coating.
- the middle refractive index layer can be formed using the same material, etc., except that the refractive index is different from that of the high refractive index layer.
- inorganic fine particles As the inorganic fine particles, metal (eg, Ti, Zr, In, Zn, Sn, Sb, Al) oxides are preferred, and zirconium oxide fine particles are most preferred from the viewpoint of refractive index. However, from the viewpoint of conductivity, it is preferable to use inorganic fine particles whose main component is an oxide of at least one kind of metal of Sb, In, and Sn.
- the refractive index can be adjusted to a predetermined refractive index by changing the amount of the inorganic fine particles.
- the average particle diameter of the inorganic fine particles in the layer is preferably 1 to 120 nm, more preferably 5 to 100 nm, and further preferably 10 to 100 nm when zirconium oxide is used as a main component. Within this range, haze is suppressed, dispersion stability, and adhesion with the upper layer due to moderate irregularities on the surface become favorable, which is preferable.
- the inorganic fine particles mainly composed of zirconium oxide preferably have a refractive index of 1.9 to 2.8, more preferably 2.1 to 2.8, and more preferably 2.2 to 2.8. Most preferred.
- the amount of the inorganic fine particles added varies depending on each layer, and the high refractive index layer is 40 to 90% by mass, preferably 50 to 85% by mass, preferably 60 to 80% by mass with respect to the solid content of the entire high refractive index layer. Further preferred.
- the medium refractive index layer is 1 to 60% by mass, preferably 3 to 50% by mass, based on the solid content of the entire medium refractive index layer.
- the thickness of the antireflective layer comprising the low refractive index layer and the high refractive index layer varies depending on the structure of the antireflective layer, but is preferably the same thickness as the visible light wavelength or less.
- the optical film thickness nH ⁇ d of the high refractive index layer is 500 ⁇ 4 nH ⁇ d (nm) ⁇ 750
- the optical film thickness nL ⁇ d of the low refractive index layer is: It is designed to satisfy 400 ⁇ 4 nL ⁇ d (nm) ⁇ 650.
- nH and nL are the refractive indexes of the high refractive index layer and the low refractive index layer, respectively, and d is the thickness of the layer.
- Examples of the antireflection layer used in the present invention include JP2003-177209, JP2008-262187, JP2010-170089, JP2004-309711, JP2011-191735, JP2004-322380, and JP2009. -3354, JP-A 2010-72039, and JP-A 2010-256705 can also be suitably used.
- the low refractive index layer of the present invention may contain other components in addition to those described above as long as they do not lose the effects of the invention.
- Other components include, but are not limited to, for example, inorganic or organic pigments, polymers, polymerization initiators, polymerization inhibitors, antioxidants, dispersants, surfactants, light stabilizers, leveling agents, An antistatic agent, an ultraviolet absorber, a catalyst, an infrared absorber, a flame retardant, an antifoaming agent, conductive fine particles, a conductive resin, and the like can be added.
- the low refractive index layer of the present invention may be provided with only one of the functions described above, or may be combined.
- PET film Polyethylene terephthalate
- the unstretched PET sheet may have a single layer structure or a multilayer structure by a coextrusion method.
- the obtained unstretched PET sheet is subjected to crystal orientation by uniaxial stretching or biaxial stretching.
- the film is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially stretched PET film, and then the end of the film is held with a clip Then, it is led to a hot air zone heated to 80 to 180 ° C. and stretched 2.5 to 5.0 times in the width direction.
- uniaxial stretching the film is stretched 2.5 to 5.0 times in the tenter. After stretching, the film is led to a heat treatment zone of 140 to 240 ° C., and heat treatment is performed for 1 to 60 seconds to complete crystal orientation.
- the easy adhesion layer can be provided after the production of the film or in the production process.
- any known method can be used as a method for applying this coating solution to the PET film.
- reverse roll coating method gravure coating method, kiss coating method, die coater method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, impregnation coating method, curtain coating method, etc. It is done. These methods are applied alone or in combination.
- the thickness of the easily adhesive layer finally obtained is preferably 0.03 to 0.20 g / m 2 . If it is less than 0.03 g / m ⁇ 2 >, adhesiveness will fall, and if it is thicker than 0.20 g / m ⁇ 2 >, since blocking property and slipperiness will fall, it is unpreferable.
- the low refractive index layer when the low refractive index layer is provided, it can be provided in the same manner as the easy adhesion layer.
- the polarizing plate of the present invention is a polarizing plate having a polarizer protective film on both sides of a polarizer, and the polarizer protective film on at least one surface is the above-mentioned easily adhesive polyester film for protecting a polarizer.
- the other polarizer protective film may be an easily adhesive polyester film for protecting a polarizer of the present invention, or a film having no birefringence such as a triacetyl cellulose film, an acrylic film, or a norbornene-based film. It is also preferable to use it.
- the polarizer examples include a polyvinyl alcohol film containing a dichroic material such as iodine.
- the polarizer protective film is bonded to the polarizer directly or via an adhesive layer, but it is preferable to bond the polarizer protective film via an adhesive from the viewpoint of improving adhesiveness. In that case, it is preferable to arrange
- a preferable polarizer for bonding the polyester film of the present invention for example, iodine or dichroic material is dyed and adsorbed on a polyvinyl alcohol film, uniaxially stretched in a boric acid aqueous solution, and the stretched state is maintained.
- cleaning and drying is mentioned.
- the stretching ratio of uniaxial stretching is usually about 4 to 8 times.
- Polyvinyl alcohol is suitable as the polyvinyl alcohol film.
- “Kuraray Vinylon” [manufactured by Kuraray Co., Ltd.]
- “Tosero Vinylon” [manufactured by Tosero Co., Ltd.]
- “Nippon Vinylon” [Nippon Synthetic Chemical Co., Ltd.
- Commercial products such as “made” can be used.
- Examples of the dichroic material include iodine, a disazo compound, and a polymethine dye.
- the adhesive applied to the polarizer is preferably an aqueous one, that is, an adhesive component dissolved in water or dispersed in water.
- a polyvinyl alcohol resin, a urethane resin, or the like is used as a main component, and a composition containing an isocyanate compound, an epoxy compound, or the like can be used as necessary in order to improve adhesiveness.
- the thickness of the adhesive layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- polyvinyl alcohol resin As the main component of the adhesive, in addition to partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, amino group-modified A modified polyvinyl alcohol resin such as polyvinyl alcohol may be used.
- the concentration of the polyvinyl alcohol resin in the adhesive is preferably 1 to 10% by mass, and more preferably 2 to 7% by mass.
- the polyester film for protecting a polarizer of the present invention is preferably used on the viewing side of the viewing side polarizing plate or the light source side of the light source side polarizing plate, and particularly when used on the light source side of the light source side polarizing plate, the brightness of the liquid crystal display device. Can be improved.
- the polyester film for protecting a polarizer of the present invention is used on the light source side of the light source side polarizing plate, light is incident from the side having a low average reflectance, and the luminance of the liquid crystal display device can be improved.
- light source side means the light source side starting from an image display cell (for example, a liquid crystal cell) out of two polarizing plates used in the image display device, and “viewing side” It means the side opposite to the light source side starting from the image display cell.
- Glass transition temperature In accordance with JIS K7121, a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC6200) was used to raise 10 mg of a resin sample over a temperature range of 25 to 300 ° C. at 20 ° C./min. The extrapolated glass transition start temperature obtained from the curve was defined as the glass transition temperature.
- Acid value 1 g (solid content) of a sample was dissolved in 30 ml of chloroform or dimethylformamide, and titrated with 0.1 N potassium hydroxide ethanol solution using phenolphthalein as an indicator to determine the carboxyl groups per gram of the sample. The amount (mg) of KOH required for neutralization was determined.
- Saponification degree Residual acetic acid groups (mol%) of the polyvinyl alcohol resin were quantified using sodium hydroxide according to JIS-K6726, and the value was defined as the saponification degree (mol%). The sample was measured three times, and the average value was defined as the saponification degree (mol%).
- Total light transmittance of polyester film for protecting polarizer The total light transmittance of the polyester film for protecting a polarizer was measured using a turbidimeter (Nippon Denshoku, NDH2000) in accordance with JIS K7105. In addition, the light was applied from the surface opposite to the surface having the easy-adhesion layer of the polarizer protective film.
- the polyvinyl alcohol resin layer after drying the polyvinyl alcohol aqueous solution (Pura117 made from Kuraray) adjusted to solid content concentration 5 mass% on the surface of the easily adhesive layer of the polyester film for protecting a polarizer is 2 ⁇ m. Then, it was applied with a wire bar and dried at 70 ° C. for 5 minutes.
- As the polyvinyl alcohol aqueous solution a solution in which a red dye was added so as to facilitate the determination was used.
- the prepared evaluation target film was attached to a glass plate having a thickness of 5 mm to which a double-sided tape was attached, and the opposite surface of the evaluation target laminated film on which the polyvinyl alcohol resin layer was formed was attached to the double-sided tape.
- the PVA adhesion rate was 100, and when all the PVA layer was peeled off, the PVA adhesion rate was 0. In addition, what was partially peeled within one square was also included in the number of peeled.
- the refractive index of the low refractive index layer provided in the laminated polyester film for protecting a polarizer of the present invention was measured by the following method.
- the coating solution used for the low refractive index layer is applied to a glass plate so that the thickness after drying is about 4 ⁇ m, dried and cured, and then measured with an Abbe refractometer (NAR-4T, manufactured by Atago Co., Ltd., measurement wavelength 589 nm). This value was taken as the refractive index of the low refractive index layer.
- copolyester resin (A-1) was light yellow and transparent.
- the reduced viscosity of the copolyester resin (A-1) was measured and found to be 0.70 dl / g.
- the glass transition temperature by DSC was 40 ° C.
- copolymer polyester resins (A-2) to (A-5) having different compositions were obtained.
- Table 1 shows the composition (mol% ratio) and other characteristics of these copolyester resins measured by 1H-NMR.
- polyvinyl alcohol resins (B-2) to (B-7) were used in place of the polyvinyl alcohol resin (B-1) to prepare aqueous solutions, which were designated as (Bw-2) to (Bw-7), respectively.
- Table 2 shows the degree of saponification of the polyvinyl alcohol resins (B-1) to (B-7).
- reaction solution temperature was lowered to 50 ° C., and 47 parts by mass of methyl ethyl ketoxime was added dropwise.
- the infrared spectrum of the reaction solution was measured to confirm that the absorption of isocyanate groups had disappeared, and a block polyisocyanate aqueous dispersion (C-1) having a solid content of 75% by mass was obtained.
- a urethane resin D-1 having an aliphatic polycarbonate polyol as a constituent component was prepared by the following procedure. In a four-necked flask equipped with a stirrer, Dimroth condenser, nitrogen inlet tube, silica gel drying tube, and thermometer, 43.75 parts by mass of 4,4-diphenylmethane diisocyanate, 12.85 parts by mass of dimethylolbutanoic acid, several 153.41 parts by mass of polyhexamethylene carbonate diol having an average molecular weight of 2000, 0.03 parts by mass of dibutyltin dilaurate, and 84.00 parts by mass of acetone as a solvent were added and stirred at 75 ° C.
- a low refractive index layer coating solution (D-1) was prepared with the following composition. Water 53.50% by mass Isopropanol 30.00% by mass Polyurethane resin (D-1U) 12.00% by mass Block isocyanate-based crosslinking agent (C-1) 2.40% by mass Particles 1.50% by mass (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass) Surfactant 0.60% by mass (Silicone, solid content concentration 10% by mass)
- a low refractive index layer coating solution (D-2) was prepared with the following composition. Water 56.37% by mass Isopropanol 30.00% by mass Acrylic resin 9.13% by mass (RX2035A, Nippon Carbide, solid content 46%) Block isocyanate-based crosslinking agent (C-1) 2.40% by mass Particles 1.50% by mass (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass) Surfactant 0.60% by mass (Silicone, solid content concentration 10% by mass)
- a low refractive index layer coating solution (D-3) was prepared with the following composition.
- Block isocyanate-based crosslinking agent (C-1) 2.40% by mass Particles 1.50% by mass
- Surfactant 0.60% by mass (Silicone, solid content concentration 10% by mass)
- Formation of hard coat layer D-4 A coating liquid for forming a hard coat layer having the following composition was applied to the surface of the polyester film manufactured in the examples described later on the side opposite to the surface to be bonded to the polarizer, using a # 10 wire bar, and at 70 ° C. for 1 minute. Dry and remove the solvent. Next, the film coated with the hard coat layer was irradiated with 300 mJ / cm 2 ultraviolet rays using a high-pressure mercury lamp to obtain a polarizer protective film having a hard coat layer with a thickness of 5 ⁇ m.
- antiglare layer D-5 (Formation of antiglare layer D-5)
- the antiglare layer-forming coating solution having the following composition was applied to the surface of the polyester film produced in the examples described later on the side opposite to the surface to be bonded to the polarizer, using a # 5 wire bar, and at 70 ° C. for 1 minute. Dry and remove the solvent.
- the film on which the antiglare layer was applied was irradiated with 300 mJ / cm 2 of ultraviolet rays using a high pressure mercury lamp to obtain a polarizer protective film having an antiglare layer (D-5) having a thickness of 5 ⁇ m.
- Coating solution for forming antiglare layer Toluene 34 parts by weight Pentaerythritol triacrylate 50 parts by weight Silica (average particle size 1 ⁇ m) 12 parts by weight silicone (leveling agent) 1 part by weight photopolymerization initiator 1 part by weight (Irgacure 184 manufactured by Ciba Specialty Chemicals)
- (Formation of antireflection layer D-6) Apply a coating solution for forming a medium refractive index layer of the following composition to the surface opposite to the surface to be bonded to the polarizer of the polyester film produced in the examples described later using a bar coater, and dry at 70 ° C. for 1 minute. Then, a medium refractive index layer having a dry film thickness of 5 ⁇ m was obtained by irradiating ultraviolet rays of 400 mJ / cm 2 using a high pressure mercury lamp. Next, on the formed medium refractive index layer, using a bar coater, a coating solution for forming a high refractive index layer having the following composition is formed by the same method as that for the medium refractive index layer.
- a coating solution for forming a low refractive index layer was formed by the same method as that for the middle refractive index layer, and a polyester film for protecting a polarizer was obtained, in which an antireflection layer (D-6) was laminated.
- Medium refractive index layer coating solution (refractive index 1.52) Dipentaerythritol hexaacrylate 70 parts by weight 1,6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane 30 parts by weight Photopolymerization initiator 4 parts by weight (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 184) Isopropanol 100 parts by weight Coating solution for forming a high refractive index layer (refractive index 1.64) ITO fine particles (average particle size 0.07 ⁇ m) 85 parts by weight tetramethylol methane triacrylate 15 parts by weight photopolymerization initiator (KAYACURE BMS, manufactured by Nippon
- Example 1 Preparation of coating solution for easy adhesion layer The following coating agent was mixed to prepare a coating solution in which the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was 70/30.
- the polyester aqueous dispersion uses an aqueous dispersion (Aw-1) in which a polyester resin having an acid value of 2 KOH mg / g is dispersed, and the polyvinyl alcohol aqueous solution is an aqueous solution in which polyvinyl alcohol having a saponification degree of 74 mol% is dissolved. (Bw-4) was used.
- the unstretched PET sheet was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed to obtain a uniaxially stretched PET film.
- the coating solution for the easy adhesion layer and the coating solution for the low refractive index layer D-1 were applied to both surfaces of the PET film by a roll coating method, and then dried at 80 ° C. for 15 seconds.
- the coating amount after drying (after biaxial stretching) was adjusted to 0.12 g / m 2 .
- the film was stretched 4.0 times in the width direction at 150 ° C. with a tenter, and heated at 230 ° C. for 0.5 seconds with the length in the width direction fixed, and further at 230 ° C. for 10 seconds.
- % Relaxation treatment in the width direction was performed to obtain a polarizer protective polyester film having a thickness of 38 ⁇ m.
- the evaluation results are shown in Table 3.
- Example 2 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion of the easy adhesion layer was changed to an aqueous dispersion (Aw-2) in which a polyester resin having an acid value of 4 KOHmg / g was dispersed. Obtained.
- Example 3 A polyester film for protecting a polarizer was prepared in the same manner as in Example 1 except that the polyester aqueous dispersion of the easy adhesion layer was changed to an aqueous dispersion (Aw-3) in which a polyester resin having an acid value of 6 KOHmg / g was dispersed. Obtained.
- Example 4 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution of the easy adhesion layer was changed to a polyvinyl alcohol aqueous solution (Bw-3) having a saponification degree of polyvinyl alcohol of 79 mol%. It was.
- Example 5 A polarizer-protected polyester film was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution (Bw-2) in which the saponification degree of polyvinyl alcohol in the easy-adhesion layer was 83 mol% was changed.
- Example 6 In the same manner as in Example 1 except that the easy-adhesion layer was mixed with the following coating agent and the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was changed to 60/40. A polyester film for protecting a child was obtained.
- Example 7 In the same manner as in Example 1 except that the easy-adhesion layer was mixed with the following coating agent and the mass ratio of the polyester resin (A) / polyvinyl alcohol resin (B) was changed to 80/20. A polyester film for protecting a child was obtained.
- Example 8 In the same manner as in Example 1, except that the easy-adhesion layer was mixed with the following coating agent and the mass ratio of the polyester resin (A) / polyvinyl alcohol resin (B) was changed to 50/50, the polarization was changed. A polyester film for protecting a child was obtained.
- Example 9 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the coating solution composition of the easy adhesion layer was changed as follows. 40.87% by mass of water Isopropanol 30.00% by mass Polyester water dispersion (Aw-1) 11.67% by mass Polyvinyl alcohol aqueous solution (Bw-4) 15.00% by mass Melamine-based crosslinking agent (C-2) 0.71% by mass (Nicarac MX-042, manufactured by Sanwa Chemical Co., Ltd., solid content 70%) 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass) Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Example 10 Polyester for protecting a polarizer in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution of the easy-adhesion layer was changed to an aqueous solution (Bw-5) in which polyvinyl alcohol having a saponification degree of polyvinyl alcohol of 70 mol% was dissolved. A film was obtained.
- Example 11 Polyester for protecting a polarizer in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution of the easy-adhesion layer was changed to an aqueous solution (Bw-6) in which polyvinyl alcohol having a saponification degree of polyvinyl alcohol of 67 mol% was dissolved. A film was obtained.
- Example 12 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the coating solution composition of the easy adhesion layer was changed as follows. 40.33% by mass of water Isopropanol 30.00% by mass Polyester water dispersion (Aw-1) 11.67% by mass Polyvinyl alcohol aqueous solution (Bw-2) 15.00% by mass Oxazoline-based crosslinking agent (C-3) 1.25% by mass (Epocross WS-500, manufactured by Nippon Shokubai, solid concentration 40% by mass) 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass) Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Example 13 A polyester film for protecting a polarizer was prepared in the same manner as in Example 1 except that the polyester aqueous dispersion of the easy adhesion layer was changed to an aqueous dispersion (Aw-5) in which a polyester resin having an acid value of 10 KOHmg / g was dispersed. Obtained.
- Example 14 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the coating solution for the low refractive index layer was changed to D-2.
- Example 15 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the coating solution for the low refractive index layer was changed to D-3.
- Example 16 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that D-4 was formed on the low refractive index layer D-1 in Example 1.
- Example 17 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that D-5 was formed on the low refractive index layer D-1 in Example 1.
- Example 18 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that D-6 was formed on the low refractive index layer D-1 in Example 1.
- Example 19 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the thickness of the low refractive index layer D-1 was changed to 0.06 g / m 2 .
- Example 20 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the thickness of the low refractive index layer D-1 was changed to 0.18 g / m 2 .
- Comparative Example 1 The same procedure as in Example 1 was conducted except that the following coating agent was mixed and the coating solution for the easy-adhesion layer was changed so that the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was 100/0. Thus, a polyester film for protecting a polarizer was obtained.
- Polyester water dispersion (Aw-1) 16.66 mass%
- Block isocyanate-based crosslinking agent (C-1) 0.67% by mass 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
- Catalyst Organic tin compound, solid content concentration 14% by mass
- Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Comparative Example 2 The same procedure as in Example 1 was followed, except that the following coating agent was mixed and the coating solution for the easy-adhesion layer was changed so that the mass ratio of polyester resin (A) / polyvinyl alcohol resin (B) was 0/100. Thus, a polyester film for protecting a polarizer was obtained.
- Block isocyanate-based crosslinking agent (C-1) 0.67% by mass 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass)
- Catalyst Organic tin compound, solid content concentration 14% by mass
- Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Comparative Example 3 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to an aqueous dispersion (Aw-4) in which a polyester resin having an acid value of 25 KOH mg / g was dispersed.
- Comparative Example 4 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was changed to an aqueous solution (Bw-1) in which polyvinyl alcohol having a saponification degree of 88 mol% was dissolved.
- Comparative Example 5 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the polyvinyl alcohol aqueous solution was changed to an aqueous solution (Bw-7) in which polyvinyl alcohol having a saponification degree of 40 mol% was dissolved.
- Comparative Example 6 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the following coating agent was mixed and the coating solution for the easy adhesion layer was changed so as not to mix the crosslinking agent. 41.58% by mass of water Isopropanol 30.00% by mass Polyester water dispersion (Aw-1) 11.67% by mass Polyvinyl alcohol aqueous solution (Bw-4) 15.00% by mass 1.25% by mass of particles (Silica sol with an average particle size of 100 nm, solid content concentration of 40% by mass) Surfactant 0.5% by mass (Silicone, solid content concentration 10% by mass)
- Comparative Example 7 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the low refractive index layer was not provided.
- Comparative Example 8 A polyester film for protecting a polarizer was obtained in the same manner as in Example 1 except that the thickness of the low refractive index layer D-1 was changed to 0.02 g / m 2 .
- Reference example 1 The result of having performed the said adhesive test using the TAC film (The Fuji Film Co., Ltd. product, thickness 80micrometer, saponification-processed) is shown as a film for polarizer protection.
- the easily-adhesive polyester film for protecting a polarizer of the present invention has high adhesiveness with a polarizer / water-based adhesive and high transmittance, and can be suitably used as a polarizer protecting member.
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Abstract
Description
項1.
偏光子との易接着層を片面に有するポリエステルフィルムであって、前記易接着層が、ポリエステル系樹脂(A)とポリビニルアルコール系樹脂(B)と架橋剤(C)を含有し、前記ポリエステル系樹脂(A)の酸価が20KOHmg/g以下であり、前記ポリビニルアルコール系樹脂(B)のけん化度が60~85モル%であり、前記ポリエステルフィルムの前記片面とは反対の面の波長400~700nmの光の平均絶対反射率が6%以下である、偏光子保護用ポリエステルフィルム。
項2.
前記反対の面に、ポリエステルフィルムよりも屈折率の低い低屈折率層を有する、項1記載の偏光子保護用ポリエステルフィルム。
項3.
前記低屈折率層が、ハードコート層、防眩層及び反射防止層からなる群より選択される少なくとも一つの機能層である、項1又は2記載の偏光子保護用ポリエステルフィルム
項4.
前記ポリエステル樹脂(A)が5-スルホイソフタル酸成分をジカルボン酸成分中1~15モル%含有する、項1~3のいずれかに記載の偏光子保護用ポリエステルフィルム。
項5.
前記架橋剤(C)がイソシアネート化合物又はメラミン化合物である、項1~4のいずれかに記載の偏光子保護用ポリエステルフィルム。
項6.
前記易接着層中、ポリエステル系樹脂(A)、ポリビニルアルコール系樹脂(B)および架橋剤(C)の質量比が以下の式を満足する、項1~5のいずれかに記載の偏光子保護用ポリエステルフィルム。
0.8≦(A)/(B)≦5
2≦((A)+(B))/(C)≦50
項7.
偏光子の両面に偏光子保護フィルムを有してなる偏光板であって、少なくとも一方の偏光子保護フィルムが項1~6のいずれかに記載の偏光子保護用ポリエステルフィルムである偏光板。
項8.
項7記載の偏光板を少なくとも1つ有する画像表示装置。
本発明で基材として用いるポリエステルフィルムは、主としてポリエステル樹脂より構成されるフィルムである。ここで、「主としてポリエステル樹脂より構成されるフィルム」とは、ポリエステル樹脂を50質量%以上含有する樹脂組成物から形成されるフィルムであり、他のポリマーとブレンドする場合は、ポリエステル樹脂が50質量%以上含有していることを意味し、他のモノマーと共重合する場合は、ポリエステル構造単位を50モル%以上含有することを意味する。好ましくは、ポリエステルフィルムは、ポリエステル樹脂を90質量%以上、より好ましくは95質量%以上、更に好ましくは100質量%含有する。
本発明のポリエステルフィルムは、偏光子及びその片面又は両面に設けられる水系接着剤等のポリビニルアルコール系樹脂層との接着性を向上させるために、その少なくとも片面に、酸価が20KOHmg/g以下であるポリエステル系樹脂(A)、けん化度が60~85モル%であるポリビニルアルコール系樹脂(B)、及び、架橋剤(C)を含有する樹脂組成物から形成される易接着層が積層されている。
本発明の易接着層に用いるポリエステル系樹脂(A)は、ジカルボン酸成分とジオール成分とが重縮合してなる共重合体であり、ジカルボン酸成分およびジオール成分としては前述の材料を用いることができる。ポリエステルフィルム基材との接着性を向上させる観点から、ポリエステルフィルム中のジカルボン酸成分と同一又は類似する構造・性質を有するジカルボン酸成分をポリエステル系樹脂(A)のジカルボン酸成分として用いることが好ましい。よって、例えば、ポリエステルフィルムのジカルボン酸成分として芳香族ジカルボン酸が採用される場合は、ポリエステル系樹脂(A)のジカルボン酸成分として芳香族ジカルボン酸を使用することが好ましい。そのような芳香族ジカルボン酸成分としては、テレフタル酸およびイソフタル酸が最も好ましい。全ジカルボン酸成分に対し、10モル%以下の範囲で、他の芳香族ジカルボン酸を加えて共重合させてもよい。
ポリビニルアルコール系樹脂は、特に限定されないが、例えば、ポリ酢酸ビニルをけん化して得られたポリビニルアルコール;その誘導体;更に酢酸ビニルと共重合性を有する単量体との共重合体のけん化物;ポリビニルアルコールをアセタール化、ウレタン化、エーテル化、グラフト化、リン酸エステル化等した変性ポリビニルアルコール;などが挙げられる。前記単量体としては、(無水)マレイン酸、フマール酸、クロトン酸、イタコン酸、(メタ)アクリル酸等の不飽和カルボン酸及びそのエステル類;エチレン、プロピレン等のα-オレフィン、(メタ)アリルスルホン酸(ソーダ)、スルホン酸ソーダ(モノアルキルマレート)、ジスルホン酸ソーダアルキルマレート、N-メチロールアクリルアミド、アクリルアミドアルキルスルホン酸アルカリ塩、N-ビニルピロリドン、N-ビニルピロリドン誘導体等が挙げられる。これらポリビニルアルコール系樹脂は1種のみ用いても良いし2種以上を併用しても良い。
架橋剤(C)としては、水酸基と架橋性を有するものであれば特に限定されないが、メラミン系、イソシアネート系、カルボジイミド系、オキサゾリン系、エポキシ系等の化合物が挙げられる。塗布液の経時安定性の点からメラミン系、イソシアネート系、カルボジイミド系、オキサゾリン系の化合物が好ましい。さらに、架橋剤はポリビニルアルコール系樹脂(B)の水酸基と好適に架橋反応をするメラミン系化合物もしくはイソシアネート系化合物ものが好ましい。これは、カルボジイミド系架橋剤はカルボキシル基と反応するのに対し、メラミン系化合物もしくはイソシアネート系化合物は水酸基と反応するため、官能基として水酸基を有するポリビニルアルコール系樹脂(B)とより好適に架橋構造を形成するためであると考えられる。なかでも、ポリビニルアルコール系樹脂の水酸基と好適に架橋反応を形成するとともに、透明性に優れているという観点から、イソシアネート系化合物を用いることが特に好ましい。また、架橋反応を促進させるため、触媒等を必要に応じて適宜使用しても良い。
本発明の易接着層中には、本発明の効果を阻害しない範囲において公知の添加剤、例えば界面活性剤、酸化防止剤、触媒、耐熱安定剤、耐候安定剤、紫外線吸収剤、有機の易滑剤、顔料、染料、有機または無機の粒子、帯電防止剤、核剤等を添加しても良い。
本発明の偏光子保護用ポリエステルフィルムの光の透過率を向上させるために、易接着層が設けられる面と反対の面の波長400~700nmの光の平均絶対反射率は6%以下であることが好ましい。平均絶対反射率は、より好ましくは5%以下であり、さらに好ましくは4.5%以下である。平均絶対反射率が、6%より大きいと、透過しようとする可視光のフィルム表面での反射が大きくなり、透過率が低下する。一方、6%以下であると、フィルム表面での反射が抑制され、透過率の高い偏光子保護用ポリエステルフィルムを提供することができる。
低屈折率層に使用されるウレタン樹脂は、構成成分として、少なくともポリオール成分、ポリイソシアネート成分を含み、さらに必要に応じて鎖延長剤を含むことが好ましい。ウレタン樹脂は、これら構成成分が主としてウレタン結合により共重合された高分子化合物である。
低屈折率層に使用されるポリエステル樹脂としては以下のものがあげられる。ポリエステル樹脂の数平均分子量は15000以上であることが好ましい。数平均分子量が低い場合、末端のカルボン酸基が増加するため、加水分解が促進され、高温高湿下の密着性が得られないだけでなく、基材フィルムとの密着性も低下させてしまう。また、上記数平均分子量は、20000以上がより好ましく、さらに製造可能な限り、高い方が好ましい。しかし、数平均分子量が大きくなると、塗布液への溶解性が低下する場合もあることから、上記数平均分子量は、60000以下であることが好ましい。
低屈折率層に使用されるアクリル樹脂には、特に限定されないがアクリル系、メタアクリル系のモノマーに代表されるような、炭素-炭素二重結合を持つ重合性モノマーからなる重合体が使用できる。これらは、単独重合体あるいは共重合体いずれでも差し支えない。また、それら重合体と他のポリマー(例えばポリエステル、ポリウレタン等)との共重合体も含まれる。例えば、ブロック共重合体、グラフト共重合体である。あるいは、ポリエステル溶液、またはポリエステル分散液中で炭素-炭素二重結合を持つ重合性モノマーを重合して得られたポリマー(場合によってはポリマーの混合物)も含まれる。同様にポリウレタン溶液、ポリウレタン分散液中で炭素-炭素二重結合を持つ重合性モノマーを重合して得られたポリマー(場合によってはポリマーの混合物)も含まれる。同様にして他のポリマー溶液、または分散液中で炭素-炭素二重結合を持つ重合性モノマーを重合して得られたポリマー(場合によってはポリマー混合物)も含まれる。また、より効率よく全光線透過率を向上させるために、屈折率が低いフッ素原子含有の化合物を使用することも可能である。
低屈折率層に用いられるフッ素含有樹脂としては、特に限定されないが、以下のものが好適に用いられる。フッ素含有樹脂としては、例えば1-(メタ)アクリロイロキシ-1-パーフルオロアルキルメタン、1-(メタ)アクリロイロキシ-2-パーフルオロアルキルエタン、1,10-ビスアクリロイルオキシ-1,1,10,10-テトラヒドロパーフルオロデカン、1,10-ビスビスアクリロイルオキシ-2,9-ジヒドロキシー4,4,5,5,6,6,7,7-オクタフルオロデカン、1,9-ビスビスアクリロイルオキシ-2,10-ジヒドロキシー4,4,5,5,6,6,7,7-オクタフルオロデカン、2,9-ビスビスアクリロイルオキシ-1,10-ジヒドロキシー4,4,5,5,6,6,7,7-オクタフルオロデカン、1,2-ジ(メタ)アクリロイルオキシ-3-パーフルオロアルキルブタン、2-ヒドロキシ-1H,1H,2H,3H,3H-パーフルオロアルキル-2’,2’-ビス{(メタ)アクリロイルオキシメチル}プロピオナート、α,ω-ジ(メタ)アクリロイルオキシメチルパーフルオロアルカン、α,β,ψ,ω-テトラキス{(メタ)アクリロイルオキシ}-αH,αH,βH,γH,γH,χH,χH,ψH,ωH,ωH-パーフルオロアルカン等が好ましい。
低屈折率層に用いられるポリビニルアルコール樹脂としては、特に限定されないが、本明細書の易接着層に使用するものと同じものを使用することができる。
低屈折率層にハードコート性を持たせることについては、前述したとおりである。なお、ハードコート層に使用される樹脂としては、前述の電子線又は紫外線による硬化する樹脂、好ましくは電子線又は紫外線により硬化するアクリル樹脂を用いることが好ましい。
低屈折率層に防眩性を付与する方法としては、公知の技術を用いることができる。例えば、ポリエステルフィルム上に凹凸形状を形成し、外光を散乱させて外光の反射や像の映り込みによる視認性の低下を防止することができる。凹凸を形成する方法としては、大粒径または凝集性のある粒子を含んだ樹脂を塗工し、フィルム表面に凹凸形状を形成する方法、または、層表面に凹凸を有するフィルムをラミネートして凹凸形状を転写することによって防眩層を形成する方法、前記粒子は含有せず、ナノインプリントで凹凸を形成する方法があり、1種類もしくは2種類以上を組み合わせて使用することができる。
本発明の低屈折率層とポリエステルフィルムの間に防眩層を積層し、防眩性反射防止層とすることができる。防眩性反射防止層の積層には、公知の技術を用いることができる。このとき防眩層の屈折率は、低屈折率層よりも高くすることで、本発明の効果を保つことができる。
低屈折率層とポリエステルフィルムの間に、ポリエステルフィルム側から順に中屈折率層、高屈折率層、もしくは、高屈折率層のみを積層し、反射防止層とすることができる。反射防止層としては、本発明の効果を失わない範囲で、上記以外に公知の技術を用いて積層することもできる。
本発明のポリエステルフィルムの反射防止層の高屈折率層、中屈折率層は、無機材料、有機材料などを組み合わせて構成される。高屈折率層の屈折率は、低屈折率層より高く、1.60以上であることがよく、1.60~1.90であることが好ましい。1.60未満であると十分な反射防止効果が得られず、1.90を超える樹脂層をウェットコーティングで形成することは困難になる。中屈折率層の屈折率は、高屈折率層よりも低く、低屈折率層よりも高く、1.50~1.65の範囲であることが好ましい。
上記無機微粒子としては、金属(例Ti、Zr、In、Zn、Sn、Sb、Al)の酸化物が好ましく、屈折率の観点から、酸化ジルコニウムの微粒子が最も好ましい。ただし、導電性の観点からは、Sb、In、Snのうちの少なくとも1種類の金属の酸化物を主成分とする無機微粒子を用いることが好ましい。無機微粒子の量を変化させることで所定の屈折率に調整することができる。層中の無機微粒子の平均粒径は、酸化ジルコニウムを主成分として用いた場合、1~120nmであることが好ましく、さらに好ましくは5~100nm、10~100nmがさらに好ましい。この範囲内で、ヘイズを抑え、分散安定性、表面の適度の凹凸による上層との密着性が良好となり、好ましい。
本発明の偏光子保護用易接着性ポリエステルフィルムの製造方法について、ポリエチレンテレフタレート(以下、PETと略記する)フィルムを例にして説明するが、当然これに限定されるものではない。
本発明の偏光板は、偏光子の両面に偏光子保護フィルムを有してなる偏光板であって、すくなくとも一方の面の偏光子保護フィルムが前記偏光子保護用易接着性ポリエステルフィルムであることが好ましい。他方の偏光子保護フィルムは、本発明の偏光子保護用易接着性ポリエステルフィルムであっても良いし、トリアセチルセルロースフィルムやアクリルフィルム、ノルボルネン系フィルムに代表されるような複屈折が無いフィルムを用いることも好ましい。
JIS K7121に準拠し、示差走査熱量計(セイコーインスツルメンツ製、DSC6200)を使用して、樹脂サンプル10mgを25~300℃の温度範囲にわたって20℃/minで昇温させ、DSC曲線から得られた補外ガラス転移開始温度をガラス転移温度とした。
樹脂0.03gをテトラヒドロフラン 10ml に溶かし、GPC-LALLS装置低角度光散乱光度計 LS-8000(東ソー株式会社製、テトラヒドロフラン溶媒、リファレンス:ポリスチレン)を用い、カラム温度30℃、流量1ml/分、カラム(昭和電工社製shodex KF-802、804、806)を用い、数平均分子量を測定した。
樹脂を重クロロホルムに溶解し、ヴァリアン社製核磁気共鳴分析計(NMR)ジェミニ-200を用いて、1H-NMR分析を行ってその積分比より各組成のモル%比を決定した。
1g(固形分)の試料を30mlのクロロホルムまたはジメチルホルムアミドに溶解し、フェノールフタレインを指示薬として0.1Nの水酸化カリウムエタノール溶液で滴定して、試料1g当たりのカルボキシル基を中和するのに必要なKOHの量(mg)を求めた。
JIS-K6726に準じて水酸化ナトリウムを用いて、ポリビニルアルコール樹脂の残存酢酸基(モル%)を定量し、その値をけん化度(モル%)とした。同サンプルについて3度測定し、その平均値をけん化度(モル%)とした。
偏光子保護用ポリエステルフィルムの全光線透過率はJIS K 7105に準拠し、濁度計(日本電色製、NDH2000)を用いて測定した。尚、偏光子保護フィルムの易接着層を有する面とは反対側の面から光線をあてて測定した。
偏光子保護ポリエステルフィルムのヘイズはJIS K 7136に準拠し、濁度計(日本電色製、NDH2000)を用いて測定した。尚、偏光子保護フィルムの易接着層を有する面とは反対側の面から光線をあてて測定した。
偏光子保護用ポリエステルフィルムの易接着層表面に、固形分濃度5質量%に調整したポリビニルアルコール水溶液(クラレ製 PVA117)を、乾燥後のポリビニルアルコール樹脂層の厚みが、2μmになるようにワイヤーバーで塗布し、70℃で5分間乾燥した。ポリビニルアルコール水溶液には、判定が容易となるよう赤色染料を加えたものを使用した。作成した評価対象フィルムを、両面テープを貼り付けた厚さ5mmのガラス板に、評価対象の積層フィルムのポリビニルアルコール樹脂層が形成された面の反対面を上記両面テープに貼り付けた。次いで、ポリビニルアルコール樹脂層を貫通して、基材フィルムに達する100個の升目状の切り傷を、隙間間隔2mmのカッターガイドを用いて付けた。次いで、粘着テープ(ニチバン社製セロテープ(登録商標) CT-24;24mm幅)を升目状の切り傷面に貼り付けた。貼り付け時に界面に残った空気を消しゴムで押して、完全に密着させた後、粘着テープを勢いよく垂直に引き剥がす作業を1回、5回、10回実施した。ポリビニルアルコール樹脂層が剥がれていない升目の個数を数え、PVA接着性とした。即ち、PVA層が全く剥がれていない場合を、PVA接着率100とし、PVA層が全て剥がれた場合は、PVA接着率0とした。なお、1個の升目内で部分的に剥がれているものも、剥がれた個数に含めた。
偏光子保護用積層フィルムの低屈折率層の絶対反射率の平均値の測定方法は、ポリエステルフィルムの測定裏面(易接着層)に黒色テープ(日東電工製、ビニルテープNo21:黒)を貼りあわせた。その後、分光光度計(島津製作所、UV-3150)を使用し、入射角:5°、波長送り速度:高速(約700nm/min)、サンプリング間隔:0.5nm、スペクトルバンド幅:1nmで、低屈折率層表面を波長範囲300~800nmの絶対反射率を測定し、400~700nmの平均値を算出し、平均反射率とした。
本発明の偏光子保護用積層ポリエステルフィルムに設ける低屈折率層の屈折率は、以下の方法で測定した。低屈折率層に用いる塗布液を乾燥後の厚みが約4μmになるようにガラス板に塗布し、乾燥、硬化後に、アッベ屈折率計(アタゴ社製、NAR-4T、測定波長589nm)で測定した値を低屈折率層の屈折率とした。
攪拌機、温度計、および部分還流式冷却器を具備するステンレススチール製オートクレーブに、ジメチルテレフタレート194.2質量部、ジメチルイソフタレート184.5質量部、ジメチルー5-ナトリウムスルホイソフタレート14.8質量部、ジエチレングリコール233.5質量部、エチレングリコール136.6質量部、およびテトラーnーブチルチタネート0.2質量部を仕込み、160℃から220℃の温度で4時間かけてエステル交換反応を行なった。次いで255℃まで昇温し、反応系を徐々に減圧した後、30Paの減圧下で1時間30分反応させ、共重合ポリエステル樹脂(A-1)を得た。得られた共重合ポリエステル樹脂(A-1)は、淡黄色透明であった。共重合ポリエステル樹脂(A-1)の還元粘度を測定したところ,0.70dl/gであった。DSCによるガラス転移温度は40℃であった。
攪拌機、温度計と還流装置を備えた反応器に、ポリエステル樹脂(A-1)30質量部、エチレングリコールn-ブチルエーテル15質量部を入れ、110℃で加熱、攪拌し樹脂を溶解した。樹脂が完全に溶解した後、水55質量部をポリエステル溶液に攪拌しつつ徐々に添加した。添加後、液を攪拌しつつ室温まで冷却して、固形分30質量%の乳白色のポリエステル水分散体(Aw-1)を作製した。同様にポリエステル樹脂(A-1)の代わりにポリエステル樹脂(A-2)~(A-5)を使用して、水分散体を作製し、それぞれポリエステル水分散体(Aw-2)~(Aw-5)とした。
攪拌機と温度計を備えた容器に、水90質量部を入れ、攪拌しながら重合度500のポリビニルアルコール樹脂(クラレ製)(B-1)10質量部を徐々に添加した。添加後、液を攪拌しながら、95℃まで加熱し、樹脂を溶解させた。溶解後、攪拌しながら室温まで冷却して、固形分10質量%のポリビニルアルコール水溶液(Bw-1)を作成した。同様に、ポリビニルアルコール樹脂(B-1)の代わりにポリビニルアルコール樹脂(B-2)~(B-7)を使用し水溶液を作成し、それぞれ(Bw-2)~(Bw-7)とした。ポリビニルアルコール樹脂(B-1)~(B-7)のけん化度を表2に示す。
攪拌機、温度計、還流冷却管を備えたフラスコにヘキサメチレンジイソシアネートを原料としたイソシアヌレート構造を有するポリイソシアネート化合物(旭化成ケミカルズ製、デュラネートTPA)100質量部、プロピレングリコールモノメチルエーテルアセテート55質量部、ポリエチレングリコールモノメチルエーテル(平均分子量750)30質量部を仕込み、窒素雰囲気下、70℃で4時間保持した。その後、反応液温度を50℃に下げ、メチルエチルケトオキシム47質量部を滴下した。反応液の赤外スペクトルを測定し、イソシアネート基の吸収が消失したことを確認し、固形分75質量%のブロックポリイソシアネート水分散液(C-1)を得た。
脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂D-1を次の手順で作製した。撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、4,4-ジフェニルメタンジイソシアネート43.75質量部、ジメチロールブタン酸12.85質量部、数平均分子量2000のポリヘキサメチレンカーボネートジオール153.41質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン8.77質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min-1で攪拌混合しながら、ポリウレタンプレポリマー溶液を添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分35%の水溶性ポリウレタン樹脂を調製した。得られた脂肪族系ポリカーボネートポリオールを構成成分とするポリウレタン樹脂(D-1U)のガラス転移点温度は-30℃であった。
以下の組成で低屈折率層塗布液(D-1)を調整した。
水 53.50質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂(D-1U) 12.00質量%
ブロックイソシアネート系架橋剤(C-1) 2.40質量%
粒子 1.50質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.60質量%
(シリコン系、固形分濃度10質量%)
以下の組成で低屈折率層塗布液(D-2)を調整した。
水 56.37質量%
イソプロパノール 30.00質量%
アクリル樹脂 9.13質量%
(RX2035A、日本カーバイド製、固形分46%)
ブロックイソシアネート系架橋剤(C-1) 2.40質量%
粒子 1.50質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.60質量%
(シリコン系、固形分濃度10質量%)
以下の組成で低屈折率層塗布液(D-3)を調整した。
水 51.50質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 14.00質量%
ブロックイソシアネート系架橋剤(C-1) 2.40質量%
粒子 1.50質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.60質量%
(シリコン系、固形分濃度10質量%)
後述する実施例で製造したポリエステルフィルムの偏光子と接着する面とは反対側の面に、下記組成のハードコート層形成用塗布液を#10ワイヤーバーを用いて塗布し、70℃で1分間乾燥し、溶剤を除去した。次いで、ハードコート層を塗布したフィルムに高圧水銀灯を用いて300mJ/cm2の紫外線を照射し、厚み5μmのハードコート層を有する偏光子保護フィルムを得た。
ハードコート層形成用塗布液
メチルエチルケトン 65.00質量%
ジペンタエリスリトールヘキサアクリレート 27.20質量%
(新中村化学製A-DPH)
ポリエチレンジアクリレート 6.80質量%
(新中村化学製A-400)
光重合開始剤 1.00質量%
(チバスペシャリティーケミカルズ社製イルガキュア184)
後述する実施例で製造したポリエステルフィルムの偏光子と接着する面とは反対側の面に、下記組成の防眩層形成用塗布液を#5ワイヤーバーを用いて塗布し、70℃で1分間乾燥し、溶剤を除去した。次いで、防眩層を塗布したフィルムに高圧水銀灯を用いて300mJ/cm2の紫外線を照射し、厚み5μmの防眩層(D-5)を有する偏光子保護フィルムを得た。
防眩層形成用塗布液
トルエン 34重量部
ペンタエリスリトールトリアクリレート 50重量部
シリカ(平均粒径1μm) 12重量部
シリコーン(レベリング剤) 1重量部
光重合開始剤 1重量部
(チバスペシャリティーケミカルズ社製イルガキュア184)
後述する実施例で製造したポリエステルフィルムの偏光子と接着する面とは反対側の面に、下記組成の中屈折率層形成用塗布液をバーコーターを用いて塗布し、70℃1分間乾燥後、高圧水銀灯を用いて400mJ/cm2の紫外線を照射し、乾燥膜厚5μmの中屈折率層を得た。次に、形成した中屈折率層の上に、バーコーターを用いて、下記組成の高屈折率層形成用塗布液を中屈折率層と同様の方法で形成し、さらにその上に下記組成の低屈折率層形成用塗布液を中屈折率層と同様の方法で形成し、反射防止層(D-6)を積層した、偏光子保護用ポリエステルフィルムを得た。
中屈折率層形成用塗布液(屈折率1.52)
ジペンタエリスリトールヘキサアクリレート 70重量部
1,6-ビス(3-アクリロイルオキシ-2-ヒドロキシプロピルオキシ)ヘキサン
30重量部
光重合開始剤 4重量部
(チバスペシャルティケミカルズ(株)製、イルガキュア184)
イソプロパノール 100重量部
高屈折率層形成用塗布液(屈折率1.64)
ITO微粒子(平均粒径0.07μm) 85重量部
テトラメチロールメタントリアクリレート 15重量部
光重合開始剤(KAYACURE BMS、日本化薬製) 5重量部
ブチルアルコール 900重量部
低屈折率層形成用塗布液(屈折率1.42)
1,10-ジアクリロイルオキシ-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-ヘキサデカフルオロデカン 70重量部
ジペンタエリスリトールヘキサアクリレート 10重量部
シリカゲル微粒子(XBA-ST、日産化学製) 60重量部
光重合開始剤(KAYACURE BMS、日本化薬製) 5重量部
(1)易接着層の塗布液の調整
下記の塗剤を混合し、ポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が70/30になる塗布液を作成した。ポリエステル水分散体は、酸価が2KOHmg/gであるポリエステル樹脂が分散した水分散体(Aw-1)を使用し、ポリビニルアルコール水溶液は、けん化度が74モル%であるポリビニルアルコールが溶解した水溶液(Bw-4)を使用した。
水 40.61質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 11.67質量%
ポリビニルアルコール水溶液(Bw-4) 15.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
フィルム原料ポリマーとして、固有粘度(溶媒:フェノール/テトラクロロエタン=60/40)が0.62dl/gで、かつ粒子を実質上含有していないPET樹脂ペレットを、133Paの減圧下、135℃で6時間乾燥した。その後、押し出し機に供給し、約280℃でシート状に溶融押し出しして、表面温度20℃に保った回転冷却金属ロール上で急冷密着固化させ、未延伸PETシートを得た。
易接着層のポリエステル水分散体を酸価が4KOHmg/gのポリエステル樹脂が分散した水分散体(Aw-2)に変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
易接着層のポリエステル水分散体を酸価が6KOHmg/gのポリエステル樹脂が分散した水分散体(Aw-3)に変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
易接着層のポリビニルアルコール水溶液を、ポリビニルアルコールのけん化度が79モル%であるポリビニルアルコール水溶液(Bw-3)に変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
易接着層のポリビニルアルコールのけん化度が83モル%であるポリビニルアルコール水溶液(Bw-2)に変更した以外は、実施例1と同様にして、偏光子保護ポリエステルフィルムを得た。
易接着層を下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が60/40になるように変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
水 37.28質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 10.00質量%
ポリビニルアルコール水溶液(Bw-4) 20.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
易接着層を下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が80/20になるように変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
水 43.95質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 13.33質量%
ポリビニルアルコール水溶液(Bw-4) 10.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
易接着層を下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が50/50になるように変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
水 33.95質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 8.33質量%
ポリビニルアルコール水溶液(Bw-4) 25.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
易接着層の塗布液組成を下記の通り変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
水 40.87質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 11.67質量%
ポリビニルアルコール水溶液(Bw-4) 15.00質量%
メラミン系架橋剤(C-2) 0.71質量%
(ニカラックMX-042 三和ケミカル製 固形分濃度70%)
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
易接着層のポリビニルアルコール水溶液を、ポリビニルアルコールのけん化度が70モル%であるポリビニルアルコールが溶解した水溶液(Bw-5)に変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
易接着層のポリビニルアルコール水溶液を、ポリビニルアルコールのけん化度が67モル%であるポリビニルアルコールが溶解した水溶液(Bw-6)に変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
易接着層の塗布液組成を下記の通り変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
水 40.33質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 11.67質量%
ポリビニルアルコール水溶液(Bw-2) 15.00質量%
オキサゾリン系架橋剤(C-3) 1.25質量%
(エポクロスWS-500、日本触媒製、固形分濃度40質量%)
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
易接着層のポリエステル水分散体を酸価が10KOHmg/gのポリエステル樹脂が分散した水分散体(Aw-5)に変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
低屈折率層の塗布液をD-2に変更した以外は、実施例1と同様にして偏光子保護用ポリエステルフィルムを得た。
低屈折率層の塗布液をD-3に変更した以外は、実施例1と同様にして偏光子保護用ポリエステルフィルムを得た。
実施例1の低屈折率層D-1上に、D-4を形成した以外は、実施例1と同様にして偏光子保護用ポリエステルフィルムを得た。
実施例1の低屈折率層D-1上に、D-5を形成した以外は、実施例1と同様にして偏光子保護用ポリエステルフィルムを得た。
実施例1の低屈折率層D-1上に、D-6を形成した以外は、実施例1と同様にして偏光子保護用ポリエステルフィルムを得た。
低屈折率層D-1の膜厚を0.06g/m2にした以外は、実施例1と同様にして偏光子保護用ポリエステルフィルムを得た。
低屈折率層D-1の膜厚を0.18g/m2にした以外は、実施例1と同様にして偏光子保護用ポリエステルフィルムを得た。
下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が100/0になるように易接着層の塗布液を変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
水 50.62質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 16.66質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
下記の塗剤を混合しポリエステル系樹脂(A)/ポリビニルアルコール系樹脂(B)の質量比が0/100になるように易接着層の塗布液を変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
水 17.28質量%
イソプロパノール 30.00質量%
ポリビニルアルコール水溶液(Bw-4) 50.00質量%
ブロックイソシアネート系架橋剤(C-1) 0.67質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
触媒
(有機スズ系化合物 固形分濃度14質量%) 0.3質量%
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
ポリエステル水分散体を酸価が25KOHmg/gのポリエステル樹脂が分散した水分散体(Aw-4)に変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
ポリビニルアルコール水溶液を、けん化度が88モル%であるポリビニルアルコールが溶解した水溶液(Bw-1)に変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
ポリビニルアルコール水溶液を、けん化度が40モル%であるポリビニルアルコールが溶解した水溶液(Bw-7)に変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
下記の塗剤を混合し架橋剤を混合しないように易接着層の塗布液を変更した以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
水 41.58質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(Aw-1) 11.67質量%
ポリビニルアルコール水溶液(Bw-4) 15.00質量%
粒子 1.25質量%
(平均粒径100nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.5質量%
(シリコン系、固形分濃度10質量%)
低屈折率層を設けなかった以外は、実施例1と同様にして、偏光子保護用ポリエステルフィルムを得た。
低屈折率層D-1の膜厚を0.02g/m2にした以外は、実施例1と同様にして偏光子保護用ポリエステルフィルムを得た。
偏光子保護用フィルムとしてTACフィルム(富士フイルム(株)社製、厚み80μm、けん化処理済)を用い、前記接着性試験を行なった結果を示す。
Claims (8)
- 偏光子との易接着層を片面に有するポリエステルフィルムであって、
前記易接着層が、ポリエステル系樹脂(A)とポリビニルアルコール系樹脂(B)と架橋剤(C)を含有し、
前記ポリエステル系樹脂(A)の酸価が20KOHmg/g以下であり、
前記ポリビニルアルコール系樹脂(B)のけん化度が60~85モル%であり、
前記ポリエステルフィルムの前記片面とは反対の面の波長400~700nmの光の平均絶対反射率が6%以下である、偏光子保護用ポリエステルフィルム。 - 前記反対の面に、前記ポリエステルフィルムよりも屈折率の低い低屈折率層を有する、請求項1記載の偏光子保護用ポリエステルフィルム。
- 前記低屈折率層が、ハードコート層、防眩層及び反射防止層からなる群より選択される少なくとも一つの機能層である、請求項1又は2記載の偏光子保護用ポリエステルフィルム。
- 前記ポリエステル樹脂(A)が5-スルホイソフタル酸成分をジカルボン酸成分中1~15モル%含有する、請求項1~3のいずれかに記載の偏光子保護用ポリエステルフィルム。
- 前記架橋剤(C)がイソシアネート化合物又はメラミン化合物である、請求項1~4のいずれかに記載の偏光子保護用ポリエステルフィルム。
- 前記易接着層中、ポリエステル系樹脂(A)、ポリビニルアルコール系樹脂(B)および架橋剤(C)の質量比が以下の式を満足する、請求項1~5のいずれかに記載の偏光子保護用ポリエステルフィルム。
0.8≦(A)/(B)≦5
2≦((A)+(B))/(C)≦50 - 偏光子の両面に偏光子保護フィルムを有してなる偏光板であって、
少なくとも一方の偏光子保護フィルムが請求項1~6のいずれかに記載の偏光子保護用ポリエステルフィルムである偏光板。 - 請求項7記載の偏光板を少なくとも1つ有する画像表示装置。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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JP2014502936A JP5850135B2 (ja) | 2012-08-07 | 2013-08-06 | 偏光子保護用ポリエステルフィルム、偏光板および液晶表示装置 |
KR1020157005523A KR101767791B1 (ko) | 2012-08-07 | 2013-08-06 | 편광자 보호용 폴리에스테르 필름, 편광판 및 액정표시장치 |
CN201380042126.9A CN104520738B (zh) | 2012-08-07 | 2013-08-06 | 偏振片保护用聚酯薄膜、偏光板以及液晶显示装置 |
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JP2015152837A (ja) * | 2014-02-17 | 2015-08-24 | 大日本印刷株式会社 | 積層体、積層体の製造方法、画像表示装置、画像表示装置の製造方法及び偏光板の光透過率改善方法 |
JP2017193117A (ja) * | 2016-04-21 | 2017-10-26 | 三菱ケミカル株式会社 | 積層ポリエステルフィルム |
JP2021104649A (ja) * | 2019-12-27 | 2021-07-26 | 三菱ケミカル株式会社 | 積層造形用サポート材 |
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JP5994469B2 (ja) * | 2012-08-07 | 2016-09-21 | 東洋紡株式会社 | 偏光子保護用ポリエステルフィルム |
JP6734745B2 (ja) * | 2015-10-14 | 2020-08-05 | 日東電工株式会社 | 偏光子およびその製造方法 |
JP7195039B2 (ja) * | 2015-10-16 | 2022-12-23 | 株式会社Adeka | 樹脂組成物およびこれを用いた光学フィルム |
KR20190100916A (ko) * | 2016-12-28 | 2019-08-29 | 니폰 제온 가부시키가이샤 | 필름 |
KR102186080B1 (ko) | 2017-06-27 | 2020-12-03 | 주식회사 엘지화학 | 접착제 조성물, 이를 포함하는 접착제층을 포함하는 보호필름 및 편광판, 및 이를 포함하는 화상표시장치 |
JP2021509427A (ja) | 2017-12-28 | 2021-03-25 | 日東電工株式会社 | ガラスユニットの製造方法および粘着シート |
CN111629901B (zh) * | 2018-01-19 | 2022-05-06 | 东洋纺株式会社 | 易粘接性聚酯薄膜 |
JP6580769B2 (ja) * | 2018-02-07 | 2019-09-25 | 日東電工株式会社 | 偏光板および画像表示装置 |
KR102052843B1 (ko) * | 2019-01-07 | 2019-12-06 | 도레이첨단소재 주식회사 | 편광자 보호용 폴리에스테르 필름과 그 제조방법 및 이를 구비하는 편광판 |
JP7240938B2 (ja) * | 2019-04-15 | 2023-03-16 | 住友化学株式会社 | 光学積層体及び画像表示装置 |
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KR20150039825A (ko) | 2015-04-13 |
TWI522246B (zh) | 2016-02-21 |
KR101767791B1 (ko) | 2017-08-11 |
TW201412553A (zh) | 2014-04-01 |
CN104520738A (zh) | 2015-04-15 |
CN104520738B (zh) | 2017-02-01 |
JPWO2014024855A1 (ja) | 2016-07-25 |
JP5850135B2 (ja) | 2016-02-03 |
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