WO2010134416A1 - 光学用易接着性ポリエステルフィルム - Google Patents
光学用易接着性ポリエステルフィルム Download PDFInfo
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- WO2010134416A1 WO2010134416A1 PCT/JP2010/057130 JP2010057130W WO2010134416A1 WO 2010134416 A1 WO2010134416 A1 WO 2010134416A1 JP 2010057130 W JP2010057130 W JP 2010057130W WO 2010134416 A1 WO2010134416 A1 WO 2010134416A1
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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
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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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
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
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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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/72—Cured, e.g. vulcanised, cross-linked
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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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
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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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
- B32B2551/00—Optical elements
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
Definitions
- the present invention relates to an optically easily adhesive polyester film.
- it is attached to the front of a display screen such as a touch panel, a liquid crystal display (LCD), a television or computer cathode ray tube (CRT), a plasma display (PDP), an organic electroluminescence (organic EL), etc.
- the present invention relates to an optically easily adhesive polyester film that imparts antireflection properties to suppress glare, iris-like colors, etc., and is excellent in adhesion to a hard coat layer and adhesion after high-temperature and high-humidity treatment.
- a hard coat film in which a transparent hard coat layer is laminated is used on the front surface of displays such as touch panels, computers, televisions, and liquid crystal display devices, and decorative materials.
- a transparent biaxially oriented polyester film is generally used as the transparent plastic film of the substrate, and in order to improve the adhesion between the polyester film of the substrate and the hard coat layer, these intermediate layers can be easily used.
- a coating layer having adhesiveness is provided.
- the hard coat film is required to have temperature, humidity, light durability, transparency, chemical resistance, scratch resistance, antifouling property and the like. Further, since the hard coat film is often used on the surface of a display or a decorative material, visibility and design are required. Therefore, in order to suppress glare and iris-like color caused by reflected light when viewed from an arbitrary angle, the antireflection of a multilayer structure in which a high refractive index layer and a low refractive index layer are laminated on top of the hard coat layer. It is common practice to provide a layer.
- the iris-like color (interference spots) of the hard coat film is the difference between the refractive index of the base polyester film (eg, 1.62-1.65) and the refractive index of the hard coat layer made of acrylic resin (eg, 1.49). It is said that it occurs because of the large difference.
- a coating layer is provided on the polyester film of the base material, the refractive index difference between the polyester film and the coating layer, the refraction of the coating layer and the hard coat layer
- a method is disclosed in which the refractive index of the coating layer is controlled by the contents of the resin constituting the coating layer and the high refractive additive so as to reduce the difference in rate.
- Patent Document 1 a water-soluble polyester resin and a water-soluble metal chelate compound or metal acylate compound
- Patent Document 2 a polymer binder and a high refractive index metal oxide.
- the main component of the polyester resin used for controlling the refractive index is a naphthalene dicarboxylic acid component or a short-chain diol component
- the hardness of the resin composition is relatively high, It is a hard coating layer. Therefore, there was a situation in which particles in the coating layer dropped off (powders) during film cutting and adhered as foreign matter.
- an optically easy-adhesive polyester film that has an effect of suppressing interference spots that can be applied in a wide range even with various solvents, and that has less scratching of the coating layer even during high-speed processing, and has a stable interference spot reduction effect. is there. That is, the present invention suppresses the iris-like color under a fluorescent lamp, is excellent in adhesion to the hard coat layer, is excellent in adhesion at high temperature and high humidity, and is resistant to the coating layer even during high-speed post-processing.
- An object is to provide an optically easy-adhesive polyester film having shaving properties and an optically laminated polyester film obtained by laminating a hard coat layer on the film.
- the present inventors have added a large particle having an average particle size of 200 nm or more and 700 nm or less to the coating layer having a predetermined refractive index.
- the surprising effect of stably suppressing interference spots is found, and the coating layer is scraped by using a polyester resin containing a long-chain dicarboxylic acid component and / or a long-chain diol component having a specific carbon number.
- the present invention is an optically easily adhesive polyester film having a coating layer containing a polyester resin, particles A and particles B on at least one surface of the polyester film, wherein the polyester resin is naphthalenedicarboxylic acid as an acid component. And a dicarboxylic acid component represented by the following formula (1) and / or a diol component represented by the following formula (2), wherein the particles A have a refractive index of 1.7 or more and 3.0 or less. It is an easily adhesive polyester film for optics, wherein the particle B is a particle having an average particle diameter of 200 nm or more and 700 nm or less.
- the present invention also provides the above-mentioned easily adhesive polyester film for optics, wherein the coating layer contains a crosslinking agent.
- the crosslinking agent is at least one crosslinking agent selected from a urea crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an isocyanate crosslinking agent, an oxazoline crosslinking agent, and a carbodiimide crosslinking agent.
- the easy-adhesive polyester film for optical use according to the present invention.
- the present invention also provides an optically laminated polyester film obtained by laminating a hard coat layer made of an electron beam, an ultraviolet curable acrylic resin, or a siloxane-based thermosetting resin on the coating layer of the optically easy-adhesive polyester film. It is.
- the optically easy-adhesive polyester film of the present invention is excellent in suppressing interference spots when a hard coat layer is laminated on the easy-adhesive layer of the film, and has excellent adhesion with the hard coat layer and adhesiveness under high temperature and high humidity. In addition to being excellent in (moisture and heat resistance), the shaving property of the coating layer can be remarkably suppressed. Therefore, it is suitable as a base film for an optically laminated polyester film in which a hard coat layer is laminated.
- the polyester film used as a substrate in the present invention is a film composed of a polyester resin, and mainly contains at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate as a constituent component.
- polyester resins polyethylene terephthalate is most preferable from the balance between physical properties and cost.
- these polyester films can improve chemical resistance, heat resistance, mechanical strength, etc. by biaxially stretching.
- the biaxially stretched polyester film may be a single layer or a multilayer. Moreover, as long as it exists in the range with the effect of this invention, each of these layers can contain various additives in a polyester resin as needed. Examples of 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.
- inert particles are included in the polyester film of the base material.
- the film of the present invention is used as a base film for an optical member, it is required to have excellent handling properties while maintaining high transparency.
- the transparency is preferably such that the total light transmittance of the optically easy-adhesive polyester film is 85% or more, more preferably 87% or more, and further 88% or more. Preferably, 89% or more is even more preferable, and 90% or more is particularly preferable.
- the content of the inert particles in the base film is as small as possible. Therefore, it is preferable to make a multilayer structure in which particles are contained only in the surface layer of the film, or to contain fine particles only in the coating layer without substantially containing particles in the film.
- an inorganic and / or heat-resistant polymer particle is contained in the aqueous coating solution in order to improve the handleability of the film. It is important to form irregularities on the surface of the coating layer.
- substantially no inert 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, Preferably, the content is below the detection 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 intermediate layer does not substantially contain inert particles, and the outermost layer contains inert particles only in the two- and three-layer structure. It is preferable that both can be achieved.
- a base film imparted with moldability by a polyester resin containing a copolymer component may be used.
- the easily adhesive film for optics of the present invention includes a polyester containing naphthalene dicarboxylic acid as an acid component and a dicarboxylic acid component represented by the following formula (1) and / or a diol component represented by the following formula (2). It is important to provide a coating layer containing a resin, metal oxide particles (particle A) having a refractive index of 1.7 to 3.0 and particles (particle B) having an average particle size of 200 nm to 700 nm. That is, according to the following achievement means of the present invention.
- Refractive index control of coating layer In the optically easy-adhesive film of the present invention, it is necessary to adjust the refractive index of the coating layer in the vicinity of the middle between the hard coat layer and the base polyester film. Since the refractive index of the hard coat layer varies depending on the composition of the resin used in the hard coat layer, it is desirable to adjust the refractive index of the coating layer accordingly. It is necessary to adjust to the range of 6 to 1.7. By doing in this way, each interface refractive index difference is made small and interference spots are suppressed. In general, a coating layer having easy adhesion has a low refractive index (around 1.50).
- naphthalenedicarboxylic acid is used as an acid component for the resin used in the coating layer.
- metal oxide particles (particle A) having a refractive index of 1.7 or more and 3.0 or less are added. With such a configuration, it is possible to obtain a coating layer having a high refractive index while having adhesion. Details of these compositions will be described later.
- Such random light scattering may cause a phase disorder of the reflected light generated at the interface between the coating layer and the base polyester film, resulting in an effect of suppressing interference spots. Since the coating layer of the optically easy-adhesive film of this application has such a configuration, it is not necessary to control the coating thickness as in the prior art, and it can be applied to a wide range of coating solutions for forming a hard coat layer consisting of various solvents. It became.
- the thickness of the coating layer is preferably smaller than the average particle size of the particles B, and the thickness of the coating layer is preferably less than 1/1 of the average particle size of the particles B, 1/2 The following is more preferable. Moreover, 1/15 or more of the average particle diameter of the particle
- grains B is preferable, as for the thickness of an application layer, 1/10 or more is more preferable, and 1/7 or more is further more preferable. When the thickness of the coating layer is less than 1/15 of the average particle diameter of the particles B, the transparency may be lowered.
- Polyester resin containing a long-chain dicarboxylic acid component and / or diol component uses a relatively hard polyester resin containing a naphthalenedicarboxylic acid component as described above, while having an average particle size of 200 nm. A relatively large particle of 700 nm or less is used. Therefore, when the line speed in the post-processing increases due to the improvement of productivity efficiency, it is considered that the coating layer is scraped or the particles are dropped. Therefore, as a result of intensive studies, the present inventor has found that the use of a long-chain dicarboxylic acid component and / or a diol component as a component of the polyester resin exhibits remarkable abrasion resistance of the coating layer.
- the polyester resin used for the coating layer of the present invention includes naphthalenedicarboxylic acid as an acid component, and a dicarboxylic acid component represented by the following formula (1) and / or a diol component represented by the following formula (2). .
- naphthalenedicarboxylic acid as an acid component
- a dicarboxylic acid component represented by the following formula (1)
- / or a diol component represented by the following formula (2). .
- (1) HOOC— (CH 2 ) n —COOH (where n is an integer satisfying 4 ⁇ n ⁇ 10)
- HO— (CH 2 ) n —OH where n is an integer satisfying 4 ⁇ n ⁇ 10)
- the polyester resin is given flexibility, and even a relatively large particle can be easily retained, and the coating layer Can be remarkably suppressed.
- n is less than 4, such an effect cannot be obtained, and the wear of the coating layer may occur.
- n exceeds 10
- the upper limit of n is more preferably 9 or less, and further preferably 8 or less.
- the abrasion resistance of the coating layer can be measured by a measurement method described later. That is, in the abrasion resistance test of the coating layer to be described later, it is preferably less than or equal to the extent that powder fall can be slightly confirmed depending on the location on the black mount, and more preferably powder fall cannot be confirmed on the black mount (that is, That is, there is no powder falling off in the abrasion resistance test of the coating layer described later).
- the degree of powder falling can be confirmed by visual observation, fluorescent X-ray analysis, XMA, ESCA or the like.
- “no powder fall-off” means that when the powder is inorganic particles, more specifically, the inorganic particles on the mount are below the detection limit in the fluorescent X-ray analysis.
- the present invention controls the iris-like color under a fluorescent lamp while maintaining the adhesiveness with the hard coat layer and the adhesiveness under high temperature and high humidity (humidity and heat resistance) according to the above aspect, and is excellent. Abrasion resistance of the coating layer. Further, the configuration of the present invention will be described in detail below.
- the present invention it is necessary to contain a polyester resin in the coating layer, and it is necessary to contain naphthalenedicarboxylic acid as an acid component of the polyester resin.
- naphthalenedicarboxylic acid By including naphthalenedicarboxylic acid, the refractive index increases and it becomes easy to control the iris color under a fluorescent lamp. In addition, the moisture and heat resistance can be improved.
- naphthalenedicarboxylic acid 2,6-naphthalenedicarboxylic acid is preferable.
- the proportion of the naphthalenedicarboxylic acid in the polyester resin is preferably 20 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, and still more preferably 60 mol% or more as the acid component.
- the proportion of the naphthalenedicarboxylic acid in the polyester resin is preferably 90 mol% or less, more preferably 85 mol% or less, and further preferably 80 mol% or less as the acid component.
- the proportion of the naphthalenedicarboxylic acid in the polyester resin is appropriately adjusted so that the refractive index of the coating layer together with the particles A is in the above-mentioned range. May decrease. Moreover, when it exceeds 90 mol%, the adhesiveness of resin may fall.
- the polyester resin of the present invention needs to contain at least naphthalenedicarboxylic acid, a dicarboxylic acid component of the following formula (1) and / or a diol component of the following formula (2) as an acid component.
- the dicarboxylic acid component of the following formula (1) and / or the diol component of the following formula (2) in the polyester resin is preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably 20 mol% or more.
- the dicarboxylic acid component of the following formula (1) and / or the diol component of the following formula (2) in the polyester resin is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. .
- the abrasion resistance of the coating layer may be deteriorated depending on the ratio of other components. If it is 70 mol% or more, the refractive index is lowered, and the effect of suppressing iris-like color under a fluorescent lamp may be insufficient.
- the structural component of a polyester resin it can carry out suitably also by NMR and a mass spectrometer.
- Examples of the dicarboxylic acid component of the formula (1) include adipic acid, sebacic acid, azelaic acid and the like.
- Examples of the diol component of the formula (2) include butanediol and hexanediol.
- 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.
- polyester resin When the polyester resin is used as an aqueous coating liquid, a water-soluble or water-dispersible polyester resin is used. It is preferable to copolymerize a compound containing an acid base.
- the acid component in the polyester resin may further include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, trimellitic acid, pyromellitic acid Dimer acid, 5-sodium sulfoisophthalic acid, 4-sodium sulfonaphthalene-2,7-dicarboxylic acid and the like may be used.
- diol component examples include ethylene glycol, propane glycol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, xylene glycol, ethylene oxide adduct of bisphenol A, and the like.
- the polyester resin is preferably contained in the coating layer in an amount of 30% by mass to 90% by mass in the total solid components. More preferably, it is 40% by mass or more and 80% by mass or less.
- the content of the polyester resin is large, the adhesion with the hard coat layer under high temperature and high humidity decreases, and conversely, when the content is small, the adhesion with the polyester film under normal temperature and high temperature and high humidity. Sex is reduced.
- a crosslinking agent may be contained in order to form a crosslinked structure in the coating layer.
- a crosslinking agent By containing a crosslinking agent, it becomes possible to further improve the adhesion under high temperature and high humidity. Moreover, since the solvent resistance to the hard coat coating solution solvent is improved by introducing a cross-linked structure into the coating layer, it is possible to more suitably suppress the occurrence of interference fringes due to variations in the coating layer thickness.
- the crosslinking agent include urea, epoxy, melamine, isocyanate, oxazoline, carbodiimide, and the like.
- melamine-based, isocyanate-based, oxazoline-based, and carbodiimide-based ones are preferable from the viewpoint of the stability over time of the coating liquid and the effect of improving adhesion under high-temperature and high-humidity treatment.
- a catalyst etc. are used suitably as needed.
- content in the application layer of a crosslinking agent 5 mass% or more and 50 mass% or less are preferable in all the solid components. More preferably, it is 10 mass% or more and 30 mass% or less.
- amount is small, the strength of the resin of the coating layer decreases, and the adhesion at high temperature and high humidity decreases.
- amount is large, the flexibility of the resin of the coating layer decreases and at room temperature, high temperature and high humidity. The adhesiveness of is reduced.
- metal oxide particles having a refractive index of 1.7 or more and 3.0 or less in the coating layer.
- metal oxides include TiO 2 (refractive index 2.7), ZnO (refractive index 2.0), Sb 2 O 3 (refractive index 1.9), SnO 2 (refractive index 2.1), ZrO 2 (refractive index 2.4), Nb 2 O 5 (refractive index 2.3), CeO 2 (refractive index 2.2), Ta 2 O 5 (refractive index 2.1), Y 2 O 3 (refractive) 1.8), La 2 O 3 (refractive index 1.9), In 2 O 3 (refractive index 2.0), Cr 2 O 3 (refractive index 2.5), etc., and including these metal atoms
- Examples include composite oxides.
- the coating layer of the present invention contains at least one or more of these metal oxides. If the refractive index of the metal oxide particles is 1.7 or more, it is preferable in that the refractive index of the coating layer is adjusted within the above range. Moreover, if the refractive index of a metal oxide particle is 3.0 or less, it is preferable at the point which maintains the transparency of a film.
- the content of the metal oxide particles in the coating layer is preferably controlled by the relationship between the refractive index of the metal oxide particles to be used and the refractive index of the hard coat layer to be applied. Specifically, in the total solid component, 2 mass% or more, More preferably, 5 mass% or more and 70 mass% or less are preferable. As a minimum of content of metal oxide particles, 7 mass% or more is more preferred, and 8 mass% or more is still more preferred. Moreover, as an upper limit of content of a metal oxide particle, 50 mass% or less is more preferable, 30 mass% or less is more preferable, 20 mass% or less is further more preferable, 15 mass% or less is especially preferable.
- metal oxide particles are added within the above range, and the refractive index of the coating layer is adjusted in the range of 1.5 to 1.7, preferably in the range of 1.6 to 1.7. To do. If the content of the metal oxide particles is less than 2% by mass or less than 5% by mass, it may be difficult to adjust the refractive index of the coating layer to the above range. Further, if the content of the metal oxide particles exceeds 70% by mass, the adhesion of the coating layer may be lowered, which is not preferable.
- the average particle diameter of the metal oxide particles is not particularly limited, but is preferably 1 to 100 nm from the viewpoint of maintaining the transparency of the film.
- particle B is (1) silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, satin white, aluminum silicate, Inorganic particles such as diatomaceous earth, calcium silicate, aluminum hydroxide, hydrous halloysite, magnesium carbonate, magnesium hydroxide, (2) acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / Butadiene, polystyrene / acrylic, polystyrene / isoprene, polystyrene / isoprene, methyl methacrylate / butyl methacrylate, melamine, polycarbonate, ure
- the particles (particles B) preferably have an average particle size of 200 to 700 nm.
- the particle size is small, the unevenness formation at the interface between the coating layer and the hard coat layer is small, the scattering effect is reduced, and the effect of suppressing the iris color under a fluorescent lamp tends to be insufficient. If it is large, the transparency of the coating layer may deteriorate.
- the particles (particles B) are preferably spherical particles that are difficult to aggregate.
- the effect of scattering is reduced, and not only the effect of suppressing the iris-like color under the lamp tends to be insufficient, but also an optical defect may occur.
- the spherical particles are considered preferable from the viewpoint of exhibiting the light scattering effect by the particles.
- grains B are colorless and transparent from the point which maintains the transparency of a film.
- the average particle diameter of the particles in the coating layer of the present invention is 10 or more present in the section of the coating layer by photographing a cross section of the easy-adhesive film at a magnification of 120,000 using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the maximum diameter of the particles can be measured, and the average value thereof can be obtained.
- the content of the particles B in the coating layer is preferably 0.5% by mass or more and 5% by mass or less in the total solid components.
- grains B 4 mass% or less is more preferable, 3 mass% or less is more preferable, and 2 mass% or less is especially preferable.
- the amount is small, the scattering effect is reduced, and the effect of suppressing iris-like colors under a fluorescent lamp tends to be insufficient.
- the amount is large, not only the transparency of the coating layer is deteriorated but also the film strength is lowered.
- the coating layer may contain a surfactant for the purpose of improving leveling properties during coating and defoaming the coating solution.
- the surfactant may be any of cationic, anionic and nonionic surfactants, but is preferably a silicon-based, acetylene glycol-based or fluorine-based surfactant. These surfactants are preferably contained in the coating layer within a range that does not impair the effect of suppressing the iris-like color and the adhesion under a fluorescent lamp.
- additives may be included in a range that does not impair the effect of suppressing the iris-like color and the adhesion under a fluorescent lamp.
- the additive include fluorescent dyes, fluorescent brighteners, plasticizers, ultraviolet absorbers, pigment dispersants, foam suppressors, antifoaming agents, preservatives, and the like.
- a method of providing a coating layer on a polyester film a method of coating and drying a coating solution containing a solvent, particles and a resin on the polyester film can be mentioned.
- the solvent include organic solvents such as toluene, water, and a mixed system of water and a water-soluble organic solvent.
- water alone or a mixture of a water-soluble organic solvent and water is used from the viewpoint of environmental problems. preferable.
- the laminated polyester film for optics of the present invention can be obtained by providing a hard coat layer made of an electron beam, an ultraviolet curable acrylic resin, or a siloxane thermosetting resin on the above-described polyester film coating layer.
- acrylic resin that is cured by electron beam or ultraviolet ray, it has an acrylate functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal.
- Resins polybutadiene resins, polythiol polyene resins, oligomers or prepolymers of polyfunctional compounds such as polyhydric alcohols and prepolymers, and reactive diluents such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene Monofunctional monomers such as N-vinylpyrrolidone and polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) Contains acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glyco
- acetophenones acetophenones, benzophenones, Michler benzoylbenzoate, ⁇ -amyloxime ester, tetramethyltyramium monosulfide, thioxanthone
- n-butylamine, triethylamine, tri-n-butylphosphine or the like can be used as a photosensitizer.
- the siloxane-based thermosetting resin can be produced by hydrolyzing and condensing a single or a mixture of two or more organosilane compounds under an acid or base catalyst.
- PET film Polyethylene terephthalate
- the PET resin After sufficiently drying the PET resin in a vacuum, it is supplied to an extruder, melted and extruded at about 280 ° C. from a T-die into a rotating cooling roll into a sheet, cooled and solidified by an electrostatic application method, and unstretched PET. Get a sheet.
- the unstretched PET sheet may have a single layer structure or a multilayer structure by a coextrusion method. Moreover, it is preferable not to contain an inert particle substantially in PET resin. Furthermore, in the case of a multi-layer configuration, the two-layer / three-layer configuration containing substantially no inert particles in the intermediate layer and containing inert particles only in the outermost layer can achieve both transparency and workability. This is preferable.
- the obtained unstretched PET sheet 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. Further, the end of the film is gripped with a clip, led to a hot air zone heated to 70 to 140 ° C., and stretched 2.5 to 5.0 times in the width direction. Subsequently, the film is guided to a heat treatment zone of 160 to 240 ° C., and heat treatment is performed for 1 to 60 seconds to complete crystal orientation.
- a coating solution is applied to at least one surface of the PET film to form the coating layer.
- the solid concentration of the resin composition in the coating solution is preferably 2 to 35% by weight, particularly preferably 4 to 15% by weight.
- 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 coating layer is formed by applying the coating solution to an unstretched or uniaxially stretched PET film, drying it, stretching it at least in a uniaxial direction, and then performing a heat treatment.
- the thickness of the finally obtained coating layer is preferably 20 to 350 nm, and the coating amount after drying is preferably 0.02 to 0.5 g / m 2 .
- the coating amount of the coating layer is less than 0.02 g / m 2 , not only the effect on adhesiveness is almost lost, but also the suppression of iris color under a fluorescent lamp tends to be insufficient.
- the coating amount exceeds 0.5 g / m 2 , the effect of suppressing iris-like colors under a fluorescent lamp tends to be insufficient.
- the coating layer of the optically easy-adhesive polyester film obtained in the present invention has good adhesion to a hard coat layer made of an electron beam, an ultraviolet curable acrylic resin, or a siloxane-based thermosetting resin. Also, good adhesive strength can be obtained even for applications other than optical applications.
- adhesion such as photographic photosensitive layer, diazo photosensitive layer, matte layer, magnetic layer, inkjet ink receiving layer, hard coat layer, UV curable resin, thermosetting resin, printing ink and UV ink, dry laminate, extrusion laminate, etc. Examples thereof include vacuum deposition, electron beam deposition, sputtering, ion plating, CVD, plasma polymerization and the like of an agent, a metal or an inorganic substance, or an oxide thereof, and an organic barrier layer.
- the above-mentioned electron beam, ultraviolet curable acrylic resin, or siloxane thermosetting resin is applied to the surface of the optically adhesive polyester film.
- the coating layer is provided on both surfaces, it is coated on at least one coating layer surface.
- an organic solvent such as the viscosity, wettability and coating thickness of the coating solution.
- the coating layer is obtained by curing the coating layer by applying an electron beam or ultraviolet ray and heating according to the curing conditions of the coating solution after applying the coating solution to the above-mentioned film and drying it as necessary. Then, a hard coat layer is formed.
- the thickness of the hard coat layer is preferably 1 to 15 ⁇ m.
- the thickness of the hard coat layer is less than 1 ⁇ m, the effects on the chemical resistance, scratch resistance, antifouling property and the like as the hard coat layer are almost lost.
- the thickness exceeds 15 ⁇ m, the flexibility of the hard coat layer is reduced, and the possibility of cracks and the like increases.
- the optically laminated polyester film obtained in the present invention can be used for a wide range of applications.
- an antireflection layer on the upper layer, a good antireflection film can be obtained.
- a single layer of an inorganic material such as ZnO, TiO 2 , CeO 2 , SnO 2 , ZrO 2 or the like having a high refractive index or MgF 2 or SiO 2 having a low refractive index or a metal material is used. Alternatively, it is performed by providing multiple layers.
- These layers are formed as a single layer or multiple layers of a coating layer made of a resin composition containing an inorganic material or a metal material having a high refractive index or a low refractive index, such as vapor deposition, sputtering, plasma CVD, or the like.
- the refractive index of the hard coat layer was measured using an Abbe refractometer based on JIS K 7142 for a film obtained by curing each resin used in the hard coat layer.
- the refractive index of the particles A is such that the particles A dried at 90 ° C. are suspended in various liquids of 25 ° C. having different refractive indexes, and the refractive index of the liquid in which the suspension looks most transparent is the Abbe refractive index. It was measured by a meter.
- a sample of an optically laminated polyester film was embedded in a visible light curable resin (D-800, manufactured by JEOL Datum) and cured by exposure to visible light at room temperature. From the obtained embedding block, an ultrathin section having a thickness of about 70 to 100 nm was prepared using an ultramicrotome equipped with a diamond knife, and stained in ruthenium tetroxide vapor for 30 minutes. A cross section of the hard coat layer was observed with a transmission electron microscope (TEM 2010, manufactured by JEOL Ltd.), and a photograph was taken of the stained ultrathin section. The magnification of the photograph is appropriately set in the range of 10,000 to 100,000 times. In this embodiment, the enlargement magnification is 80,000 times (acceleration voltage 200 kv).
- the average particle size of the particles A 10 or more particles having a particle size of about 100 nm or more were selected from the electron micrograph, the maximum diameter of these particles was measured, and the average value was obtained. This is to remove particles having a small particle diameter that are not clearly the particles B of the present application, such as particles A and foreign matters.
- the results of visual observation are ranked according to the following criteria.
- the observation is performed by five people who are familiar with the evaluation, and the highest rank is the evaluation rank. If two ranks have the same number, the center of the rank divided into three is adopted.
- ⁇ and ⁇ are 2 people each and ⁇ is 1 person
- ⁇ is ⁇
- ⁇ is 1 person
- ⁇ and ⁇ are 2 people each
- ⁇ , ⁇ and ⁇ are 2 people each and ⁇ is 1
- ⁇ is adopted.
- ⁇ Iridescent colors are not observed even when observed from all angles.
- ⁇ Some iris colors are observed depending on the angle.
- ⁇ Slightly iris colors are observed.
- X Clear iris colors are observed. Be done
- Adhesiveness Using the cutter guide having a gap distance of 2 mm, 100 square cuts reaching the base film through the hard coat layer are made on the hard coat layer surface using an optical laminated polyester film. Next, a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., No. 405; width of 24 mm) was attached to the cut surface having a grid shape and rubbed with an eraser to be completely adhered. Then, the cellophane adhesive tape is peeled off vertically from the hard coat layer surface of the optical laminated polyester film, and the number of squares peeled off from the hard coat layer surface of the optical laminated polyester film is visually counted. The adhesion between the film and the substrate film was determined.
- Adhesiveness (%) (1 ⁇ number of peeled squares / 100) ⁇ 100 A: 100% ⁇ : 99-90% ⁇ : 90-70% ⁇ : 69 to 0%
- the arithmetic average surface roughness is a value measured under the following conditions using a non-contact surface shape measurement system (VertScan R550H-M100). (Measurement condition) ⁇ Measurement mode: WAVE mode ⁇ Objective lens: 50 ⁇ ⁇ 0.5 ⁇ Tube lens ⁇ Measurement area 187 ⁇ 139 ⁇ m
- Total light transmittance of optically easy-adhesive polyester film The total light transmittance of the obtained optically easy-adhesive polyester film was measured in accordance with JIS K 7105 “Testing methods for optical properties of plastics”.
- copolyester resin (A-1).
- the obtained copolyester resin was light yellow and transparent.
- copolymer polyester resins (A-2) to (A-11) having different compositions were obtained.
- Table 1 shows the results of the composition and weight average molecular weight measured by 1 H-NMR for these copolyester resins.
- Polymerization of block polyisocyanate crosslinking agent 100 parts by mass of a polyisocyanate compound having an isocyanurate structure using hexamethylene diisocyanate as a raw material (manufactured by Asahi Kasei Chemicals, Duranate TPA) in a flask equipped with a stirrer, thermometer and reflux condenser, 55 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of polyethylene glycol monomethyl ether (average molecular weight 750) was charged and held at 70 ° C. for 4 hours in a nitrogen atmosphere.
- a polyisocyanate compound having an isocyanurate structure using hexamethylene diisocyanate as a raw material manufactured by Asahi Kasei Chemicals, Duranate TPA
- 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 the isocyanate group had disappeared, and a block polyisocyanate aqueous dispersion (C) having a solid content of 75% by mass was obtained.
- a dropping funnel 16 parts by mass of 2-isopropenyl-2-oxazoline as a polymerizable unsaturated monomer having an oxazoline group, methoxypolyethylene glycol acrylate (average number of moles of ethylene glycol added: 9 moles, Shin Nakamura Chemical)
- methoxypolyethylene glycol acrylate average number of moles of ethylene glycol added: 9 moles, Shin Nakamura Chemical
- Example 1 Adjustment of coating liquid The following coating agent was mixed and the coating liquid was created.
- Particle A is SnO 2 having a refractive index of 2.1
- particle B is silica particles having an average primary particle size of about 500 nm.
- Polyester aqueous dispersion (B-1) 18.19 mass%
- Particle B 0.17% by mass (Nippon Shokubai Co., Ltd. Sea Hoster KEW50, solid content concentration 15% by mass)
- PET resin pellets having an intrinsic viscosity of 0.62 dl / g and substantially free of particles are obtained at 135 ° C. under a reduced pressure of 133 Pa. Dry for hours. Thereafter, it was supplied to an extruder, melted and extruded into a sheet at about 280 ° C., and rapidly cooled and adhered and solidified by an electrostatic application method on a rotating cooling metal roll maintained at a surface temperature of 20 ° C. to obtain an unstretched PET sheet. .
- 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.
- a coating liquid for forming a hard coat layer (C-1) having the following composition was applied using a # 10 wire bar, The solvent was removed by drying at 70 ° C. for 1 minute.
- 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 an optical laminated polyester film having a hard coat layer with a thickness of 5 ⁇ m.
- the refractive index of the hard coat layer was 1.55.
- Hard coat layer forming coating solution (C-1) Isopropanol 48.47 mass% Dipentaerythritol hexaacrylate 21.25% by mass (Shin-Nakamura Chemical A-DPH) Polyethylene diacrylate 5.67% by mass (Shin-Nakamura Chemical A-400) ZrO 2 sol 23.61% by mass (Nissan Chemical OZ-30M, solid content 30% by mass) Photopolymerization initiator 1.00% by mass (Irgacure 184 manufactured by Ciba Specialty Chemicals)
- Comparative Example 1 An optically laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-10.
- Comparative Example 2 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particle A was changed to SiO 2 having a refractive index of 1.46 (Snowtex ZL manufactured by Nissan Chemical Industries, solid content concentration 40% by mass).
- Comparative Example 3 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particles B were excluded.
- Comparative Example 4 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particle B was changed to the hard coat layer forming coating solution (C-2). The refractive index of the hard coat layer was 1.55.
- Hard coat layer forming coating solution (C-2) Methyl ethyl ketone 39.00% by mass Toluene 9.47% by mass Dipentaerythritol hexaacrylate 21.25% by mass (Shin-Nakamura Chemical A-DPH) Polyethylene diacrylate 5.67% by mass (Shin-Nakamura Chemical A-400) SnO 2 sol 23.61% by mass (FSS-10T manufactured by Ishihara Sangyo Co., Ltd., solid content concentration 30% by mass) Photopolymerization initiator 1.00% by mass (Irgacure 184 manufactured by Ciba Specialty Chemicals)
- Comparative Example 5 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particles B were changed to silica particles having an average particle diameter of 100 nm (Snowtex ZL manufactured by Nissan Chemical Industries, solid content concentration 40% by mass).
- Comparative Example 6 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particles B were changed to organic particles having an average particle diameter of 2000 nm (Epester MS, manufactured by Nippon Shokubai Co., Ltd.).
- Comparative Example 7 A laminated polyester film for optics was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-11.
- Comparative Example 8 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-12.
- Example 2 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the coating solution was changed to the following. 44.54% by mass of water Isopropanol 30.00% by mass Polyester water dispersion (B-1) 12.21% by mass Block polyisocyanate aqueous dispersion (C) 3.67% by mass Particle A 9.38 mass% (Cerames S-8, manufactured by Taki Chemical Co., Ltd., solid content 8% by mass) Particle B 0.17% by mass (Nippon Shokubai Co., Ltd. Sea Hoster KEW50, solid content concentration 15% by mass) Silicon-based surfactant 0.03% by mass (Solid concentration 100% by mass)
- Example 3 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the coating solution was changed to the following.
- Water 37.29% by mass Isopropanol 30.00% by mass Polyester water dispersion (B-1) 22.09 mass%
- Particle B 0.17% by mass
- Silicon-based surfactant 0.03% by mass (Solid concentration 100% by mass)
- Example 4 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the coating solution was changed to the following. 35.76% by weight of water Isopropanol 30.00% by mass Polyester aqueous dispersion (B-1) 24.17% by mass Block polyisocyanate aqueous dispersion (C) 0.49% by mass Particle A 9.38% by mass (Cerames S-8, manufactured by Taki Chemical Co., Ltd., solid content 8% by mass) Particle B 0.17% by mass (Nippon Shokubai Co., Ltd. Sea Hoster KEW50, solid content concentration 15% by mass) Silicon-based surfactant 0.03% by mass (Solid concentration 100% by mass)
- Example 5 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particles B were changed to silica particles having an average particle size of 230 nm (Quartron PL-20 manufactured by Fuso Chemical Industries, solid content concentration: 24% by mass).
- Example 6 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particles B were changed to acrylic particles having an average particle size of 300 nm (Ganz Pearl PM-030 manufactured by Ganz Kasei Co., Ltd., solid content concentration: 41% by mass).
- Example 7 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particle B was changed to silica particles having an average particle diameter of 450 nm (MP4540M, Nissan Chemical Industries, Ltd., solid content concentration: 40% by mass).
- Example 8 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particles B were changed to crosslinked polystyrene particles having an average particle diameter of 700 nm (Glossdale 207-S manufactured by Mitsui Chemicals, solid content concentration 53 mass%).
- Example 9 Particle A is ZrO 2 having a refractive index of 2.4 (ZR-40BL manufactured by Nissan Chemical Industries, solid concentration 40% by mass), and particle B is silica particles having an average particle size of 230 nm (Quartron PL-20 manufactured by Fuso Chemical Industries, solid content).
- a laminated polyester film for optics was obtained in the same manner as in Example 1 except that the concentration was changed to 24% by mass.
- Example 10 Particle A is ZrO 2 having a refractive index of 2.4 (ZR-40BL manufactured by Nissan Chemical Industries, solid content concentration 40% by mass), particle B is an acrylic particle having an average particle size of 300 nm (Ganz Pearl PM-030 manufactured by Ganz Kasei), solid content
- An optical laminated polyester film was obtained in the same manner as in Example 1 except that the concentration was changed to 41% by mass.
- Example 11 Particle A is ZrO 2 with a refractive index of 2.4 (ZR-40BL manufactured by Nissan Chemical Industries, solid concentration 40% by mass), and particle B is a silica particle having an average particle diameter of 450 nm (MP4540M manufactured by Nissan Chemical Industries, solid concentration 40 mass). %), An optical laminated polyester film was obtained in the same manner as in Example 1.
- Example 12 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the particle A was changed to ZrO 2 having a refractive index of 2.4 (ZR-40BL manufactured by Nissan Chemical Industries, solid content concentration 40% by mass).
- Example 13 Particle A is ZrO 2 having a refractive index of 2.4 (ZR-40BL manufactured by Nissan Chemical Industries, solid concentration 40% by mass), and particle B is a crosslinked polystyrene particle having an average particle diameter of 700 nm (Glossdale 207-S manufactured by Mitsui Chemicals, solid A laminated polyester film for optics was obtained in the same manner as in Example 1 except that the partial concentration was changed to 53% by mass.
- Example 14 Particle A is TiO 2 having a refractive index of 2.7 (TTO-W-5, manufactured by Ishihara Sangyo Co., Ltd., solid content concentration: 30% by mass), and particle B is silica particles having an average particle size of 230 nm (Quatron PL-20, manufactured by Fuso Chemical Industry Co., Ltd.)
- TTO-W-5 refractive index of 2.7
- particle B silica particles having an average particle size of 230 nm
- Quatron PL-20 manufactured by Fuso Chemical Industry Co., Ltd.
- Example 15 Particle A is TiO 2 having a refractive index of 2.7 (TTO-W-5, manufactured by Ishihara Sangyo Co., Ltd., solid content concentration: 30% by mass), and particle B is an acrylic particle having an average particle size of 300 nm (Ganz Pearl PM-030, manufactured by Ganz Kasei) A laminated polyester film for optics was obtained in the same manner as in Example 1 except that the partial concentration was changed to 41% by mass.
- Example 16 Particle A is TiO 2 having a refractive index of 2.7 (TTO-W-5 manufactured by Ishihara Sangyo Co., Ltd., solid content concentration of 30% by mass), and particle B is silica particles having an average particle size of 450 nm (MP4540M manufactured by Nissan Chemical Industries, solid content concentration of 40 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the mass was changed to (% by mass).
- Example 17 An optically laminated polyester film was obtained in the same manner as in Example 1 except that the particle A was changed to TiO 2 having a refractive index of 2.7 (Ishihara Sangyo TTO-W-5, solid content concentration of 30% by mass).
- Example 18 Particle A is TiO 2 having a refractive index of 2.7 (TTO-W-5 manufactured by Ishihara Sangyo Co., Ltd., solid content concentration 30% by mass), and particle B is a crosslinked polystyrene particle having an average particle size of 700 nm (Glossdale 207-S manufactured by Mitsui Chemicals).
- a laminated polyester film for optics was obtained in the same manner as in Example 1 except that the solid content was changed to 53% by mass.
- Example 19 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the coating liquid for forming a hard coat layer (C-2) was used.
- Example 20 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the block polyisocyanate aqueous dispersion (C) was changed to a water-soluble resin (D) having an oxazoline group.
- Example 21 The laminated polyester film for optics was obtained like Example 1 except having changed the block polyisocyanate aqueous dispersion (C) into the carbodiimide water-soluble resin (E).
- Example 22 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the block polyisocyanate aqueous dispersion (C) was changed to a melamine resin (Dai Nippon Ink Becamine M-3, solid content concentration 60 mass%).
- Example 23 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-2.
- Example 24 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-3.
- Example 25 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-4.
- Example 26 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-5.
- Example 27 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-6.
- Example 28 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-7.
- Example 29 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-8.
- Example 30 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the polyester aqueous dispersion was changed to B-9.
- Example 31 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the coating solution was changed to the following.
- Water 40.16% by mass Isopropanol 30.00% by mass Polyester aqueous dispersion (B-1) 24.27% by mass
- Particle B 0.17% by mass (Nippon Shokubai Co., Ltd. Sea Hoster KEW50, solid content concentration 15% by mass)
- Example 32 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the coating solution was changed to the following.
- Water 40.16% by mass Isopropanol 30.00% by mass Polyester aqueous dispersion (B-1) 24.97% by mass
- Block polyisocyanate aqueous dispersion (C) 2.86% by mass
- Particle A 1.81% by mass
- Ishihara Sangyo TTO-W-5 solid content 30% by mass
- Particle B 0.17% by mass
- Silicon-based surfactant 0.03% by mass (Solid concentration 100% by mass)
- Example 33 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the coating solution was changed to the following.
- Water 40.16% by mass Isopropanol 30.00% by mass Polyester aqueous dispersion (B-1) 25.91% by mass
- Block polyisocyanate aqueous dispersion (C) 2.96% by mass Particle A 0.77% by mass (Ishihara Sangyo TTO-W-5, solid content 30% by mass)
- Particle B 0.17% by mass (Nippon Shokubai Co., Ltd. Sea Hoster KEW50, solid content concentration 15% by mass)
- the laminated polyester film for optics of Comparative Example 1 does not contain naphthalenedicarboxylic acid as an acid component in the polyester resin. Therefore, since the refractive index of the coating layer is lowered, the effect of suppressing the iris color under a fluorescent lamp is insufficient.
- silica having a low refractive index is used as the particles A. Therefore, since the refractive index of the coating layer is lowered, the effect of suppressing the iris color under a fluorescent lamp is insufficient.
- the optical laminated polyester film of Comparative Example 3 does not contain particles B having an average particle diameter of 200 nm to 700 nm. Therefore, since there is no light scattering effect at the hard coat layer / coating layer interface, the effect of suppressing iris-like colors under a fluorescent lamp is poor. Furthermore, since there is no interfacial irregularity formation by the particles B, the contact area with the hard coat layer is reduced, and the adhesiveness and heat-and-moisture resistance are inferior.
- the optical laminated polyester film of Comparative Example 4 does not contain particles B having an average particle size of 200 nm to 700 nm. Further, the hard coat layer forming coating solution (C-2) is used. C-2 dissolves or swells part of the coating interface, not only disturbs the design of the hard coat layer / coating layer interface, but also has no light scattering effect at the hard coat layer / coating layer interface. The effect of suppressing iris-like colors is poor. Furthermore, since there is no interfacial irregularity formation by the particles B, the contact area with the hard coat layer is reduced, and the adhesiveness and heat-and-moisture resistance are inferior.
- C-2 dissolves or swells part of the coating interface, not only disturbs the design of the hard coat layer / coating layer interface, but also has no light scattering effect at the hard coat layer / coating layer interface. The effect of suppressing iris-like colors is poor. Furthermore, since there is no interfacial irregularity formation by the particles B, the contact area with the hard coat layer is reduced, and
- the laminated polyester film for optics of Comparative Example 5 contains particles having an average particle size of 100 nm as particles B. Therefore, since there is no light scattering effect at the hard coat layer / coating layer interface, the effect of suppressing iris-like colors under a fluorescent lamp is poor. Furthermore, since there are few formations of interfacial irregularities by the particles B, the contact area with the hard coat layer is reduced, and the adhesiveness and heat-and-moisture resistance are inferior.
- the laminated polyester film for optics of Comparative Example 6 contained particles having an average particle diameter of 2000 nm as the particles B, but the adhesion decreased.
- the optically easy-adhesive polyester film of Comparative Example 7 does not contain a long-chain dicarboxylic acid component and a long-chain diol component as a composition component of the polyester resin. Therefore, the abrasion resistance of the coating layer is inferior.
- the optically easy-adhesive polyester film of Comparative Example 8 contains a dicarboxylic acid component and a diol component in which n is greater than 10 in Formula 1 and Formula 2 as a composition component of the polyester resin. Therefore, when the hard coat layer is laminated, the effect of suppressing interference spots is inferior.
- the optically easy-adhesive polyester film of the present invention has good processability, and prevents reflection of external light, glare, iris color, etc. when a hard coat layer is laminated on the coating layer of the film. Excellent in adhesion and excellent adhesion to hard coat layer and adhesion under high temperature and high humidity (moisture and heat resistance), touch panel, liquid crystal display (LCD), television and computer cathode ray tube (CRT), plasma display (PDP) ), An organic electroluminescence (organic EL) display screen, or the like as an icon sheet, and an anti-reflection film that provides anti-reflection properties that suppress external light reflections, glare, iris colors, etc. Suitable as a material film.
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Abstract
Description
(1)HOOC-(CH2)n-COOH (式中、nは4≦n≦10の整数)
(2)HO-(CH2)n-OH (式中、nは4≦n≦10の整数)
また、本発明は、前記塗布層に架橋剤を含むことを特徴とする前記光学用易接着性ポリエステルフィルムである。
また、本発明は、前記架橋剤が尿素系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、イソシアネート系架橋剤、オキサゾリン系架橋剤、カルボジイミド系架橋剤から選ばれた少なくとも1種の架橋剤であることを特徴とする前記光学用易接着性ポリエステルフィルムである。
また、本発明は、前記光学用易接着性ポリエステルフィルムの塗布層に、電子線または紫外線硬化型アクリル樹脂、またはシロキサン系熱硬化性樹脂からなるハードコート層を積層してなる光学用積層ポリエステルフィルムである。
本発明で基材として用いるポリエステルフィルムは、ポリエステル樹脂より構成されるフィルムであり、主に、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートの少なくとも1種を構成成分とする。これらのポリエステル樹脂の中でも、物性とコストのバランスからポリエチレンテレフタレートが最も好ましい。また、これらのポリエステルフィルムは二軸延伸することで耐薬品性、耐熱性、機械的強度などを向上させることができる。
本発明の光学用易接着性フィルムには、酸成分としてナフタレンジカルボン酸と、下記式(1)で表されるジカルボン酸成分および/または下記式(2)で表されるジオール成分とを含むポリエステル樹脂と、屈折率1.7以上3.0以下の金属酸化物粒子(粒子A)と、平均粒径200nm以上700nm以下の粒子(粒子B)を含有する塗布層に設けることが重要である。すなわち、本発明の以下のような達成手段による。
(1)HOOC-(CH2)n-COOH (式中、nは4≦n≦10の整数)
(2)HO-(CH2)n-OH (式中、nは4≦n≦10の整数)
本発明の光学易接着性フィルムは、塗布層の屈折率をハードコート層と基材ポリエステルフィルムとの中間付近に調整する必要がある。ハードコート層に使用する樹脂の組成によって、ハードコート層の屈折率は変動するため、塗布層の屈折率はそれに対応して調整することが望ましく、具体的には塗布層の屈折率を1.6~1.7の範囲に調整する必要がある。このようにすることで各界面屈折率差を小さくし、干渉斑を抑制する。一般に易接着性を有する塗布層では屈折率が低いため(1.50前後)、塗布層の屈折率を上記範囲に制御する為に本願では、塗布層の用いる樹脂を酸成分としてナフタレンジカルボン酸を含むポリエステル樹脂を用い、さらに屈折率1.7以上3.0以下の金属酸化物粒子(粒子A)を添加する。係る構成により密着性を有しながら、屈折率の高い塗布層にすることができる。これらの組成の詳細については後述する。
本発明者は塗布層組成を鋭意検討した結果、平均粒径200nm以上700nm以下の粒子(粒子B)を塗布層に添加することで干渉斑抑制効果を見いだし本発明に至った。粒子Bがこのような効果を奏する理由として、本発明者は以下のように考えている。塗布層に平均粒径の比較的大きい粒子を添加することで、塗布層とハードコート層との界面に凹凸が形成される。このような凹凸構造によって、塗布層とハードコート層との界面で光の散乱が生じる。このようなランダムな光散乱により塗布層と基材ポリエステルフィルムとの界面で生じる反射光との位相の乱れが生じ、その結果、干渉斑の抑制効果が生じると考えられる。本願の光学易接着性フィルムの塗布層はかかる構成を有するため、従来技術のように塗布厚みを高度に制御する必要もなく、各種の溶剤からなるハードコート層形成用塗布液でも広範囲に適用可能となった。
本発明の塗布層は、上記のようにナフタレンジカルボン酸成分を含む、比較的硬いポリエステル樹脂を用いながら、平均粒径200nm以上700nm以下の比較的大きい粒子を用いる。そのため、生産性効率の向上により後加工処理でのラインスピードが上昇した場合、塗布層の削れや粒子の脱落が生じることが考えられる。そこで、本発明者は鋭意検討をおこなった結果、ポリエステル樹脂の成分として、長鎖のジカルボン酸成分および/またはジオール成分を用いることで、塗布層の顕著な耐削れ性を奏することを見出した。
(1)HOOC-(CH2)n-COOH (式中、nは4≦n≦10の整数)
(2)HO-(CH2)n-OH (式中、nは4≦n≦10の整数)
(1)HOOC-(CH2)n-COOH (式中、nは4≦n≦10の整数)
(2)HO-(CH2)n-OH (式中、nは4≦n≦10の整数)
本発明の光学用積層ポリエステルフィルムは、前述のポリエステルフィルムの塗布層に、電子線または紫外線硬化型アクリル樹脂またはシロキサン系熱硬化性樹脂からなるハードコート層を設けることにより得られる。
本発明の光学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。
本発明の光学用積層ポリエステルフィルムの製造方法について、PET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。
JIS K 7367-5に準拠し、溶媒としてフェノール(60質量%)と1,1,2,2-テトラクロロエタン(40質量%)の混合溶媒を用い、30℃で測定した。
ハードコート層の屈折率は、ハードコート層に用いる各樹脂を硬化させた膜について、JIS K 7142に基づき、アッベ屈折率計を用いて測定を行った。
粒子Aの屈折率は、90℃で乾固させた粒子Aを、屈折率の異なる種々の25℃の液体に懸濁させ、懸濁液が最も透明にみえる液の屈折率をアッべ屈折率計によって測定した。
光学用積層ポリエステルフィルムの試料を可視光硬化型樹脂(日本電子データム社製、D-800)に包埋し、室温で可視光にさらして硬化させた。得られた包埋ブロックから、ダイアモンドナイフを装着したウルトラミクロトームを用いて70~100nm程度の厚みの超薄切片を作製し、四酸化ルテニウム蒸気中で30分間染色した。この染色された超薄切片を、透過型電子顕微鏡(日本電子株式会社製、TEM2010)を用いて、ハードコート層の断面を観察し、写真を撮影した。写真の拡大倍率は、10,000~100,000倍の範囲で適宜設定する。なお、本実施例では、拡大倍率を80,000倍(加速電圧200kv)とした。粒子Aの平均粒径を求める場合は、電顕微鏡写真から粒径が約100nm以上の粒子を10個以上選別し、それらの粒子の最大径を測定し、その平均値を求めた。これは、粒子Aや異物など明らかに本願の粒子Bでない、粒径の小さい粒子を除くためである。
光学用積層ポリエステルフィルムを10cm(フィルム幅方向)×15cm(フィルム長手方向)の面積に切り出し、試料フィルムを作成した。得られた試料フィルムのハードコート層とは反対面に、黒色光沢テープ(日東電工製、ビニルテープNo21;黒)を張り合わせた。この試料フィルムのハードコート面を上面にして3波長形昼白色(ナショナル パルック、F.L
15EX-N 15W)を光源として斜め上から目視でもっとも反射が強く見える位置関係(光源からの距離40~60cm、フィルム面の垂線に対して15~45°の角度)で観察した。
◎:あらゆる角度からの観察でも虹彩状色彩が見られない
○:ある角度によっては僅かに虹彩状色彩が見られる
△:僅かに虹彩状色彩が観察される
×:はっきりとした虹彩状色彩が観察される
光学用積層ポリエステルフィルムに、隙間間隔2mmのカッターガイドを用いて、ハードコート層を貫通して基材フィルムに達する100個のマス目状の切り傷をハードコート層面につける。次たで、セロハン粘着テープ(ニチバン社製、405番;24mm幅)をマス目状の切り傷面に貼り付け、消しゴムでこすって完全に密着させた。その後、垂直にセロハン粘着テープを光学用積層ポリエステルフィルムのハードコート層面から引き剥がして、光学用積層ポリエステルフィルムのハードコート層面から剥がれたマス目の数を目視で数え、下記の式からハードコート層と基材フィルムとの密着性を求めた。なお、マス目の中で部分的に剥離しているものも剥がれたマス目として数え、下記の基準でランク分けをした。
密着性(%)=(1-剥がれたマス目の数/100)×100
◎:100%
○:99~90%
△:90~70%
×:69~0%
光学用積層ポリエステルフィルムを、高温高湿槽中で60℃、95RH%の環境下500時間放置し、次いで、光学用積層ポリエステルフィルムを取りだし、室温常湿で12時間放置した。その後、前記(5)と同様の方法でハードコート層と基材フィルムの接密着性を求め、下記の基準でランク分けをした。
◎:100%
○:99~90%
△:90~70%
×:69~0%
摩擦堅牢度試験機(大栄科学精器製作所製、RT-200)に光学用易接着性ポリエステルフィルムを3cm(フィルム幅方向)×20cm(フィルム長手方向)を取り付け、おもり(300g)を付けた荷重ヘッド部(2cmx2cm、200g)と試料フィルムの接触部にアルミ箔(厚さ80μm、算術的平均表面粗さ0.03μm)を用い、10cmの距離を1往復20秒の速度で10往復させた。黒台紙の上に得られた試料フィルムをのせ、粉落ちしているか目視で確認した。
◎:黒台紙上で粉落ちが確認できない。
○:黒台紙上で場所によってわずかな粉落ちが確認できる。
△:黒台紙上で全体的にわずかな粉落ちが確認できる。
×:黒台紙上で粉落ちがはっきりと確認できる。
(測定条件)
・測定モード:WAVEモード
・対物レンズ:50倍
・0.5×Tubeレンズ
・測定面積 187×139μm
得られた光学用易接着性ポリエステルフィルムの全光線透過率はJIS K 7105「プラスチックの光学的特性試験方法」に準拠して測定した。
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、2,6-ナフタレンジカルボン酸ジメチル302.9質量部、ジメチルー5-ナトリウムスルホイソフタレート47.4質量部、エチレングリコール198.6質量部、1,6-ヘキサンジオール118.2質量部、およびテトラーnーブチルチタネート0.4質量部を仕込み、160℃から220℃まで4時間かけてエステル交換反応を行なった。さらに、セバシン酸121.4重量部を加え、エステル化反応を行なった.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は、淡黄色透明であった。
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)20質量部、エチレングリコールt-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65質量部を上記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20質量%の乳白色のポリエステルの水分散液(B-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-12)を使用して、水分散液を作製し、水分散液(B-2)~(B-12)とした。
撹拌機、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)を得た。
温度計、窒素ガス導入管、還流冷却器、滴下ロート、および攪拌機を備えたフラスコに水性媒体としてのイオン交換水58質量部とイソプロパノール58質量部との混合物、および、重合開始剤(2,2’-アゾビス(2-アミジノプロパン)・二塩酸塩)4質量部を投入した。一方、滴下ロートに、オキサゾリン基を有する重合性不飽和単量体としての2-イソプロペニル-2-オキサゾリン16質量部、メトキシポリエチレングリコールアクリレート(エチレングリコールの平均付加モル数・9モル、新中村化学製)32質量部、およびメタクリル酸メチル32質量部の混合物を投入し、窒素雰囲気下、70℃において1時間にわたり滴下した。滴下終了後、反応溶液を9時間攪拌し、冷却することで固形分濃度40質量%のオキサゾリン基を有する水溶性樹脂(D)を得た。
撹拌機、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168質量部とポリエチレングリコールモノメチルエーテル(M400、平均分子量400)220質量部を仕込み、120℃で1時間、撹拌し、更に4,4’−ジシクロヘキシルメタンジイソシアネート26質量部とカルボジイミド化触媒として3−メチル−1−フェニル−2−フォスフォレン−1−オキシド3.8質量部(全イソシイアネートに対し2重量%)を加え、窒素気流下185℃で更に5時間撹拌した。反応液の赤外スペクトルを測定し、波長2200〜2300cm-1の吸収が消失したことを確認した。60℃まで放冷し、イオン交換水を567質量部加え、固形分40質量%のカルボジイミド水溶性樹脂(E)を得た。
(1)塗布液の調整
下記の塗剤を混合し、塗布液を作成した。粒子Aは屈折率2.1のSnO2、粒子Bは平均1次粒径 約500nmのシリカ粒子である。
水 40.16質量%
イソプロパノール 30.00質量%
ポリエステル水分散液(B-1) 18.19質量%
ブロックポリイソシアネート水分散液(C)
2.08質量%
粒子A
9.37質量%
(多木化学製セラメースS-8、固形分濃度8質量%)
粒子B 0.17質量%
(日本触媒製シーホスターKEW50、固形分濃度15質量%)
シリコン系界面活性剤 0.03質量%
(固形分濃度100%)
フィルム原料ポリマーとして、固有粘度が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静電印加法により急冷密着固化させ、未延伸PETシートを得た。
前記の光学用易接着性ポリエステルフィルムの塗布層面に、下記組成のハードコート層形成用塗布液(C-1)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光学用積層ポリエステルフィルムを得た。ハードコート層の屈折率は1.55であった。
ハードコート層形成用塗布液(C-1)
イソプロパノール 48.47質量%
ジペンタエリスリトールヘキサアクリレート 21.25質量%
(新中村化学製A-DPH)
ポリエチレンジアクリレート 5.67質量%
(新中村化学製A-400)
ZrO2ゾル 23.61質量%
(日産化学工業製OZ-30M、固形分濃度30質量%)
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)
ポリエステル水分散液をB-10に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率1.46のSiO2(日産化学工業製スノーテックスZL、固形分濃度40質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Bを除いた以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Bを除き、ハードコート層形成用塗布液(C-2)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。ハードコート層の屈折率は1.55であった。
ハードコート層形成用塗布液(C-2)
メチルエチルケトン 39.00質量%
トルエン 9.47質量%
ジペンタエリスリトールヘキサアクリレート 21.25質量%
(新中村化学製A-DPH)
ポリエチレンジアクリレート 5.67質量%
(新中村化学製A-400)
SnO2ゾル 23.61質量%
(石原産業製FSS-10T、固形分濃度30質量%)
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)
粒子Bを平均粒径100nmのシリカ粒子(日産化学工業製スノーテックスZL、固形分濃度40質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Bを平均粒径2000nmの有機粒子(日本触媒製エポスターMS)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-11に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-12に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
塗布液を下記に変更したこと以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
水 44.54質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(B-1) 12.21質量%
ブロックポリイソシアネート水分散液(C)
3.67質量%
粒子A 9.38質量%
(多木化学製セラメースS-8、固形分濃度8質量%)
粒子B 0.17質量%
(日本触媒製シーホスターKEW50、固形分濃度15質量%)
シリコン系界面活性剤 0.03質量%
(固形分濃度100質量%)
塗布液を下記に変更したこと以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
水 37.29質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(B-1) 22.09質量%
ブロックポリイソシアネート水分散液(C)
1.04質量%
粒子A
9.38質量%
(多木化学製セラメースS-8、固形分濃度8質量%)
粒子B
0.17質量%
(日本触媒製シーホスターKEW50、固形分濃度15質量%)
シリコン系界面活性剤 0.03質量%
(固形分濃度100質量%)
塗布液を下記に変更したこと以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
水 35.76質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(B-1) 24.17質量%
ブロックポリイソシアネート水分散液(C)
0.49質量%
粒子A
9.38質量%
(多木化学製セラメースS-8、固形分濃度8質量%)
粒子B 0.17質量%
(日本触媒製シーホスターKEW50、固形分濃度15質量%)
シリコン系界面活性剤 0.03質量%
(固形分濃度100質量%)
粒子Bを平均粒径230nmのシリカ粒子(扶桑化学工業製クォートロンPL-20、固形分濃度24質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Bを平均粒径300nmのアクリル粒子(ガンツ化成製ガンツパールPM-030、固形分濃度41質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Bを平均粒径450nmのシリカ粒子(日産化学工業製MP4540M、固形分濃度40質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Bを平均粒径700nmの架橋ポリスチレン粒子(三井化学製グロスデール207-S、固形分濃度53質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.4のZrO2(日産化学工業製ZR-40BL、固形分濃度40質量%)、粒子Bを平均粒径230nmのシリカ粒子(扶桑化学工業製クォートロンPL-20、固形分濃度24質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.4のZrO2(日産化学工業製ZR-40BL、固形分濃度40質量%)、粒子Bを平均粒径300nmのアクリル粒子(ガンツ化成製ガンツパールPM-030、固形分濃度41質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.4のZrO2(日産化学工業製ZR-40BL、固形分濃度40質量%)、粒子Bを平均粒径450nmのシリカ粒子(日産化学工業製MP4540M、固形分濃度40質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.4のZrO2(日産化学工業製ZR-40BL、固形分濃度40質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.4のZrO2(日産化学工業製ZR-40BL、固形分濃度40質量%)、粒子Bを平均粒径700nmの架橋ポリスチレン粒子(三井化学製グロスデール207-S、固形分濃度53質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.7のTiO2(石原産業製TTO-W-5、固形分濃度30質量%)、粒子Bを平均粒径230nmのシリカ粒子(扶桑化学工業製クォートロンPL-20、固形分濃度24質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.7のTiO2(石原産業製TTO-W-5、固形分濃度30質量%)、粒子Bを平均粒径300nmのアクリル粒子(ガンツ化成製ガンツパールPM-030、固形分濃度41質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.7のTiO2(石原産業製TTO-W-5、固形分濃度30質量%)、粒子Bを平均粒径450nmのシリカ粒子(日産化学工業製MP4540M、固形分濃度40質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.7のTiO2(石原産業製TTO-W-5、固形分濃度30質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
粒子Aを屈折率2.7のTiO2(石原産業製TTO-W-5、固形分濃度30質量%)、粒子Bを平均粒径700nmの架橋ポリスチレン粒子(三井化学製グロスデール207-S、固形分濃度53質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ハードコート層形成用塗布液(C-2)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ブロックポリイソシアネート水分散液(C)をオキサゾリン基を有する水溶性樹脂(D)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ブロックポリイソシアネート水分散液(C)をカルボジイミド水溶性樹脂(E)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ブロックポリイソシアネート水分散液(C)をメラミン樹脂(大日本インキ製ベッカミンM-3、固形分濃度60質量%)に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-2に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-3に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-4に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-5に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-6に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-7に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-8に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
ポリエステル水分散液をB-9に変更した以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
塗布液を下記に変更したこと以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
水 40.16質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(B-1) 24.27質量%
ブロックポリイソシアネート水分散液(C)
2.78質量%
粒子A
2.59質量%
(石原産業製TTO-W-5、固形分濃度30質量%)
粒子B 0.17質量%
(日本触媒製シーホスターKEW50、固形分濃度15質量%)
シリコン系界面活性剤 0.03質量%
(固形分濃度100質量%)
塗布液を下記に変更したこと以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
水 40.16質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(B-1) 24.97質量%
ブロックポリイソシアネート水分散液(C)
2.86質量%
粒子A
1.81質量%
(石原産業製TTO-W-5、固形分濃度30質量%)
粒子B 0.17質量%
(日本触媒製シーホスターKEW50、固形分濃度15質量%)
シリコン系界面活性剤 0.03質量%
(固形分濃度100質量%)
塗布液を下記に変更したこと以外は実施例1と同様にして光学用積層ポリエステルフィルムを得た。
水 40.16質量%
イソプロパノール 30.00質量%
ポリエステル水分散体(B-1) 25.91質量%
ブロックポリイソシアネート水分散液(C)
2.96質量%
粒子A
0.77質量%
(石原産業製TTO-W-5、固形分濃度30質量%)
粒子B 0.17質量%
(日本触媒製シーホスターKEW50、固形分濃度15質量%)
シリコン系界面活性剤 0.03質量%
(固形分濃度100質量%)
Claims (4)
- ポリエステルフィルムの少なくとも片面に、ポリエステル樹脂と粒子Aと粒子Bを含有する塗布層を有する光学用易接着性ポリエステルフィルムであって、
前記ポリエステル樹脂が、酸成分としてナフタレンジカルボン酸と、下記式(1)で表されるジカルボン酸成分および/または下記式(2)で表されるジオール成分とを含み、
前記粒子Aが、屈折率1.7以上3.0以下の金属酸化物粒子であり、
前記粒子Bが、平均粒径200nm以上700nm以下の粒子である、光学用易接着性ポリエステルフィルム。
(1)HOOC-(CH2)n-COOH (式中、nは4≦n≦10の整数)
(2)HO-(CH2)n-OH (式中、nは4≦n≦10の整数) - 前記塗布層が架橋剤を含むことを特徴とした請求項1に記載の光学用易接着性ポリエステルフィルム。
- 前記架橋剤が尿素系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、イソシアネート系架橋剤、オキサゾリン系架橋剤、カルボジイミド系架橋剤から選ばれた少なくとも1種の架橋剤であることを特徴とする請求項2に記載の光学用易接着性ポリエステルフィルム。
- 請求項1~3のいずれかに記載の光学用易接着性ポリエステルフィルムの塗布層に、電子線または紫外線硬化型アクリル樹脂、またはシロキサン系熱硬化性樹脂からなるハードコート層を積層してなる光学用積層ポリエステルフィルム。
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Also Published As
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KR101607728B1 (ko) | 2016-03-30 |
TW201102416A (en) | 2011-01-16 |
JP2011005858A (ja) | 2011-01-13 |
TWI354008B (en) | 2011-12-11 |
JP2011005854A (ja) | 2011-01-13 |
CN102438831B (zh) | 2015-08-05 |
JP4547644B1 (ja) | 2010-09-22 |
JP5531817B2 (ja) | 2014-06-25 |
CN102438831A (zh) | 2012-05-02 |
KR20120024809A (ko) | 2012-03-14 |
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