WO2022113577A1 - 易接着性ポリエステルフィルム - Google Patents
易接着性ポリエステルフィルム Download PDFInfo
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- WO2022113577A1 WO2022113577A1 PCT/JP2021/038751 JP2021038751W WO2022113577A1 WO 2022113577 A1 WO2022113577 A1 WO 2022113577A1 JP 2021038751 W JP2021038751 W JP 2021038751W WO 2022113577 A1 WO2022113577 A1 WO 2022113577A1
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- polyester film
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- film
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Classifications
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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
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- 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
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- 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
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C09D167/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl - and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention can secure low coherence that can solve the problem of rainbow unevenness when a functional layer such as a hard coat layer is laminated, and has excellent adhesion to the functional layer, blocking resistance, and easy adhesion.
- polyester film More specifically, the present invention relates to an easily adhesive polyester film that is also suitably used in clearer optical applications.
- a hard coat film on which a transparent hard coat layer is laminated is used on the front surface of touch panels, computers, televisions, displays such as liquid crystal displays, and decorative materials.
- a transparent polyester film is generally used as the transparent plastic film of the base material, and in order to improve the adhesion between the polyester film of the base material and the hard coat layer, the surface of the polyester film is used as an intermediate layer thereof. In many cases, a coating layer having easy adhesion is provided.
- the hard coat film is required to have temperature, humidity, durability against light, transparency, chemical resistance, scratch resistance, stain resistance, and the like. Further, since it is often used on the surface of displays and decorative materials, visibility and design are required. Therefore, in order to suppress glare and iris-like color due to reflected light when viewed from an arbitrary angle, anti-reflection of a multi-layer structure in which a high-refractive index layer and a low-refractive index layer are laminated on the upper layer of the hard coat layer. It is also common to provide layers.
- an object of the present invention is to provide an easily adhesive polyester film having improved adhesion reliability, and in particular, by suppressing deterioration of adhesion over time, it is easy to be suitably used for optical applications and the like.
- the purpose is to provide an adhesive polyester film.
- a coating layer is formed by curing a composition containing a polyester having a polycyclic aromatic skeleton and a cross-linking agent having at least one skeleton selected from an aliphatic, alicyclic, and heterocyclic skeletons on at least one side of the polyester film.
- FT-IR Fourier transform infrared spectroscopy
- the easily adhesive polyester film according to the first aspect wherein the polyester having a polycyclic aromatic skeleton is a polyester having a naphthalene skeleton. 3.
- the cross-linking agent having at least one skeleton selected from the aliphatic, alicyclic, and heterocyclic group is an isocyanate cross-linking agent having at least one skeleton selected from the aliphatic, alicyclic, and heterocyclic group.
- an easily adhesive polyester film that ensures adhesion reliability for a long period of time can be provided, and can be widely applied to optical applications and the like.
- polyester film used as a base material in the present invention is a film mainly composed of polyester resin.
- the "film mainly composed of polyester resin” means a film formed from a resin composition containing 50% by mass or more of polyester resin.
- the polyester resin contains 50% by mass or more, and when copolymerized with other monomers, it means that it contains 50 mol% or more of polyester structural units.
- the polyester film contains 90% by mass or more, more preferably 95% by mass or more, still more preferably 100% by mass of the polyester resin.
- the material of the polyester resin is not particularly limited, but a copolymer formed by polycondensing 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, and diphenyl.
- Decarboxylic acid diphenoxyetanedicarboxylic acid, diphenylsulfoncarboxylic acid, anthracendicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydro Isophthalic acid, malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid , Dimeric acid, sebacic acid, suberic acid, dodecadicarboxylic acid and the like.
- diol component constituting the polyester resin examples include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decamethylene glycol, and 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.
- dicarboxylic acid component and the diol component constituting the polyester resin one kind or two or more kinds may be used respectively. Further, other acid components such as trimellitic acid and other hydroxyl group 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 viewpoint of the balance between physical properties and cost. It is also a preferred embodiment to include other copolymerization components or other polymers in order to control optical properties such as polarization.
- Preferred copolymerization components from the viewpoint of controlling the optical properties of the polyester film include diethylene glycol and a copolymerization component having norbornene in the side chain.
- the film may contain inert particles, but in order to maintain high transparency, the inert particles in the film may be contained.
- the content is preferably as low as possible. Therefore, either a multilayer structure in which particles are contained only in the surface layer of the film, or particles are not substantially contained in the film, and fine particles are contained only in the coating layer laminated on at least one side of the polyester film. Is preferable.
- substantially free of particles means, for example, in the case of inorganic particles, 50 ppm or less, preferably 10 ppm or less, most preferably detected when the element derived from the particles is quantitatively analyzed by fluorescent X-ray analysis. It means the content below the limit. This is unavoidable in the film because the contaminant components derived from foreign substances and the stains attached to the raw material resin or the line or device in the manufacturing process of the film are peeled off even if the particles are not positively added to the base film. This is because it may be mixed in.
- the polyester film has a multi-layer structure
- the two-kind three-layer structure in which the inner layer does not substantially contain the inert particles and only the outermost layer contains the inert particles achieves both transparency and processability. It is possible and preferable.
- the polyester film used as a base material may be a single layer or a laminated layer of two or more types.
- various additives can be contained in the film, if necessary, as long as the effect of the present invention is exhibited.
- the additive include antioxidants, lightfasteners, antigelling agents, organic wetting agents, antistatic agents, ultraviolet absorbers, surfactants and the like.
- the film has a laminated structure, it is also preferable to contain additives according to the function of each layer, if necessary. For example, in order to prevent photodegradation of the polarizing element, it is also a preferable embodiment to add an ultraviolet absorber or the like to the inner layer.
- Polyester film can be manufactured according to a conventional method. For example, it can be obtained by melt-extruding the polyester resin into a film and cooling and solidifying it 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 horizontal uniaxial stretching method, a longitudinal / horizontal sequential biaxial stretching method, a longitudinal / horizontal simultaneous biaxial stretching method and the like can be adopted.
- the stretching may be carried out before laminating the easy-adhesive layer described later, or may be carried out after laminating the easy-adhesive layer. It is also possible to uniaxially stretch in the vertical or horizontal direction before laminating the easy-adhesive layer, and then stretch in the other direction after laminating the coating layer.
- the easy-adhesive polyester film of the present invention is obtained by laminating an easy-adhesive coating layer on a base film made of polyester as described above.
- the coating layer contains a binder resin and additives.
- the binder resin constituting the coating layer it is a resin having easy adhesiveness, and polyester is suitable from the viewpoint of particle retention and adhesion. Further, in the present invention, polyester having a polycyclic aromatic skeleton is most suitable. Is. This is compatible with the composition of the hard coat layer described later, but is also suitable from the viewpoint of conjugated interaction when the composition of the hard coat layer has an aromatic skeleton.
- polyester having a polycyclic aromatic skeleton examples include a polyester having a naphthalene skeleton, a polyester having a fluorene skeleton, a polyester having an anthracene skeleton, and a polyester having a phenanthrene skeleton.
- the binder resin constituting the coating layer does not contain urethane resin.
- Urethane resin is sometimes used from the viewpoint of elasticity and easy moldability of the coating film, but it is obvious that the urethane resin contains the urea compound as an impurity, and the amount of the urea compound present in the coating layer is high. If the amount is too large, it may be difficult to satisfy the characteristics related to the relative absorption strength ratio described later, and it is preferable that the urethane resin is not contained from the viewpoint of maintaining the stability of adhesion over time.
- the polyester is preferably contained in the coating layer in an amount of 10% by mass or more and 90% by mass or less as a percentage of the solid content mass of the polyester resin with respect to the sum of the solid content masses of the resin and the cross-linking agent. More preferably, it is 15% by mass or more and 85% by mass or less.
- the content of the polyester resin is 90% by mass or less, the adhesion with the hard coat layer under high temperature and high humidity is maintained, which is preferable.
- the content is 10% by mass or more, the adhesion to the polyester film at room temperature and high temperature and high humidity is easily maintained, which is preferable.
- a cross-linking agent capable of producing a urea group by a side reaction of cross-linking
- specific cross-linking agents include isocyanate-based cross-linking agents and carbodiimide-based cross-linking agents.
- an isocyanate cross-linking agent is preferable because of the stability of the coating liquid over time and the effect of improving the adhesion under high-temperature and high-humidity treatment.
- an isocyanate having at least one skeleton selected from an aliphatic, alicyclic, and heterocyclic group is most suitable.
- a catalyst or the like can be appropriately used in the composition for forming the coating layer, if necessary.
- aliphatic isocyanate examples include 1,4-diisocyanatobutane, 1,5-pentamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,12 &#.8722; Dodecane diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4 − trimethyl − 1,6-hexamethylene diisocyanate, 3,5,5-trimethyl − 1,6-hexamethylene diisocyanate and the like can be mentioned.
- alicyclic isocyanate examples include cyclohexanediisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethanediisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, cyclohexyl1, Examples thereof include 4 − diisocyanate, 1,1-bis (isocyanatomethyl) cyclohexane, 2,4-hexahydrotoluene diisocyanate, and 2,6-hexahydrotoluene diisocyanate.
- heterocyclic isocyanate examples include 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, and 2,5-bis (isocyanatomethyl).
- Tetrahydrothiophene 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-ditian, 2,5-bis (isocyanatomethyl) -1,4-ditian, 4,5- Diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolan, 2,6 − Di (isocyanatemethyl) furan, 5,5'-methylenebisflufurylisocyanate, 5,5'-isopropyridenebisflufurylisocyanate, or diisocyanate trimer, which has a triazine ring called isocyanurate.
- isocyanate having an aromatic skeleton is not included in the composition for forming a coating layer because it easily reacts with moisture in the air due to its high reactivity and promotes the formation of urea compounds more than necessary. Is preferable. Further, from the viewpoint of weather resistance, an isocyanate having at least one skeleton of an aliphatic, an alicyclic, or a heterocyclic group is preferable.
- the solid content in the composition for forming the coating layer of the cross-linking agent is preferably 5% by mass or more and 50% by mass or less as the percentage of the solid content mass of the cross-linking agent with respect to the sum of the solid content mass of the resin and the cross-linking agent. .. More preferably, it is 10% by mass or more and 45% by mass or less. It is more preferably 10% by mass or more and 30% by mass or less, and most preferably 10% by mass or more and 20% by mass or less.
- it is 5% by mass or more, the strength of the resin of the coating layer is maintained and the adhesion under high temperature and high humidity is good, and when it is 50% by mass or less, the flexibility of the resin of the coating layer is maintained. Adhesion at room temperature, high temperature and high humidity is maintained, which is preferable.
- a composition containing a polyester having a polycyclic aromatic skeleton and a cross-linking agent having at least one skeleton selected from an aliphatic, alicyclic, and heterocyclic skeleton is cured. It is preferable to be.
- the expression that this composition is cured is described as such because it is difficult to appropriately express the chemical composition after reaction curing with a cross-linking agent.
- additives such as surfactants, antioxidants, heat-resistant stabilizers, weather-resistant stabilizers, ultraviolet absorbers, organic lubricants, and pigments are used as long as the effects of the present invention are not impaired.
- Dyes, organic or inorganic particles, antistatic agents, nucleating agents and the like may be added. However, it is preferable not to use substances that are not preferable in the environment or the like.
- the particles contained in the coating layer include, for example, titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay and the like, or a mixture thereof, and other general ones.
- Inorganic particles such as calcium phosphate, mica, hectrite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride and others, and organic particles such as styrene, acrylic, melamine, benzoguanamine and silicone. Examples include polymer particles.
- the average particle size of the inert particles in the coating layer is preferably 0.04 to 2.0 ⁇ m, more preferably 0.1 to 1.0 ⁇ m.
- the average particle size of the inert particles is 0.04 ⁇ m or more, it becomes easy to form irregularities on the film surface, so that the handleability such as slipperiness and winding property of the film is improved, and the film is bonded. It has good workability and is preferable.
- the average particle size of the inert particles is 2.0 ⁇ m or less, the particles are less likely to fall off, which is preferable.
- the particle concentration in the coating layer is preferably 1 to 20% by mass in the solid component.
- the thickness of the coating layer can be appropriately set in the range of 0.001 to 2.00 ⁇ m, but the range of 0.01 to 1.00 ⁇ m is preferable in order to achieve both workability and adhesiveness. It is more preferably 0.02 to 0.80 ⁇ m, and even more preferably 0.05 to 0.50 ⁇ m.
- the thickness of the coating layer is 0.001 ⁇ m or more, the adhesiveness is good and it is preferable.
- the thickness of the coating layer is 2.00 ⁇ m or less, blocking is less likely to occur, which is preferable.
- the present invention focuses on a change in the abundance of a urea compound in which a cross-linking agent component present in a coating layer forming composition is deformed by a reaction with moisture in the air or the like.
- the peak of 1640 cm -1 attributed to the urea compound does not always appear exactly at 1640 cm -1 , and there is a width of about 1640 ⁇ 5 cm -1 . Further, the peak of 1410 cm -1 attributed to the polyester resin having a polycyclic aromatic skeleton does not always appear exactly 1410 cm -1 , and there is a width of about 1410 ⁇ 5 cm -1 .
- Relative absorption strength ratio (X) obtained by evaluating the easy-adhesive polyester film after film formation and relative obtained by evaluating the easy-adhesive polyester film after holding for 24 hours in an environment of 80 ° C. and 90% RH. It is preferable that the absorption intensity ratio (Y) satisfies the relationship of the following (1). 110 ⁇ (Y / X) x 100 ⁇ 140 ... (1)
- the term "after film formation" as used in the present invention refers to a sample placed in a certain environment after film production, and is within 240 hours.
- the constant environment means an environment in which the temperature is 5 ° C. or higher and 40 ° C. or lower, and the humidity is 30% RH to 60% RH or lower. If the sample is kept in these ranges, no change with time is confirmed, and it can be confirmed that it can be said to be in the initial state, which is preferable.
- the (Y / X) ⁇ 100 of the coating layer existing on the film surface is preferably 140 or less, more preferably 130 or less.
- the proportion of urea in the coating layer is not too large, and the urea compound having a polar group adsorbs more moisture in the air, which causes a problem that the stability over time and reliability of adhesion are deteriorated. It is preferable because it can be prevented.
- the (Y / X) ⁇ 100 is 110 or more, the content of the original cross-linking agent is not insufficient, the reaction such as cross-linking is appropriately performed, and adhesion and adhesion reliability are obtained, which is preferable.
- the easily adhesive polyester film can be evaluated by the ratio of the relative absorption strength before and after being left in a room temperature environment where it is normally left for several weeks to several months, but it is difficult to measure the leaving. As a substitute measure, it is decided to evaluate by leaving it for 24 hours in a high temperature and high humidity environment of 80 ° C. and 90% RH at an accelerated rate.
- the ratio of the resin and the cross-linking agent in the coating layer it is preferable to control the ratio of the resin and the cross-linking agent in the coating layer.
- the values of X and Y increase, and when the total solid content of the resin component and the cross-linking agent component is 100% by mass, the solid content of the resin component Is preferably 70% by mass or more. It is more preferably 75% by mass or more, still more preferably 80% by mass or more.
- the ratio of the cross-linking agent is not too large, the ratio of the excess urea compound can be reduced, and the relational expression (1) can be easily satisfied.
- the solid content of the cross-linking agent component is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass. It is as follows.
- the value of X is preferably 1.78 or less. It is more preferably 1.60 or less, still more preferably 1.41 or less.
- the value of X is preferably 1.10 or more, which is satisfactory as an addition ratio for constructing a cross-linking reaction with a resin, and is preferable because the adhesion to a hard coat layer under high temperature and high humidity is easily satisfied.
- the value of X is more preferably 1.15 or more, still more preferably 1.20 or more.
- the value of Y is preferably 2.70 or less. It is more preferably 2.30 or less, still more preferably 1.85 or less.
- the value of Y is 0.90 or more, the addition ratio for constructing the cross-linking reaction with the resin is satisfactory, and the adhesion to the hard coat layer under high temperature and high humidity is easily satisfied, which is preferable.
- the value of Y is more preferably 1.20 or more, still more preferably 1.40 or more.
- the coating layer forming composition may contain a surfactant for the purpose of improving the leveling property at the time of coating and defoaming the coating liquid.
- the surfactant may be any of a cationic type, an anion type, nonionic type and the like, but a silicone type, an acetylene glycol type or a fluorine type surfactant is preferable. It is preferable that these surfactants are contained in the coating layer forming composition to the extent that the effect of suppressing iris-like color under fluorescent light and the adhesion are not impaired.
- the coating method either a so-called in-line coating method in which the polyester base film is applied at the same time as the film is formed, or a so-called offline coating method in which the polyester base film is applied separately with a coater after the film is formed can be applied.
- the in-line coating method is more efficient and more preferred.
- any known method can be used as the method for applying the coating liquid to the polyethylene terephthalate (hereinafter abbreviated as PET) film.
- PET polyethylene terephthalate
- reverse roll coat method gravure coat method, kiss coat method, die coater method, roll brush method, spray coat method, air knife coat method, wire bar coat method, pipe doctor method, impregnation coat method, curtain coat method, etc. Be done. These methods are applied alone or in combination.
- a method of applying a coating liquid containing a solvent, particles and a resin to the polyester film and drying it can be mentioned.
- the solvent include water or a mixed system of water and an organic solvent, but water alone or a mixture of water and a water-soluble organic solvent is preferable from the viewpoint of environmental problems.
- water-soluble organic solvents include alcohols such as isopropyl alcohol and ethanol, ketones such as methyl ethyl ketone, ethers such as butyl cell solve, amines such as triethanolamine, and amides such as N-methylpyrrolidone. The system can be mentioned.
- the solid content concentration of the coating liquid depends on the type of binder resin, the type of solvent, and the like, but is preferably 2% by mass or more, and more preferably 4% by mass.
- the solid content concentration of the coating liquid is preferably 35% by mass or less, more preferably 15% by mass or less.
- the drying temperature after coating also depends on the type of binder resin, the type of solvent, the presence or absence of a cross-linking agent, the solid content concentration, etc., but is preferably 80 ° C. or higher, and preferably 250 ° C. or lower.
- the polyester film used as the base material of the easily adhesive polyester film of the present invention can be produced according to a general method for producing a polyester film.
- a non-oriented polyester obtained by melting a polyester resin and extruding it into a sheet is stretched in the vertical direction at a temperature equal to or higher than the glass transition temperature by utilizing the speed difference of the rolls, and then stretched in the horizontal direction by a tenter.
- Examples thereof include a method of applying heat treatment.
- the polyester film in the present invention may be a uniaxially stretched film or a biaxially stretched film, but when the biaxially stretched film is used as a protective film on the front surface of the liquid crystal panel, it is observed from directly above the film surface.
- rainbow-shaped color spots are not seen, but it should be noted that rainbow-shaped color spots may be observed when observed from an oblique direction.
- the biaxially stretched film consists of a refractive index ellipsoid having different refractive indexes in the traveling direction, the width direction, and the thickness direction, and the retardation becomes zero depending on the light transmission direction inside the film (refractive index ellipsoid). This is because there is a direction (where the body looks like a perfect circle). Therefore, when the liquid crystal display screen is observed from a specific diagonal direction, a point where the retardation becomes zero may occur, and a rainbow-shaped color spot may occur concentrically around the point.
- this angle ⁇ increases as the birefringence in the film surface increases, and the rainbow-shaped color.
- the spots are hard to see. Since the angle ⁇ tends to be small in the biaxially stretched film, the uniaxially stretched film is preferable because the iridescent color spots are difficult to see.
- a completely uniaxial (uniaxially symmetric) film is not preferable because the mechanical strength in the direction orthogonal to the orientation direction is significantly reduced.
- the present invention has biaxiality (biaxial symmetry) in a range that does not substantially generate iridescent color spots or in a range that does not cause iridescent color spots in the viewing angle range required for a liquid crystal display screen. It is preferable to do.
- the laminated polyester film mainly used for optical applications in the present invention is a hard coat layer made of an electron beam, an ultraviolet curable acrylic resin, a siloxane thermosetting resin, or the like on a coating layer of the easily adhesive polyester film of the present invention. Etc. can be provided.
- the functional layer includes an antiglare layer, an antiglare antireflection layer, an antireflection layer, a low reflection layer, and the above-mentioned hard coat layer for the purpose of preventing reflection, glare, rainbow unevenness, and scratches.
- a layer with functionality such as an antistatic layer.
- the functional layer various types known in the art can be used, and the type thereof is not particularly limited. Hereinafter, each functional layer will be described.
- a known hard coat layer can be used for forming the hard coat layer, and is not particularly limited, but polymerized by drying, heat, a chemical reaction, or irradiation with any one of electron beam, radiation, and ultraviolet rays.
- / or reactive resin compounds can be used.
- curable resins include melamine-based, acrylic-based, silicone-based, and polyvinyl alcohol-based curable resins, and photocurable acrylic-based curable resins in terms of obtaining high surface hardness or optical design. Resin is preferred.
- an acrylic curable resin a polyfunctional (meth) acrylate-based monomer or an acrylate-based oligomer can be used, and examples of the acrylate-based oligomer include polyester acrylate-based, epoxy acrylate-based, urethane acrylate-based, and poly. Examples thereof include ether acrylate-based, polybutadiene acrylate-based, and silicone acrylate-based.
- the above hard coat layer may have an antiglare function (anti-glare function) that scatters external light.
- the anti-glare function (anti-glare function) is obtained by forming irregularities on the surface of the hard coat layer.
- the haze of the film is ideally preferably 0 to 50%, more preferably 0 to 40%, and particularly preferably 0 to 30%.
- 0% is ideal, and may be 0.2% or more, or 0.5% or more.
- the refractive index is adjusted for the hard coat layer and the functional layer.
- a reflectance 0 to 1.0%, more preferably 0 to 0.8%, and particularly preferably 0 to 0.5%.
- 0% is ideal, and may be 0.05% or more, or 0.1% or more.
- the aromatic component in order to adjust the refractive index, is 5 mol% or more and 20 mol% or less with respect to the total number of moles of the monomers and oligomers constituting the resin. It is common to use a resin contained in a proportion.
- the easily adhesive polyester film of the present invention and the laminated polyester film in which a functional layer is laminated on the coating layer thereof are mainly used for all optical films, such as prism lens sheets, AR (anti-reflection) films, hard coat films, and diffusion.
- optical films such as prism lens sheets, AR (anti-reflection) films, hard coat films, and diffusion.
- LCDs such as plates and shatterproof films
- base films for optical members such as flat TVs and CRTs, near-infrared absorption filters for front plates for plasma displays, and transparent conductive films such as touch panels and electroluminescence. It can be suitably used.
- the acrylic resin cured by an electron beam or ultraviolet rays for forming the hard coat layer described above has an acrylate-based functional group, and is, for example, a relatively low molecular weight polyester resin, a polyether resin, or an acrylic resin.
- Monofunctional and polyfunctional monomers such as acrylates, ethylhexyl (meth) acrylates, styrene, methylstyrene, N-vinylpyrrolidone, for example, trimethylolpropanetri (meth) acrylates, hexanediol (meth) acrylates, tripropylene glycol di.
- (Meta) acrylate diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. Can be used.
- acetophenones In the case of an electron beam or ultraviolet curable resin, acetophenones, benzophenones, Mihiler benzoyl benzoate, ⁇ -amyloxime ester, tetramethyltylaum monosulfide, and thioxanthone are used as photopolymerization initiators in the above-mentioned resin.
- a photosensitizer n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used.
- the silicone-based (siloxane-based) thermosetting resin can be produced by hydrolyzing and condensing the organosilane compound alone or by mixing two or more of them under an acid or base catalyst.
- the above-mentioned electron beam or ultraviolet curable acrylic resin, oligomer, monomer or siloxane-based thermosetting resin is coated on the coated layer surface of the above-mentioned easy-adhesive polyester film. If the coating layer is provided on both sides, the coating is applied to at least one coating layer surface.
- the coating liquid does not need to be diluted in particular, but there is no particular problem even if it is diluted with an organic solvent as necessary for the viscosity, wettability, coating film thickness and the like of the coating liquid.
- the coating layer is formed by applying the coating liquid to the above-mentioned film, drying it if necessary, and then curing the coating layer by irradiating with an electron beam or ultraviolet rays and heating according to the curing conditions of the coating liquid. , Form a hardcourt layer.
- the thickness of the hard coat layer is preferably 1 to 15 ⁇ m.
- the thickness of the hard coat layer is 1 ⁇ m or more, the effects on the chemical resistance, scratch resistance, antifouling property, etc. of the hard coat layer are efficiently exhibited, which is preferable.
- the thickness is 15 ⁇ m or less, the flexibility of the hard coat layer is maintained and there is no possibility of cracks or the like, which is preferable.
- scratch resistance it is preferable that scratches are not noticeable visually when the coated surface is abraded with a black mount. If the scratches are not noticeable in the above evaluation, they are not easily scratched when passing through the guide roll, which is preferable from the viewpoint of handleability and the like.
- the easily adhesive polyester film and the laminated polyester film of the present invention are mainly used for optical applications, it is preferable that they have high transparency.
- the lower limit of haze is ideally 0%, and the closer it is to 0%, the more preferable.
- the upper limit of the haze is preferably 2%, and when it is 2% or less, the light transmittance is good and a clear image can be obtained on the liquid crystal display device, which is preferable.
- the haze of the polyester film can be measured, for example, according to the method described below.
- the adhesion between the easily adhesive layer coating layer and the hard coat layer is preferably 95% or more according to the evaluation by the measurement method described later. It is more preferably 98% or more, still more preferably 100%. When it is 95% or more, it can be said that the adhesion between the coating layer and the hard coat layer is sufficiently maintained.
- the adhesion between the easy-adhesion layer and the hardcoat layer evaluated according to the method described later under high temperature and high humidity conditions of 80 ° C. and 95% RH is the same as described above, and the adhesion is preferably 95% or more. It is more preferably 98% or more, still more preferably 100%. When it is 95% or more, the adhesion between the easy-adhesive layer and the hard coat layer is satisfied under high temperature and high humidity conditions, and the passability in the post-processing step is satisfied.
- the easily adhesive polyester film can be evaluated by the adhesion after being left in a room temperature environment where it is normally left for several weeks to several months, but since it is difficult to measure the leaving, it is a substitute measure. Therefore, it is decided to accelerate the evaluation by leaving it for 24 hours in a high temperature and high humidity environment of 80 ° C. and 90% RH.
- the easily adhesive polyester film of the present invention can be used for various purposes, it is preferably used in the manufacturing process of a polarizing plate used in a liquid crystal display device, and is particularly preferably used as a protective film for a polarizing element constituting the polarizing plate. It is something that can be done.
- most of the splitters are made of polyvinyl alcohol, and the easily adhesive polyester film of the present invention is bonded by using polyvinyl alcohol or an adhesive to which a cross-linking agent is added, if necessary. At that time, it is more preferable that the coating layer of the easily adhesive polyester film of the present invention is used not on the surface on the side to be adhered to the polarizing element but on the opposite surface.
- the surface of the easily adhesive polyester film of the present invention to be adhered to the polarizing element contains, for example, a polyester resin, a polyvinyl alcohol resin, and a cross-linking agent as described in International Publication No. 2012/105607. It is preferable that the layers are laminated.
- Average particle size [Measurement method using a scanning electron microscope]
- the average particle size of the above particles can be measured by the following method. The particles are photographed with a scanning electron microscope (SEM), and the maximum diameter of 300 to 500 particles (between the two most distant points) is magnified so that the size of one of the smallest particles is 2 to 5 mm. Distance) is measured, and the average value is taken as the average particle size.
- the average particle size of the particles present in the coating layer in the present invention can be measured by the measuring method.
- the average particle size of the particles can also be obtained by a dynamic scattering method at the time of producing the particles or a film.
- the sol was diluted with a dispersion medium, measured with a submicron particle analyzer N4 PLUS (manufactured by Beckman Coulter) using the parameters of the dispersion medium, and calculated by the Cumulant method to obtain an average particle size.
- the dynamic light scattering method the average particle size of the particles in the sol is observed, and when there is agglomeration of the particles, the average particle size of those agglomerated particles is observed.
- the refractive index of the particles can be measured by the following method. After the inorganic particles are dried at 150 ° C., the powder crushed in a dairy pot is immersed in solvent 1 (which has a lower refractive index than the particles), and then solvent 2 (which has a higher refractive index than the particles) is added little by little to make the fine particles almost transparent. It was added until it became. The refractive index of this liquid was measured using an Abbe refractometer (Abbe refractometer manufactured by Atago Co., Ltd.). The measurement was performed at 23 ° C. with a D line (wavelength 589 nm).
- solvent 1 and the solvent 2 those that can be mixed with each other are selected, and depending on the refractive index, for example, 1,1,1,3,3,3-hexafluoro-2-propanol, 2-propanol, chloroform, tetrachloride.
- solvents such as carbon, toluene and glycerin.
- Adhesion A hard coat layer described in the above item of forming a hard coat layer was formed on the easy-adhesion layer of the polyester film obtained in the example.
- the easy-adhesive polyester film on which a hard coat is formed is in accordance with the description of 8.5.1 of JIS-K5400-1990, and the adhesion between the hard coat layer and the base film is determined.
- a cellophane adhesive tape (manufactured by Nichiban, No. 405; 24 mm width) is attached to the cut surface in the shape of a grid, and rubbed with an eraser to completely adhere. After that, the cellophane adhesive tape is vertically peeled off from the hard coat layer surface of the hard coat laminated polarizing element protective film, and the number of squares peeled off from the hard coat layer surface of the hard coat laminated polarizing element protective film is visually counted, and the following formula is used.
- Adhesion (%) ⁇ 1- (number of peeled squares / 100) ⁇ x 100
- the height of the peak top from the baseline was determined by using the line connecting the valley of about 1420 cm -1 and the valley of about 1390 cm -1 as the baseline (I 1410 ).
- the relative absorption intensity ratio is obtained by calculating the ratio of I 1640 and I 1410 (I 1640 / I 1410 ).
- the measurement was performed with the data "I 1640 / I 1410 (X)” measured and calculated immediately after the film formation, and after the film formation, it was left in a high temperature and high humidity bath at 80 ° C. and 90% RH for 24 hours, and then.
- the measured and calculated data "I 1640 / I 1410 (Y)” using a sample left at room temperature (20 ° C., 65% RH) for 12 hours was obtained, and "(Y / X) x 100" was calculated.
- the ester exchange reaction was carried out at a temperature of 220 ° C. for 4 hours. Then, the temperature was raised to 255 ° C., the reaction system was gradually reduced in pressure, and then the reaction was carried out under a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolymerized polyester resin (B).
- the obtained copolymerized polyester resin (B) was pale yellow and transparent.
- the reduced viscosity of the copolymerized polyester resin (B) was measured and found to be 0.69 dl / g.
- the glass transition temperature by DSC was 30 ° C., and the number average molecular weight was 21000.
- copolymerized polyester resin (D) for coating layer 194.2 parts by mass of dimethyl terephthalate, 184.5 parts by mass of dimethyl isophthalate, 14.8 parts by mass of dimethyl-5-sodium sulfoisophthalate, 233.5 parts by mass of diethylene glycol, 136.6 parts by mass of ethylene glycol, and tetra-n.
- a copolymerized polyester resin (D) was obtained in the same manner as in the polymerization of the resin (A) except that the amount of butyl titanate was 0.2 parts by mass.
- the reduced viscosity of the obtained copolymerized polyester resin (D) was measured and found to be 0.70 dl / g.
- the glass transition temperature by DSC was 40 ° C.
- a polyester resin (B) aqueous dispersion (resin B solution) (Bw) in which the copolymerized polyester resin (B) was dissolved was prepared by the same method.
- a polyester resin (C) aqueous dispersion (resin C solution) (Cw) in which the copolymerized polyester resin (C) was dissolved was prepared by the same method.
- a polyester resin (D) aqueous dispersion (resin D solution) (Dw) in which the copolymerized polyester resin (D) was dissolved was prepared by the same method.
- a water-soluble polyurethane resin solution (resin E solution) having a solid content of 37% by mass was prepared by removing acetone and a part of water under reduced pressure.
- the glass transition temperature of the obtained polyurethane resin was ⁇ 30 ° C.
- cross-linking agent S solution a carbodiimide-based cross-linking agent having a solid content of 40% by mass.
- Zirconia particles 2283.6 g of pure water and 403.4 g of oxalic acid dihydrate were put into a 3 liter glass container and heated to 40 ° C. to prepare a 10.72 mass% oxalic acid aqueous solution. While stirring this aqueous solution, gradually add 495.8 g of zirconium oxycarbonate powder (ZrOCO 3 , manufactured by AMR International Corp., containing 39.76% by mass in terms of ZrO 2 ) and mixing for 30 minutes. , 90 ° C. for 30 minutes.
- ZrOCO 3 zirconium oxycarbonate powder
- the transmittance measured by adjusting the sol to a ZrO 2 concentration of 2.0% by mass with pure water was 88%.
- the particles were observed with a transmission electron microscope, most of them were aggregated particles of ZrO 2 primary particles of around 7 nm.
- 4000 g of zirconia sol having a ZrO 2 concentration of 4.0% by mass obtained by performing the above hydrothermal treatment was washed and concentrated while gradually adding pure water using an ultrafiltration device to obtain a ZrO 2 concentration.
- 953 g of zirconia sol having a permeability of 76% at 13.1% by mass, pH 4.9, and a ZrO 2 concentration of 13.1% by mass was obtained.
- the refractive index of the obtained zirconia-based fine particles was 1.75.
- zirconia sol After adding 3.93 g of a 20 mass% citrate aqueous solution and 11.0 g of a 25 mass% tetramethylammonium hydroxide aqueous solution to 300 g of the zirconia sol having a ZrO 2 concentration of 13.1 mass% obtained by the above washing and concentration. Further, when the mixture was further concentrated with an ultrafiltration device, 129 g of a high concentration zirconia sol having a ZrO 2 concentration of 30.5% by mass was obtained. The obtained high-concentration zirconia sol had a pH of 9.3 and an average particle diameter of 19 nm by a dynamic light scattering method. In addition, this zirconia sol had no precipitate and was stable for more than 1 month under the condition of 50 ° C.
- titanium tetrachloride aqueous solution containing 7.75% by mass of titanium tetrachloride manufactured by Osaka Titanium Technologies Co., Ltd.
- ammonia water containing 15% by mass of ammonia manufactured by Ube Kosan Co., Ltd.
- titanium-based fine particles (primary particles) composed of a composite oxide containing titanium and tin having a rutile-type crystal structure. rice field.
- the content of the metal component contained in the titanium-based fine particles was measured, TiO 2 87.2% by mass, SnO 2 11.0% by mass, and K 2 O were measured based on the oxide conversion standard of each metal component. It was 1.8% by mass.
- the pH of the mixed aqueous solution was 10.0.
- the aqueous dispersion sol containing the titanium-based fine particles is transparent milky white, and the average particle size of the titanium-based fine particles contained in the aqueous dispersion sol is 35 nm, and the coarse particles having a particle diameter of 100 nm or more are further formed.
- the distribution frequency was 0%.
- the refractive index of the obtained titanium-based fine particles was 2.42.
- zirconia / titania mixed sol The zirconia particles and the titania particles obtained above were mixed at the respective ratios to prepare a zirconia / titania mixed sol having a solid content concentration of 13% by mass.
- a coating liquid for forming a hard coat layer having the following composition is applied to the surface of the polyester film produced in the examples described later on the surface opposite to the surface to be adhered to the polarizing element using a # 14 wire bar, and the temperature is 70 ° C. for 1 minute. It was dried and the solvent was removed. Next, the film coated with the hard coat layer was irradiated with ultraviolet rays of 300 mJ / cm 2 using a high-pressure mercury lamp to obtain a polarizing element protective film having a hard coat layer having a thickness of 7 ⁇ m.
- the coating liquid used to form the hard coat was prepared as follows.
- Example 1 (Adjustment of coating liquid) The coating liquid having the following composition was adjusted. Water 36.47 parts by mass Isopropyl alcohol 37.42 parts by mass Silica sol 1.21 parts by mass (Silica sol with an average particle size of 40 nm, solid content concentration 40% by mass) Silica sol 1.11 parts by mass (silica sol with average particle size 450 nm, solid content concentration 40% by mass) Resin A solution 20.06 parts by mass (solid content concentration 25% by mass) Crosslinking agent P solution 3.14 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass
- substantially no particles are prepared at 135 ° C. under a reduced pressure of 133 Pa. Dry for hours.
- it was supplied to an extruder, melt-extruded into a sheet at about 280 ° C., and rapidly cooled and adhered and solidified on a rotary cooling metal roll maintained at a surface temperature of 20 ° C. to obtain an unstretched PET sheet.
- This 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 peripheral speed difference to obtain a uniaxially stretched PET film.
- the coating liquid was applied to one side of the PET film by a roll coating method, dried at 80 ° C., and adjusted so that the coating amount after drying after final stretching was 0.12 g / m 2 .
- the film was stretched 4.0 times in the width direction at 150 ° C., heated at 230 ° C. with the length of the film fixed in the width direction, and further relaxed in the width direction at 230 ° C. , An easily adhesive polyester film having a thickness of 38 ⁇ m was obtained.
- the adhesion of the hard coat layer of the obtained laminated polyester film was evaluated, the adhesion was 100%.
- the obtained easily adhesive polyester film was left in a high temperature and high humidity bath for 24 hours in an environment of 80 ° C. and 90 RH%, and then left at room temperature for 12 hours. After that, the absorbance was measured on the easy-adhesion layer of the easily-adhesive polyester film after the treatment by infrared spectroscopy, and the relative absorption intensity ratio "(I 1640 / I 1410 ) (Y)" was calculated. It became .750.
- a hard coat layer was formed on the easy-adhesive layer of the easily-adhesive polyester film after the treatment by using the coating liquid L for forming the hard coat layer to obtain a laminated polyester film.
- the adhesion of the hard coat layer of the obtained laminated polyester film was evaluated, the adhesion was 100%. Further, the adhesiveness (moisture and heat resistance) of the easily adhesive polyester film after being left in a 90% RH environment at 80 ° C. was evaluated and found to be 100%.
- Example 2 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid having the following composition was adjusted.
- Crosslinking agent P solution 2.35 parts by mass (solid content concentration 40% by mass)
- Surfactant 0.25 parts by mass (fluorine-based, solid content concentration 10% by mass)
- Example 3 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid having the following composition was adjusted.
- Example 4 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid was adjusted using the cross-linking agent Q solution. The evaluation of the obtained easily adhesive polyester film was carried out in the same manner as in Example 1, and the results are as shown in Table 1.
- Example 5 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid was adjusted using the cross-linking agent R solution. The evaluation of the obtained easily adhesive polyester film was carried out in the same manner as in Example 1, and the results are as shown in Table 1.
- Example 6 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid was adjusted using the cross-linking agent S solution. The evaluation of the obtained easily adhesive polyester film was carried out in the same manner as in Example 1, and the results are as shown in Table 1.
- Example 7 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid was adjusted using the resin B solution. The evaluation of the obtained easily adhesive polyester film was carried out in the same manner as in Example 1, and the results are as shown in Table 1.
- Example 8 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid was adjusted using the resin C solution.
- the evaluation of the obtained easily adhesive polyester film was carried out in the same manner as in Example 1, and the results are as shown in Table 1.
- Example 9 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid having the following composition was adjusted.
- Surfactant 0.25 parts by mass (fluorine-based, solid content concentration 10% by mass)
- Example 10 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid having the following composition was adjusted.
- Surfactant 0.25 parts by mass (fluorine-based, solid content concentration 10% by mass)
- Example 11 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid having the following composition was adjusted. 36.47 parts by mass of water isopropyl alcohol 37.42 parts by mass Zirconia / titania mixed sol 1.21 parts by mass (75% by mass of zirconia with respect to the total mass of zirconia / titania, Solid content concentration 13% by mass) Silica sol 1.11 parts by mass (silica sol with average particle size 450 nm, solid content concentration 40% by mass) Resin A solution 20.06 parts by mass (solid content concentration 25% by mass) Crosslinking agent P solution 3.14 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass
- Example 12 to 13 An easy-adhesive polyester film was obtained in the same manner as in Example 1 except that the type of the hard coat liquid to be applied onto the obtained easily adhesive polyester film was changed as shown in Table 1. The evaluation of the obtained easily adhesive polyester film was carried out in the same manner as in Example 1, and the results are as shown in Table 1.
- Example 2 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid having the following composition was adjusted.
- Crosslinking agent P solution 6.74 parts by mass (solid content concentration 40% by mass)
- Surfactant 0.25 parts by mass (fluorine-based, solid content concentration 10% by mass)
- Example 5 An easily adhesive polyester film was obtained in the same manner as in Example 1 except that the coating liquid was adjusted using the cross-linking agent T solution. The evaluation of the obtained easily adhesive polyester film was carried out in the same manner as in Example 1, and the results are as shown in Table 1.
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Abstract
Description
しかしながら、いずれも密着性は確認されているものの、長期使用に対する信頼性を担保した易接着性ポリエステルフィルムは得られていなかった。
すなわち、本発明は、以下の構成によりなる。
1. ポリエステルフィルムの少なくとも片面に、多環芳香族骨格を有するポリエステルと、脂肪族、脂環族、複素環族から選ばれる少なくとも一つの骨格を有する架橋剤を含む組成物が硬化されてなる塗布層を有する易接着性ポリエステルフィルムであって、前記塗布層のポリエステルフィルムと接していない側の表面を、フーリエ変換型赤外分光法(FT-IR)にて測定した際、ウレア基に帰属する1640cm-1をピークとする吸収強度(I1640)と、ポリエステルのCH伸縮に帰属する1410cm-1をピークとする吸収強度(I1410)との相対吸収強度比(I1640/I1410)を規定するとき、以下の関係を満足する易接着性ポリエステルフィルム。
製膜後の易接着性ポリエステルフィルムを評価して得られた相対吸収強度比(X)と、80℃90%RH環境で24時間放置した後のポリエステルフィルムを評価して得られた相対吸収強度比(Y)が、下記式(1)の関係を満たす
110 ≦ (Y/X)×100 ≦ 140 ・・・(1)
2. 前記多環芳香族骨格を有するポリエステルが、ナフタレン骨格を有するポリエステルである上記第1に記載の易接着性ポリエステルフィルム。
3. 前記脂肪族、脂環族、複素環族から選ばれる少なくとも一つの骨格を有する架橋剤が、脂肪族、脂環族、複素環族から選ばれる少なくとも一つの骨格を有するイソシアネート架橋剤である上記第1又は第2に記載の易接着性ポリエステルフィルム。
4. 前記塗布層表面に、芳香族骨格を有する樹脂を含むハードコート層を設けたとき、その密着性が95%以上となる上記第1~第3のいずれかに記載の易接着性ポリエステルフィルム。
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ることを意味する。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。
以上を用いても良い。また、トリメリット酸などのその他の酸成分やトリメチロールプロ
パンなどのその他の水酸基成分を適宜添加しても良い。
本発明の易接着性ポリエステルフィルムは、上記のようなポリエステル製の基材フィルム上に、易接着性の塗布層が積層されているものである。塗布層中は、バインダー樹脂および添加剤を含んでいる。
塗布層を構成するバインダー樹脂としては易接着性を有する樹脂であり、粒子の保持、密着性の観点から、ポリエステルが適しており、さらに本発明においては、多環芳香族骨格を有するポリエステルが最適である。これは、後述するハードコート層の組成との相性もあるが、ハードコート層の組成が、芳香族骨格を有している場合に、共役相互作用の観点からも好適である。
本発明における塗布層中には、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、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よい。しかしながら、環境等において好ましくない物質は使用しない方が好ましい。
110 ≦ (Y/X)×100 ≦ 140 ・・・(1)
例えば、水溶性の有機溶剤の例としては、イソプロピルアルコール、エタノール等のアルコール系、メチルエチルケトン等のケトン系、ブチルセルソルブ等のエーテル系、トリエタノールアミン等のアミン系、N-メチルピロリドン等のアミド系が挙げられる。
本発明の易接着性ポリエステルフィルムの基材となるポリエステルフィルムは、一般的なポリエステルフィルムの製造方法に従って製造することができる。例えば、ポリエステル樹脂を溶融し、シート状に押出し成形された無配向ポリエステルをガラス転移温度以上の温度において、ロールの速度差を利用して縦方向に延伸した後、テンターにより横方向に延伸し、熱処理を施す方法が挙げられる。
本発明において主に光学用途に用いられる積層ポリエステルフィルムは、本発明の易接着性ポリエステルフィルムの塗布層上に、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等からなるハードコート層等を設けることにより得られる。
本発明における易接着性ポリエステルフィルムを用いた積層ポリエステルフィルムの製造方法について説明するが、説明した具体例に限定されるものではない。
〔走査型電子顕微鏡による測定法〕
上記の粒子の平均粒径の測定は下記の方法により行うことができる。粒子を走査型電子顕微鏡(SEM)で写真を撮り、最も小さい粒子1個の大きさが2~5mmとなるような倍率で、300~500個の粒子の最大径(最も離れた2点間の距離)を測定し、その平均値を平均粒径とする。本発明における塗布層中に存在する粒子の平均粒径は当該測定法により測定できる。
粒子の平均粒径は、粒子やフィルムの製造時においては動的散乱法により求めることもできる。ゾルを分散媒で希釈し、分散媒のパラメーターを用いてサブミクロン粒子アナライザーN4 PLUS(ベックマン・コールター社製)にて測定し、キュムラント法にて演算することで平均粒子径を得た。動的光散乱法ではゾル中の粒子の平均粒子径が観測され、粒子同士の凝集があるときは、それらの凝集粒子の平均粒子径が観測される。
粒子の屈折率測定は下記の方法により行うことができる。無機粒子を150℃で乾燥後、乳鉢で粉砕した粉末を、溶媒1(粒子より低屈折率のもの)に浸漬した後、溶媒2(粒子より高屈折率のもの)を少量ずつ微粒子がほぼ透明になるまで添加した。この液の屈折率をアッベの屈折計(株式会社アタゴ製アッベ屈折率計)を用いて測定した。測定は23℃、D線(波長589nm)で行われた。上記溶媒1と溶媒2は互いに混合可能なものを選定し、屈折率に応じて、例えば1,1,1,3,3,3-ヘキサフルオロ-2-プロパノール、2-プロパノール、クロロホルム、四塩化炭素、トルエン、グリセリン等の溶媒が挙げられる。
易接着性ポリエステルフィルムのヘイズはJIS K 7136:2000に準拠し、濁度計(日本電色製、NDH2000)を用いて測定した。
実施例で得られたポリエステルフィルムの易接着層上に、前述のハードコート層の形成の項目で記述したハードコート層を形成した。ハードコートを形成した易接着用ポリエステルフィルムをJIS-K5400-1990の8.5.1の記載に準拠し、ハードコート層と基材フィルムとの密着性を求める。
密着性(%)={1-(剥がれたマス目の数/100)}×100
得られた易接着性ポリエステルフィルムを、高温高湿槽中で80℃、90%RHの環境下24時間放置し、次いで、室温(20℃、65%RH)で12時間放置した。その後、前記と同様の方法でハードコート層を形成し、基材フィルムとの密着性を求めた。
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。
得られた光学用易接着性ポリエステルフィルムについて、以下の条件でFT-IR ATR測定を行った。
装置 : Cary670FTIR(Agilent社製)
アクセサリ : SPECTRA-Tech Foundation Thunder Dome Ge45°一回反射
検出器 : TGS
分解能 : 4cm-1
積算回数 : 128回
1640cm-1のピーク強度は、約1540cm-1の谷から水平にベースラインを引き、ベースラインからのピークトップの高さを求めた(I1640)。
1410cm-1のピーク強度は、約1420cm-1の谷と約1390cm-1の谷を結んだ線をベースラインとし、ベースラインからのピークトップの高さを求めた(I1410)。
相対吸収強度比は、I1640とI1410の比(I1640/I1410)を算出して求める。
測定は、製膜直後に測定、算出したデータ「I1640/I1410(X)」と、製膜後、高温高湿槽中で80℃、90%RHの環境下24時間放置し、次いで、室温(20℃、65%RH)で12時間放置した試料を用いた測定、算出したデータ「I1640/I1410(Y)」を得て、「(Y/X)×100」を算出した。
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342.0質量部、ジメチルテレフタレート35.0質量部、ジメチル-5-ナトリウムスルホイソフタレート35.5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℃の温度で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60.7質量部を加え、エステル化反応を行った。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)を得た。得られた共重合ポリエステル樹脂(A)は、淡黄色透明であった。共重合ポリエステル樹脂(A)の還元粘度を測定したところ,0.72dl/gであった。DSCによるガラス転移温度は40℃、数平均分子量は20000であった。
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293.0質量部、ジメチルテレフタレート128.0質量部、ジメチル-5-ナトリウムスルホイソフタレート41.6質量部、エチレングリコール125.0質量部、ジエチレングリコール105.0質量部、1,6-ヘキサンジオール142.0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℃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(B)を得た。得られた共重合ポリエステル樹脂(B)は、淡黄色透明であった。共重合ポリエステル樹脂(B)の還元粘度を測定したところ、0.69dl/gであった。DSCによるガラス転移温度は30℃、数平均分子量は21000であった。
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145.6質量部、ジメチル-5-ナトリウムスルホイソフタレート14.8質量部、アゼライン酸ジメチル43.3質量部、エチレングリコール80.7質量部、9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレン131.6質量部、3-メチル-1,5-ペンタンジオール70.9質量部、およびテトラ-n-ブチルチタネート0.4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(C)を得た。得られた共重合ポリエステル樹脂(C)は、淡黄色透明であった。共重合ポリエステル樹脂(C)の還元粘度を測定したところ、0.65dl/gであった。DSCによるガラス転移温度は40℃、数平均分子量は19000であった。
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-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質量部とした以外は、樹脂(A)の重合と同様にして、共重合ポリエステル樹脂(D)を得た。得られた共重合ポリエステル樹脂(D)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、共重合ポリエステル樹脂(A)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25.0質量%の乳白色のポリエステル樹脂(A)水分散体(樹脂A溶液)(Aw)を作製した。
[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水分散ポリウレタン樹脂の重合]
攪拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管および温度計を備えた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質量部およ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時間攪拌し、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37質量%の水溶性ポリウレタン樹脂溶液(樹脂E溶液)を調製した。得られたポリウレタン樹脂のガラス転移温度は-30℃であった。
攪拌機、温度計、還流冷却管を備えたフラスコに、既存の方法により1,6-ヘキサメチレンジイソシアネートから作製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(NCO濃度23.1%)100質量部、N-メチルピロリドン17.5質量部に、3,5-ジメチルピラゾール35.00質量部を滴下し、窒素雰囲気下、70℃で1時間保持した。その後、ジメチロールプロピオン酸12.50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後、N,N-ジメチルエタノールアミン8.72質量部を加えた。そのまま、1時間攪拌後、水を適量添加して、固形分40質量%のブロックイソシアネート系水分散液(架橋剤P溶液)を得た。
攪拌機、温度計、還流冷却管を備えたフラスコに、既存の方法によりシクロヘキサンジイソシアネートから作成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(NCO濃度23.3%)100質量部、N-メチルピロリドン17.5質量部に、3,5-ジメチルピラゾール35.00質量部を滴下し、窒素雰囲気下、70℃で1時間保持した。
その後、ジメチロールプロピオン酸12.50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後、N,N-ジメチルエタノールアミン8.72質量部を加えた。そのまま、1時間攪拌後、水を適量添加して、固形分40質量%のブロックイソシアネート系水分散液(架橋剤Q溶液)を得た。
攪拌機、温度計、還流冷却管を備えたフラスコに、既存の方法により2,5-ジイソシアナトチオフェンから作成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(NCO濃度23.1%)100質量部、N-メチルピロリドン17.5質量部に、3,5-ジメチルピラゾール35.00質量部を滴下し、窒素雰囲気下、70℃で1時間保持した。
その後、ジメチロールプロピオン酸12.50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後、N,N-ジメチルエタノールアミン8.72質量部を加えた。そのまま、1時間攪拌後、水を適量添加して、固形分40質量%のブロックイソシアネート系水分散液(架橋剤R溶液)を得た。
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(平均分子量400)220質量部を仕込み、120℃で1時間、攪拌し、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質量%)を加え、窒素気流下185℃で更に5時間攪拌した。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%のカルボジイミド系架橋剤(架橋剤S溶液)を得た。
攪拌機、温度計、還流冷却管を備えたフラスコに、既存の方法により2,4-トリレンジイソシアネートから作成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(NCO濃度22.3%)100質量部、N-メチルピロリドン17.5質量部に、3,5-ジメチルピラゾール35.00質量部を滴下し、窒素雰囲気下、70℃で1時間保持した。
その後、ジメチロールプロピオン酸12.50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後、N,N-ジメチルエタノールアミン8.72質量部を加えた。そのまま、1時間攪拌後、水を適量添加して、固形分40質量%のブロックイソシアネート系水分散液(架橋剤T溶液)を得た。
3リットルのガラス製容器に、純水2283.6gとシュウ酸二水和物403.4gとを投入し、40℃に加熱して10.72質量%シュウ酸水溶液を調製した。この水溶液を攪拌しながら、オキシ炭酸ジルコニウム粉末(ZrOCO3、AMR International Corp.製、ZrO2に換算して39.76質量%を含有する。)495.8gを徐々に添加し30分間混合した後、90℃で30分の加熱を行った。次いで、25.0質量%水酸化テトラメチルアンモニウム水溶液(多摩化学工業(株)製)1747.2gを1時間かけて徐々に添加した。この時点で混合液はスラリー状であり、ZrO2換算で4.0質量%含有した。このスラリーをステンレス製オートクレーブ容器に移し替え、145℃で5時間の水熱処理を行った。この水熱処理後の生成物は、未解膠物がなく完全にゾル化した。得られたゾルは、ZrO2として4.0質量%含有し、pH6.8、動的光散乱法による平均粒子径は19nmであった。また、ゾルをZrO2濃度2.0質量%に純水で調整して測定した透過率は88%であった。透過型電子顕微鏡により粒子を観察したところ、7nm前後のZrO2一次粒子の凝集粒子がほとんどであった。上記の水熱処理を行って得られたZrO2濃度4.0質量%のジルコニアゾル4000gを限外濾過装置を使用して、純水を徐々に添加しながら洗浄及び濃縮を行って、ZrO2濃度13.1質量%、pH4.9、ZrO2濃度13.1質量%のときの透過率76%のジルコニアゾル953gが得られた。得られたジルコニア系微粒子の屈折率は1.75であった。
上記の洗浄及び濃縮を行って得られたZrO2濃度13.1質量%のジルコニアゾル300gに20質量%クエン酸水溶液3.93g及び25質量%水酸化テトラメチルアンモニウム水溶液11.0gを添加した後、更に限外濾過装置で濃縮を行ったところ、ZrO2濃度30.5質量%の高濃度のジルコニアゾル129gが得られた。この得られた高濃度のジルコニアゾルは、pH9.3、動的光散乱法による平均粒子径19nmであった。また、このジルコニアゾルは沈降物がなく、50℃の条件下で1ヶ月以上安定であった。
四塩化チタン(大阪チタニウムテクノロジ-ズ(株)製)をTiO2換算基準で7.75質量%含む四塩化チタン水溶液12.09kgと、アンモニアを15質量%含むアンモニア水(宇部興産(株)製)4.69kgとを混合し、pH9.5の白色スラリー液を調製した。次いで、このスラリーを濾過した後、純水で洗浄して、固形分含有量が10質量%の含水チタン酸ケーキ9.87kgを得た。次に、このケーキに、過酸化水素を35質量%含む過酸化水素水(三菱瓦斯化学(株)製)11.28kgと純水20.00kgとを加えた後、80℃の温度で1時間、攪拌下で加熱し、さらに純水57.52kgを加えて、過酸化チタン酸をTiO2換算基準で1質量%含む過酸化チタン酸水溶液を98.67kg得た。この過酸化チタン酸水溶液は、透明な黄褐色でpHは8.5であった。
次に、得られた混合水溶液を室温まで冷却した後、限外濾過装置(旭化成(株)製、ACV-3010)で濃縮して、固形分含有量が10質量%の、チタン系微粒子(以下、「P-1」という)を含む水分散ゾル9.90kgを得た。このようにして得られたゾル中に含まれる固形物を上記の方法で測定したところ、ルチル型の結晶構造を有する、チタニウムおよびスズを含む複合酸化物からなるチタン系微粒子(一次粒子)であった。さらに、このチタン系微粒子中に含まれる金属成分の含有量を測定したところ、各金属成分の酸化物換算基準で、TiO2 87.2質量%、SnO2 11.0質量%、およびK2O 1.8質量%であった。また、該混合水溶液のpHは10.0であった。さらに、前記チタン系微粒子を含む水分散ゾルは透明な乳白色であり、この水分散ゾル中に含まれる前記チタン系微粒子の平均粒子径は35nmであり、さらに100nm以上の粒子径を有する粗大粒子の分布頻度は0%であった。さらに、得られたチタン系微粒子の屈折率は2.42であった。
上記で得られたジルコニア粒子とチタニア粒子をそれぞれの比率で混合することで固形分濃度13質量%のジルコニア/チタニア混合ゾルを作製した。
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#14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7μmのハードコート層を有する偏光子保護フィルムを得た。
メチルエチルケトン 64.40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)
ポリエチレングリコールジアクリレート 3.40質量%
(共栄社化学製ライトアクリレート9EG-A)
ビスフェノールAジアクリレート 4.00質量%
(共栄社化学製ライトアクリレートBP-4PA)
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)
調製したハードコート層形成用塗布液L中の全樹脂中の芳香族成分は、モル比で13.3%であった。
メチルエチルケトン 64.90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)
ポリエチレングリコールジアクリレート 5.30質量%
(共栄社化学製ライトアクリレート9EG-A)
ビスフェノールAジアクリレート 1.60質量%
(共栄社化学製ライトアクリレートBP-4PA)
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)
調製したハードコート層形成用塗布液M中の全樹脂中の芳香族成分は、モル比で5.4%であった。
メチルエチルケトン 64.10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)
ポリエチレングリコールジアクリレート 1.90質量%
(共栄社化学製ライトアクリレート9EG-A)
ビスフェノールAジアクリレート 5.80質量%
(共栄社化学製ライトアクリレートBP-4PA)
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)
調製したハードコート層形成用塗布液N中の全樹脂中の芳香族成分は、モル比で19.3%であった。
(塗布液の調整)
下記の組成の塗布液を調整した。
水 36.47質量部
イソプロピルアルコール 37.42質量部
シリカゾル 1.21質量部
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
シリカゾル 1.11質量部
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
樹脂A溶液 20.06質量部
(固形分濃度25質量%)
架橋剤P溶液 3.14質量部
(固形分濃度40質量%)
界面活性剤 0.25質量部
(フッソ系、固形分濃度10質量%)
高沸点溶媒 0.34質量部
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出して、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。
下記の組成の塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
水 36.00質量部
イソプロピルアルコール 37.42質量部
シリカゾル 1.21質量部
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
シリカゾル 1.11質量部
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
樹脂A溶液 21.32質量部
(固形分濃度25質量%)
架橋剤P溶液 2.35質量部
(固形分濃度40質量%)
界面活性剤 0.25質量部
(フッソ系、固形分濃度10質量%)
高沸点溶媒 0.34質量部
下記の組成の塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
水 36.94質量部
イソプロピルアルコール 37.42質量部
シリカゾル 1.21質量部
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
シリカゾル 1.11質量部
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
樹脂A溶液 18.81質量部
(固形分濃度25質量%)
架橋剤P溶液 3.92質量部
(固形分濃度40質量%)
界面活性剤 0.25質量部
(フッソ系、固形分濃度10質量%)
高沸点溶媒 0.34質量部
架橋剤Q溶液を用いて塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。得られた易接着性ポリエステルフィルムの評価については、実施例1と同様にして行い、その結果は、表1に記載の通りである。
架橋剤R溶液を用いて塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。得られた易接着性ポリエステルフィルムの評価については、実施例1と同様にして行い、その結果は、表1に記載の通りである。
架橋剤S溶液を用いて塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。得られた易接着性ポリエステルフィルムの評価については、実施例1と同様にして行い、その結果は、表1に記載の通りである。
樹脂B溶液を用いて塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。得られた易接着性ポリエステルフィルムの評価については、実施例1と同様にして行い、その結果は、表1に記載の通りである。
樹脂C溶液を用いて塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。得られた易接着性ポリエステルフィルムの評価については、実施例1と同様にして行い、その結果は、表1に記載の通りである。
下記の組成の塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
水 36.47質量部
イソプロピルアルコール 37.42質量部
ジルコニアゾル 1.21質量部
シリカゾル 1.11質量部
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
樹脂A溶液 20.06質量部
(固形分濃度25質量%)
架橋剤P溶液 3.14質量部
(固形分濃度40質量%)
界面活性剤 0.25質量部
(フッソ系、固形分濃度10質量%)
高沸点溶媒 0.34質量部
下記の組成の塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
水 36.47質量部
イソプロピルアルコール 37.42質量部
チタニアゾル 1.21質量部
シリカゾル 1.11質量部
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
樹脂A溶液 20.06質量部
(固形分濃度25質量%)
架橋剤P溶液 3.14質量部
(固形分濃度40質量%)
界面活性剤 0.25質量部
(フッソ系、固形分濃度10質量%)
高沸点溶媒 0.34質量部
下記の組成の塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
水 36.47質量部
イソプロピルアルコール 37.42質量部
ジルコニア/チタニア混合ゾル 1.21質量部
(ジルコニア/チタニア合計質量に対するジルコニア質量75質量%、
固形分濃度13質量%)
シリカゾル 1.11質量部
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
樹脂A溶液 20.06質量部
(固形分濃度25質量%)
架橋剤P溶液 3.14質量部
(固形分濃度40質量%)
界面活性剤 0.25質量部
(フッソ系、固形分濃度10質量%)
高沸点溶媒 0.34質量部
得られた易接着性ポリエステルフィルム上に塗布するハードコート液の種類を表1に記載通りに変更したこと以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。得られた易接着性ポリエステルフィルムの評価については、実施例1と同様にして行い、その結果は、表1に記載の通りである。
下記の組成の塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
水 35.53質量部
イソプロピルアルコール 37.42質量部
シリカゾル 1.21質量部
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
シリカゾル 1.11質量部
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
樹脂A溶液 22.57質量部
(固形分濃度25質量%)
架橋剤P溶液 1.57質量部
(固形分濃度40質量%)
界面活性剤 0.25質量部
(フッソ系、固形分濃度10質量%)
高沸点溶媒 0.34質量部
下記の組成の塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
水 38.63質量部
イソプロピルアルコール 37.42質量部
シリカゾル 1.21質量部
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
シリカゾル 1.11質量部
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
樹脂A溶液 14.30質量部
(固形分濃度25質量%)
架橋剤P溶液 6.74質量部
(固形分濃度40質量%)
界面活性剤 0.25質量部
(フッソ系、固形分濃度10質量%)
高沸点溶媒 0.34質量部
樹脂D溶液を用いて塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。得られた易接着性ポリエステルフィルムの評価については、実施例1と同様にして行い、その結果は、表1に記載の通りである。
下記の組成の塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。
水 36.80質量部
イソプロピルアルコール 37.29質量部
シリカゾル 1.33質量部
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
シリカゾル 1.23質量部
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
樹脂A溶液 13.31質量部
(固形分濃度25質量%)
樹脂E溶液 5.99質量部
(固形分濃度37質量%)
架橋剤P溶液 3.47質量部
(固形分濃度40質量%)
界面活性剤 0.25質量部
(フッソ系、固形分濃度10質量%)
高沸点溶媒 0.34質量部
架橋剤T溶液を用いて塗布液を調整した以外は、実施例1と同様にして、易接着性ポリエステルフィルムを得た。得られた易接着性ポリエステルフィルムの評価については、実施例1と同様にして行い、その結果は、表1に記載の通りである。
Claims (4)
- ポリエステルフィルムの少なくとも片面に、多環芳香族骨格を有するポリエステルと、脂肪族、脂環族、複素環族から選ばれる少なくとも一つの骨格を有する架橋剤を含む組成物が硬化されてなる塗布層を有する易接着性ポリエステルフィルムであって、前記塗布層のポリエステルフィルムと接していない側の表面を、フーリエ変換型赤外分光法(FT-IR)にて測定した際、ウレア基に帰属する1640cm-1をピークとする吸収強度(I1640)と、ポリエステルのCH伸縮に帰属する1410cm-1をピークとする吸収強度(I1410)との相対吸収強度比(I1640/I1410)を規定するとき、以下の関係を満足する易接着性ポリエステルフィルム。
製膜後の易接着性ポリエステルフィルムを評価して得られた相対吸収強度比(X)と、80℃90%RH環境で24時間放置した後のポリエステルフィルムを評価して得られた相対吸収強度比(Y)が、下記式(1)の関係を満たす
110 ≦ (Y/X)×100 ≦ 140 ・・・(1) - 前記多環芳香族骨格を有するポリエステルが、ナフタレン骨格を有するポリエステルである請求項1に記載の易接着性ポリエステルフィルム。
- 前記脂肪族、脂環族、複素環族から選ばれる少なくとも一つの骨格を有する架橋剤が、脂肪族、脂環族、複素環族から選ばれる少なくとも一つの骨格を有するイソシアネート架橋剤である請求項1又は2に記載の易接着性ポリエステルフィルム。
- 前記塗布層表面に、芳香族骨格を有する樹脂を含むハードコート層を設けたとき、その密着性が95%以上となる請求項1~3のいずれかに記載の易接着性ポリエステルフィルム。
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- 2021-10-20 KR KR1020237015958A patent/KR20230086743A/ko unknown
- 2021-10-20 WO PCT/JP2021/038751 patent/WO2022113577A1/ja active Application Filing
- 2021-10-20 CN CN202180076563.7A patent/CN116438074A/zh active Pending
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011208147A (ja) * | 2009-12-07 | 2011-10-20 | Toyobo Co Ltd | 易接着性熱可塑性樹脂フィルム |
JP2011240533A (ja) * | 2010-05-15 | 2011-12-01 | Mitsubishi Plastics Inc | 積層ポリエステルフィルム |
WO2012121042A1 (ja) * | 2011-03-09 | 2012-09-13 | 東洋紡績株式会社 | 易接着性ポリエステルフィルム |
JP2013195997A (ja) * | 2012-03-23 | 2013-09-30 | Fujifilm Corp | 複層フィルム及び光学シート |
WO2014024570A1 (ja) * | 2012-08-10 | 2014-02-13 | 東レ株式会社 | 積層ポリエステルフィルム |
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CN116438074A (zh) | 2023-07-14 |
JPWO2022113577A1 (ja) | 2022-06-02 |
KR20230086743A (ko) | 2023-06-15 |
TW202229432A (zh) | 2022-08-01 |
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