WO2011016311A1 - 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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- WO2011016311A1 WO2011016311A1 PCT/JP2010/061588 JP2010061588W WO2011016311A1 WO 2011016311 A1 WO2011016311 A1 WO 2011016311A1 JP 2010061588 W JP2010061588 W JP 2010061588W WO 2011016311 A1 WO2011016311 A1 WO 2011016311A1
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- polyester film
- mass
- layer
- crosslinking agent
- film
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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
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/286—Oximes
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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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
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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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
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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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
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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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
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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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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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
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
Definitions
- the present invention relates to an easily-adhesive polyester film excellent in adhesion and heat and moisture resistance. Specifically, it is suitable as a substrate for optical functional films such as hard coat films, antireflection films, light diffusion sheets, lens sheets, near-infrared shielding films, transparent conductive films, and antiglare films, which are mainly used for displays and the like.
- optical functional films such as hard coat films, antireflection films, light diffusion sheets, lens sheets, near-infrared shielding films, transparent conductive films, and antiglare films, which are mainly used for displays and the like.
- the present invention relates to an easily adhesive polyester film.
- the base material of an optical functional film used as a member of a liquid crystal display is a transparent thermoplastic made of polyethylene terephthalate (PET), acrylic, polycarbonate (PC), triacetylcellulose (TAC), polyolefin or the like.
- PET polyethylene terephthalate
- PC polycarbonate
- TAC triacetylcellulose
- a resin film is used.
- thermoplastic resin film When using the thermoplastic resin film as a base material for various optical functional films, functional layers corresponding to various applications are laminated. For example, in a liquid crystal display (LCD), a protective film (hard coat layer) that prevents scratches on the surface, an antireflection layer (AR layer) that prevents reflection of external light, and a prism layer that is used to collect and diffuse light And a functional layer such as a light diffusion layer for improving luminance.
- a protective film hard coat layer
- AR layer antireflection layer
- prism layer that is used to collect and diffuse light
- a functional layer such as a light diffusion layer for improving luminance.
- a functional layer such as a light diffusion layer for improving luminance.
- polyester films are widely used as substrates for various optical functional films because they are excellent in transparency, dimensional stability and chemical resistance and are relatively inexpensive.
- thermoplastic film such as a biaxially oriented polyester film or a biaxially oriented polyamide film
- the film surface is highly crystallized, so it has good adhesion to various paints, adhesives, inks, etc.
- a method of providing easy adhesion to a base film by providing a coating layer mainly composed of various resins such as polyester, acrylic, polyurethane, and acrylic graft polyester on the surface of the base polyester film is generally used.
- the polyester film before the completion of crystal orientation is coated on the base film with an aqueous coating solution containing the resin solution or a dispersion in which the resin is dispersed in a dispersion medium, and after drying, Stretch at least uniaxially, then heat treatment to complete the orientation of the polyester film (so-called in-line coating method), after the production of the polyester film, after applying a water-based or solvent-based coating liquid to the film, A drying method (so-called off-line coating method) is industrially implemented.
- LCDs displays such as PDPs
- portable devices using hard coat films as members are used in various environments, both indoors and outdoors.
- portable devices may require moisture and heat resistance that can withstand a bathroom, a hot and humid area, and the like.
- the optical functional film used for such applications is required to have high adhesion such that delamination does not occur even under high temperature and high humidity. Therefore, in the following patent document, a resin having a high glass transition temperature and a crosslinking agent are added to the coating liquid, and a hard coating layer is formed in the coating layer resin when the coating layer is formed by an in-line coating method, thereby imparting moisture and heat resistance.
- An easily adhesive polyester film is disclosed.
- the optical functional film used as a member also needs to maintain adhesiveness for a long time even under high temperature and high humidity.
- the easy-adhesion film as disclosed in the above-mentioned patent document shows good adhesion at first, but a decrease in adhesion strength is inevitable in long-term use under high temperature and high humidity. . Due to such a decrease in adhesion, there is a problem that the initial performance is not maintained for a long time.
- the present invention hardly causes a decrease in adhesion under high temperature and high humidity, which has been considered to be unavoidable in the past, and has easy adhesion with various optical resin compositions.
- a polyester film is provided.
- the adhesiveness under high temperature and high humidity refers to the use of a cutter guide having a clearance of 2 mm after laminating a photocurable resin layer and placing it in an environment of 80 ° C., 95% RH, 48 hours. Then, 100 grid-shaped cuts that penetrate the photocurable resin layer and reach the base film are made on the surface of the photocurable resin layer, and then a cellophane adhesive tape is applied to the grid-shaped cut surface and rubbed with an eraser. This means adhesion when the same part is peeled off 5 times vigorously, and adheres to criteria that are stricter than the evaluation methods described in JIS K5600-5-6.
- An object of the present invention is to exhibit an adhesiveness equivalent to the initial adhesiveness under such high temperature and high humidity.
- the present inventor is a polyester film having an application layer on at least one surface, and mainly comprises a urethane resin having an aliphatic polycarbonate polyol as a constituent component and a crosslinking agent, infrared aliphatic polycarbonate component derived from 1460 cm -1 vicinity of absorbance in the spectrum ratio of (a 1460) and 1530 cm -1 near the absorbance derived from urethane component with (a 1530) (a 1460 / a 1530) is 0. It has been found that by using a coating layer of 40 to 1.55, adhesion under high temperature and high humidity is improved, and the present invention has been achieved.
- the easily adhesive polyester film having a mass ratio of urethane resin and crosslinking agent (urethane resin / crosslinking agent) comprising an aliphatic polycarbonate polyol in the coating layer as 1/9 to 9/1. .
- At least one optical functional layer selected from a hard coat layer, a light diffusion layer, a lens layer, an electromagnetic wave absorption layer, a near infrared ray blocking layer, and a transparent conductive layer is provided on the coating layer of the easily adhesive polyester film.
- a laminated polyester film made by laminating.
- An easy-adhesive polyester film roll obtained by winding the optically easy-adhesive polyester film.
- the highly adhesive polyester film of the present invention is excellent in adhesion (humidity heat resistance) to various optical functional layers under high temperature and high humidity. Therefore, as a preferred embodiment, the adhesion at the high temperature and high humidity treatment is maintained at the same level as the initial adhesion.
- the polyester resin constituting the substrate in the present invention includes polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate, and copolymerization components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, etc. Polyester resins obtained by copolymerizing diol components, dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid can be used.
- the polyester resin suitably used in the present invention mainly contains at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate as a constituent component.
- 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.
- 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 total light transmittance of the optically easy-adhesive polyester film is preferably 85% or more, more preferably 87% or more, and 88% or more. More preferably, 89% or more is further more preferable, and 90% or more is particularly preferable.
- the content of inert particles in the base film is as small as possible. Therefore, it is a preferred embodiment that a multilayer structure in which particles are contained only in the surface layer of the film is used, or that the particles are substantially not contained in the film and fine particles are contained only in the coating layer.
- 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 also preferable 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 easy-adhesive polyester film of the present invention has a coating layer mainly composed of a urethane resin having an aliphatic polycarbonate polyol as a constituent component and a crosslinking agent, and the fat of the coating layer is measured by infrared spectroscopy.
- the ratio (A 1460 / A 1530 ) of the absorbance (A 1460 ) near 1460 cm ⁇ 1 derived from the group polycarbonate component to the absorbance (A 1530 ) near 1530 cm ⁇ 1 derived from the urethane component is 0.40 to 1.55. This is very important.
- the “main component” means that it is contained in an amount of 50% by mass or more, more preferably 70% by mass or more as the total solid component contained in the coating layer.
- the coating layer should not only be firmly cross-linked or provided with hydrolysis resistance but also be flexible enough to withstand the above stress. Is considered desirable. However, simply having flexibility is problematic in terms of solvent resistance and strength. Therefore, it is most desirable to make these conflicting characteristics compatible.
- it is a coating layer mainly composed of a urethane resin having a aliphatic polycarbonate polyol as a constituent component and a cross-linking agent, and has a wavelength of about 1460 cm ⁇ 1 derived from the aliphatic polycarbonate component measured by infrared spectroscopy.
- a urethane resin having a aliphatic polycarbonate polyol as a constituent component and a cross-linking agent
- the wavelength of about 1460 cm ⁇ 1 derived from the aliphatic polycarbonate component measured by infrared spectroscopy.
- the above-mentioned characteristics can be achieved by coexisting a predetermined amount of an aliphatic polycarbonate component having hydrolysis resistance and flexibility and a urethane component exhibiting toughness while providing solvent resistance with a crosslinking agent. Is intended.
- the absorbance in the vicinity of 1460 cm ⁇ 1 (A 1460 ) is derived from the bending vibration specific to the CH bond of the methylene group contained in the aliphatic polycarbonate component. Therefore, the absorbance (A 1460 ) in the vicinity of 1460 cm ⁇ 1 depends on the amount of the aliphatic polycarbonate polyol component constituting the urethane resin present in the coating layer. On the other hand, the absorbance around 1530 cm ⁇ 1 (A 1530 ) originates from the variable vibration that is characteristic of the N—H bond contained in the urethane component.
- the magnitude of absorbance (A 1530 ) near 1530 cm ⁇ 1 depends on the amount of urethane components (number of urethane bonds) constituting the urethane resin present in the coating layer.
- the absorbance (A 1530 ) in the vicinity of 1530 cm ⁇ 1 is the amount of urethane component (number of urethane bonds) as the sum of the amount of urethane resin and crosslinking agent present in the coating layer.
- these absorbance ratios (A 1460 / A 1530 ) indicate that both components having different characteristics coexist in a specific ratio.
- the ratio (A 1460 / A 1530 ) is 0.40 to 1.55, but the lower limit of the ratio (A 1460 / A 1530 ) is preferably 0.45, more preferably 0.8. 50.
- the upper limit of the ratio (A 1460 / A 1530 ) is preferably 1.50, more preferably 1.40, still more preferably 1.30, and still more preferably 1.20.
- the ratio (A 1460 / A 1530 ) is less than 0.40, the amount of the hard urethane component is excessive, and the stress relaxation of the coating layer is lowered, so that the heat and humidity resistance is lowered.
- the ratio (A 1460 / A 1530 ) exceeds 1.55, the aliphatic component of the flexible aliphatic polycarbonate is excessively increased, and the solvent resistance of the coating layer is lowered, so that the heat and humidity resistance is lowered. To do.
- the present invention can improve the adhesion (humidity heat resistance) to the lens layer and other optical functional layers under high temperature and high humidity according to the above-described embodiment. Further, the configuration of the present invention will be described in detail below.
- the urethane resin of the present invention includes at least a polyol component and a polyisocyanate component as constituent components, and further includes a chain extender as necessary.
- the urethane resin of the present invention is a polymer compound in which these constituent components are mainly copolymerized by urethane bonds. In this invention, it has an aliphatic polycarbonate polyol as a structural component of a urethane resin. Heat-and-moisture resistance can be improved by including a urethane resin containing an aliphatic polycarbonate as a constituent component in the coating layer of the present invention.
- the components of these urethane resins can be specified by nuclear magnetic resonance analysis or the like.
- the diol component which is a constituent component of the urethane resin of the present invention, needs to contain an aliphatic polycarbonate polyol having excellent heat resistance and hydrolysis resistance.
- an aliphatic polycarbonate polyol it is preferable to use an aliphatic polycarbonate polyol from the viewpoint of preventing yellowing.
- aliphatic polycarbonate polyol examples include aliphatic polycarbonate diols and aliphatic polycarbonate triols, and aliphatic polycarbonate diols can be preferably used.
- aliphatic polycarbonate diol that is a constituent of the urethane resin of the present invention examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexane Aliphatic polycarbonate diols obtained by reacting one or more diols such as dimethanol with carbonates such as
- the number average molecular weight of the aliphatic polycarbonate diol is preferably 1500 to 4000, more preferably 2000 to 3000.
- the ratio of the aliphatic polycarbonate component constituting the urethane resin is relatively small. Therefore, in order to make the ratio (A 1460 / A 1530 ) within the above range, it is preferable to control the number average molecular weight of the aliphatic polycarbonate diol within the above range.
- the absorbance (A 1460 ) near 1460 cm ⁇ 1 derived from the aliphatic polycarbonate component increases and the aliphatic component increases, so that the solvent resistance decreases. , The adhesion may be reduced. If the number average molecular weight of the aliphatic polycarbonate diol is small, a strong urethane component increases, and stress due to shrinkage or swelling of the photocurable resin or the like cannot be relieved, and adhesion may be lowered.
- aromatic aliphatic diisocyanates such as xamethylene diisocyanate and aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, or a poly (polysiloxane) obtained by adding one or more of these compounds with trimethylolpropane or the like in advance. Isocyanates.
- the ratio (A 1460 / A 1530 ) can also be adjusted by a chain extender.
- Chain extenders include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol, polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol, ethylenediamine Diamines such as hexamethylenediamine and piperazine, aminoalcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol, and water.
- a chain extender having a short main chain when used, the absorbance (A 1530 ) in the vicinity of 1530 cm ⁇ 1 derived from the urethane component increases, and the flexibility of the coating layer may decrease. Therefore, a chain extender having a long main chain is preferable. From the viewpoint of imparting the flexibility of the coating layer, an aliphatic diol or diamine chain extender having a length of 4 to 10 carbon atoms in the main chain is preferred. From these points, 1,4-butanediol, 1,6-hexanediol, hexamethylenediamine and the like are preferable as the chain extender used in the present invention.
- the coating layer of the present invention is preferably provided by an in-line coating method described later using an aqueous coating solution. Therefore, it is desirable that the urethane resin of the present invention is water-soluble.
- the “water-soluble” means that it dissolves in water or an aqueous solution containing less than 50% by mass of a water-soluble organic solvent.
- a sulfonic acid (salt) group or a carboxylic acid (salt) group can be introduced (copolymerized) into the urethane molecular skeleton. Since the sulfonic acid (salt) group is strongly acidic and it may be difficult to maintain moisture resistance due to its hygroscopic performance, it is preferable to introduce a weakly acidic carboxylic acid (salt) group. Moreover, nonionic groups, such as a polyoxyalkylene group, can also be introduced.
- a polyol compound having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid is introduced as a copolymer component to form a salt.
- the salt forming agent include trialkylamines such as ammonia, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, and tri-n-butylamine, N such as N-methylmorpholine and N-ethylmorpholine.
- -N-dialkylalkanolamines such as alkylmorpholines, N-dimethylethanolamine and N-diethylethanolamine. These can be used alone or in combination of two or more.
- the composition molar ratio of the polyol compound having a carboxylic acid (salt) group in the urethane resin is the same as that of the urethane resin.
- the total polyisocyanate component is 100 mol%, it is preferably 3 to 60 mol%, more preferably 5 to 40 mol%. If the composition molar ratio is less than 3 mol%, water dispersibility may be difficult. Moreover, when the said composition molar ratio exceeds 60 mol%, since water resistance falls, moist heat resistance may fall.
- the glass transition temperature of the urethane resin of the present invention is preferably less than 0 ° C, more preferably less than -5 ° C. When the glass transition temperature is less than 0 ° C., it is easy to achieve suitable flexibility from the viewpoint of stress relaxation of the coating layer.
- the urethane resin is preferably contained in an amount of 10% by mass to 90% by mass with respect to the crosslinking agent.
- the content is more preferably 20% by mass or more and 80% by mass or less.
- a self-crosslinking group may be introduced into the urethane resin itself in addition to the addition of a crosslinking agent.
- a crosslinking degree of resin increases and solvent resistance improves.
- the comparatively stable silanol group can be used suitably also in aqueous
- a resin other than the urethane resin of the present invention may be contained in order to improve adhesion.
- a urethane resin, an acrylic resin, a polyester resin, or the like containing polyether or polyester as a constituent component can be used.
- Crosslinking agent In the present invention, it is necessary to contain a crosslinking agent in the coating layer. By containing a crosslinking agent, it becomes possible to further improve the adhesion under high temperature and high humidity.
- a crosslinking agent those that react with a carboxylic acid group, a hydroxyl group, an amino group, etc. to form an amide bond, a urethane bond, or a urea bond are preferable because they are not easily deteriorated by high-temperature and high-humidity treatment.
- an ester bond or an ether bond it may be hydrolyzable, which is not preferable.
- an isocyanate type and a carbodiimide type are preferable from the viewpoint of the stability over time of the coating liquid and the effect of improving the adhesion under high temperature and high humidity treatment.
- an isocyanate-based crosslinking agent from the viewpoint that the coating layer has appropriate flexibility and suitably imparts the stress relaxation action of the coating layer.
- a catalyst etc. are used suitably as needed.
- the content of the crosslinking agent is preferably 10% by mass or more and 90% by mass or less with respect to the urethane resin. More preferably, it is 20 mass% or more and 80 mass% or less.
- the amount is small, the solvent resistance of the coating layer is reduced, and the adhesiveness under high temperature and high humidity is reduced.
- the amount is large, the flexibility of the resin of the coating layer is reduced, and at room temperature and high temperature and humidity. The adhesiveness of is reduced.
- crosslinking agents may be mixed in order to improve the coating film strength.
- a catalyst etc. are used suitably as needed.
- particles may be contained in the coating layer.
- Particles are (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, diatomaceous earth Inorganic particles such as soil, 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, urea, epoxy, urethane, phenol, di Rirufutareto systems
- the particles preferably have an average particle diameter of 1 to 500 nm.
- the average particle size is not particularly limited, but is preferably 1 to 100 nm from the viewpoint of maintaining the transparency of the film.
- the particles may contain two or more kinds of particles having different average particle diameters.
- said average particle diameter measures the maximum diameter of the 10 or more particle
- the particle content is preferably 0.5% by mass or more and 20% by mass or less.
- the amount is small, sufficient blocking resistance cannot be obtained. Further, scratch resistance is deteriorated.
- the amount is large, not only the transparency of the coating layer is deteriorated, but also the coating 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 a range that does not impair the adhesion to the optical functional layer, for example, 0.005 to 0.5% by mass in the coating solution.
- the easily adhesive polyester film of the present invention preferably has a haze value of 2.5% or less, more preferably 2.0% or less, and even more preferably 1.5% or less.
- the average particle size of the urethane resin used in the coating layer is preferably 150 nm or less, and more preferably 100 nm or less.
- additives may be contained within a range that does not impair the adhesion with the sealing material.
- the additive include fluorescent dyes, fluorescent brighteners, plasticizers, ultraviolet absorbers, pigment dispersants, foam suppressors, antifoaming agents, preservatives, and antistatic agents.
- 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, or 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.
- 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.
- 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 , the effect on adhesiveness is almost lost.
- the coating amount exceeds 0.5 g / m 2 , haze increases.
- An easy-adhesive polyester film roll obtained by winding up the easy-adhesive polyester film of the present invention is also a preferred embodiment of the present invention. Since the coating layer of the present invention has good anti-blocking properties due to the addition of a crosslinking agent, it can be suitably used even when it is a roll for improving productivity.
- the thickness of the easy-adhesive polyester film of the present invention is not particularly limited, but can be arbitrarily determined in the range of 25 to 500 ⁇ m according to the specification of the intended use.
- the upper limit of the thickness of the easily adhesive polyester film is preferably 400 ⁇ m, particularly preferably 350 ⁇ m.
- the lower limit of the film thickness is preferably 50 ⁇ m, particularly preferably 75 ⁇ m. If the film thickness is less than 25 ⁇ m, the mechanical strength tends to be insufficient. On the other hand, when the film thickness exceeds 500 ⁇ m, it tends to be difficult to wind it into a roll.
- the winding length and width are appropriately determined depending on the use of the film roll.
- the winding length of the film roll is preferably 1500 m or more, more preferably 1800 m or more.
- the upper limit of the winding length is preferably 5000 m.
- variety of a film roll is 500 mm or more, More preferably, it is 800 mm.
- 2000 mm is preferable.
- the optically laminated polyester film of the present invention is selected from a hard coat layer, a light diffusion layer, a lens layer, an electromagnetic wave absorption layer, a near-infrared shielding layer, and a transparent conductive layer on at least one side of the above-mentioned polyester film coating layer. It is obtained by laminating at least one optical functional layer.
- the shape of the lens layer is not particularly limited. For example, a prism-shaped lens, a Fresnel-shaped lens, a microlens, or the like can be suitably applied.
- the material used for the optical functional layer is not particularly limited, and a resin compound that is polymerized and / or reacted by drying, heat, chemical reaction, or irradiation with an electron beam, radiation, or ultraviolet light is used. be able to.
- a curable resin include melamine-based, acrylic-based, silicon-based, and polyvinyl alcohol-based curable resins.
- a photocurable acrylic curable resin is used. Resins are preferred.
- an acrylic curable resin a polyfunctional (meth) acrylate monomer or an acrylate oligomer can be used.
- acrylate oligomer examples include polyester acrylate, epoxy acrylate, urethane acrylate, Examples include ether acrylate, polybutadiene acrylate, and silicone acrylate.
- a coating composition for forming the optical functional layer can be obtained by mixing a reactive diluent, a photopolymerization initiator, a sensitizer and the like with these acrylic curable resins.
- the polyester film of the present invention can provide good adhesive strength even for other than the above optical uses.
- 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 infrared spectrum of the coating layer was determined as the difference spectrum between the infrared spectrum obtained from the coating layer sample piece and the spectrum of the blank sample piece.
- Absorbance around 1460 cm -1 derived from an aliphatic polycarbonate component (A 1460) is 1460 and the value of the absorption peak height having an absorption maximum in the region of ⁇ 10 cm -1
- the absorbance in the vicinity of 1530 cm -1 derived from urethane component (A 1530 ) is the value of the absorption peak height having an absorption maximum in the region of 1530 ⁇ 10 cm ⁇ 1 .
- the baseline was a line connecting the hems on both sides of each maximum absorption peak.
- Total light transmittance of easy-adhesive polyester film The total light transmittance of the obtained easily-adhesive polyester film was measured using a turbidimeter (Nippon Denshoku, NDH2000) in accordance with JIS K 7105. .
- Adhesiveness A cutter guide having a gap distance of 2 mm is provided on the surface of the optically laminated polyester film, the photocurable hard coat layer, the photocurable acrylic layer, or the photocurable urethane / acrylic layer (hereinafter referred to as an optical functional layer). Used to make 100 grid-like cuts that penetrate the optical functional layer and reach the base film. Next, a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., No. 405; 24 mm width) was attached to the cut surface of the grid and rubbed with an eraser for complete adhesion.
- Adhesiveness (%) (1 ⁇ number of peeled squares / 100) ⁇ 100 ⁇ : 100% or damage to the optical functional layer ⁇ : 99-90% ⁇ : 89-70% ⁇ : 69 to 0%
- a water-soluble polyurethane resin having a solid content of 35% was obtained in the same manner except that the polyhexamethylene carbonate diol having a number average molecular weight of 2000 in the water-soluble polyurethane resin (A-1) was changed to a polyhexamethylene carbonate diol having a number average molecular weight of 1000. (A-5) was obtained.
- a water-soluble polyurethane resin having a solid content of 35% was obtained in the same manner except that the polyhexamethylene carbonate diol having a number average molecular weight of 2000 in the water-soluble polyurethane resin (A-1) was changed to a polyhexamethylene carbonate diol having a number average molecular weight of 5000. (A-6) was obtained.
- 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, a thermometer and a 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 (B) 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. Water 55.62% by mass Isopropanol 30.00% by mass Polyurethane resin (A-1) 11.29% by mass Block polyisocyanate aqueous dispersion (B) 2.26% by mass Particles 0.71% by mass (Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass) 0.07% by mass of particles (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Surfactant 0.05% by mass (Silicon, solid content concentration of 100% by mass)
- 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.
- Both ends were trimmed, wound up by a winding device, further divided into two in the width direction and slitted to obtain a film roll having a width of 1300 mm, a film length of 3000 m, and a film thickness of 100 ⁇ m.
- Table 1 shows the evaluation results of the obtained easily adhesive polyester film.
- optical laminated polyester film (Optical laminated polyester film having a hard coat layer)
- a hard coat layer-forming coating solution (E) having the following composition was applied to the coating layer surface of the easy-adhesive polyester film using a # 10 wire bar and dried at 70 ° C. for 1 minute to remove the solvent.
- 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 having a thickness of 5 ⁇ m.
- Hard coat layer forming coating solution Methyl ethyl ketone 65.00% by mass Dipentaerythritol hexaacrylate 27.20% by mass (Shin-Nakamura Chemical A-DPH) Polyethylene diacrylate 6.80% by mass (Shin-Nakamura Chemical A-400) Photopolymerization initiator 1.00% by mass (Irgacure 184 manufactured by Ciba Specialty Chemicals)
- Optical laminated polyester film with photocurable urethane / acrylic layer About 5 g of the following photo-curing acrylic coating liquid is placed on a 1 mm thick SUS plate (SUS304) kept clean, and the film is applied so that the coating layer surface of the film sample and the photo-curing acrylic coating liquid are in contact with each other.
- the photo-curing urethane / acrylic coating solution (F) was pressure-bonded with a manually loaded rubber roller having a width of 10 cm and a diameter of 4 cm from above the sample.
- UV light of 500 mJ / cm 2 was irradiated using a high pressure mercury lamp to cure the photocurable urethane / acrylic resin.
- a film sample having a photocurable urethane / acrylic layer having a thickness of 20 ⁇ m was peeled from the SUS plate to obtain a laminated polyester film for optics.
- Light curable urethane / acrylic coating solution (F) Photo-curing acrylic resin 67.00% by mass (Shin-Nakamura Chemical A-BPE-4) Photo-curing acrylic resin 15.00% by mass (AMP-10G made by Shin-Nakamura Chemical) Light curable urethane / acrylic resin 15.00% by mass (Shin Nakamura Chemical U-6HA) Photopolymerization initiator 3.00% by mass (Irgacure 184 manufactured by Ciba Specialty Chemicals)
- Comparative Example 1 An easily adhesive polyester film and an optically laminated polyester film were obtained in the same manner as in Example 1 except that the polyurethane resin was changed to the polyurethane resin (A-5).
- Comparative Example 2 An easily adhesive polyester film and an optically laminated polyester film were obtained in the same manner as in Example 1 except that the polyurethane resin was changed to the polyurethane resin (A-6).
- Comparative Example 3 An easy-adhesive polyester film and an optically laminated polyester film were obtained in the same manner as in Example 1 except that the polyurethane resin was changed to the polyurethane resin (A-7).
- Comparative Example 4 An easy-adhesive polyester film and an optically laminated polyester film were obtained in the same manner as in Example 1 except that the polyurethane resin was changed to the polyurethane resin (A-8).
- Comparative Example 5 An easy-adhesive polyester film and an optical laminated polyester film were obtained in the same manner as in Example 1 except that the coating solution was changed to the following.
- Water 53.04 mass% Isopropanol 30.00% by mass Polyurethane resin (A-1) 16.13% by mass Particles 0.71% by mass (Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass) 0.07% by mass of particles (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass)
- Surfactant 0.05% by mass (Silicon, solid content concentration of 100% by mass)
- Example 2 An easy-adhesive polyester film and an optical laminated polyester film were obtained in the same manner as in Example 1 except that the coating solution was changed to the following.
- Polyurethane resin (A-1) 14.51% by mass
- Block polyisocyanate aqueous dispersion (B) 0.75% by mass Particles 0.71% by mass (Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass) 0.07% by mass of particles (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass)
- Example 3 An easy-adhesive polyester film and an optical laminated polyester film were obtained in the same manner as in Example 1 except that the coating solution was changed to the following.
- Polyurethane resin (A-1) 12.90% by mass
- Block polyisocyanate aqueous dispersion (B) 1.51% by mass Particles 0.71% by mass (Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass) 0.07% by mass of particles (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass)
- Example 4 An easy-adhesive polyester film and an optical laminated polyester film were obtained in the same manner as in Example 1 except that the coating solution was changed to the following.
- Water 57.35% by mass Isopropanol 30.00% by mass Polyurethane resin (A-1) 8.06% by mass Block polyisocyanate aqueous dispersion (B) 3.76% by mass Particles 0.71% by mass (Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass) 0.07% by mass of particles (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Surfactant 0.05% by mass (Silicon, solid content concentration of 100% by mass)
- Example 5 An easy-adhesive polyester film and an optical laminated polyester film were obtained in the same manner as in Example 1 except that the coating solution was changed to the following. 59.92% by mass of water Isopropanol 30.00% by mass Polyurethane resin (A-1) 3.23% by mass Block polyisocyanate aqueous dispersion (B) 6.02 mass% Particles 0.71% by mass (Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass) 0.07% by mass of particles (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Surfactant 0.05% by mass (Silicon, solid content concentration of 100% by mass)
- Example 6 An easy-adhesive polyester film and an optical laminated polyester film were obtained in the same manner as in Example 1 except that the coating solution was changed to the following. 60.79% by mass of water Isopropanol 30.00% by mass Polyurethane resin (A-1) 1.61% by mass Block polyisocyanate aqueous dispersion (B) 6.77% by mass Particles 0.71% by mass (Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass) 0.07% by mass of particles (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Surfactant 0.05% by mass (Silicon, solid content concentration of 100% by mass)
- Example 7 An easily adhesive polyester film and an optical laminated polyester film were obtained in the same manner as in Example 1 except that the polyurethane resin was changed to the polyurethane resin (A-2).
- Example 8 An easily adhesive polyester film and an optically laminated polyester film were obtained in the same manner as in Example 1 except that the polyurethane resin was changed to the polyurethane resin (A-3).
- Example 9 An easily adhesive polyester film and an optically laminated polyester film were obtained in the same manner as in Example 1 except that the polyurethane resin was changed to a silanol group-containing polyurethane resin (A-4).
- Example 10 An optical laminated polyester film was obtained in the same manner as in Example 1 except that the block polyisocyanate aqueous dispersion (B) was changed to a water-soluble resin (C) having an oxazoline group.
- Example 11 The laminated polyester film for optics was obtained like Example 1 except having changed the block polyisocyanate water dispersion (C) into the carbodiimide water-soluble resin (D).
- Example 12 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 imino / methylolmelamine (solid content concentration: 70% by mass).
- Example 13 An easy-adhesive polyester film and an optical laminated polyester film were obtained in the same manner as in Example 1 except that the coating solution was changed to the following. 62.82% by mass of water Isopropanol 30.00% by mass Polyurethane resin (A-1) 5.64% by mass Block polyisocyanate aqueous dispersion (B) 1.13% by mass 0.35% by mass of particles (Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass) 0.04% by mass of particles (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Surfactant 0.02% by mass (Silicon, solid content concentration of 100% by mass)
- the easy-adhesive polyester film of the present invention is excellent in adhesion with an optical functional layer and adhesion under high temperature and high humidity (moisture and heat resistance), and is therefore particularly suitable for optical applications and is mainly used for displays and the like. It is suitable as a base film for optical functional films such as a film and an antireflection film, a light diffusion sheet, a lens sheet, a near-infrared shielding film, a transparent conductive film, and an antiglare film.
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Abstract
Description
(1)少なくとも片面に塗布層を有するポリエステルフィルムであって、前記塗布層が、脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂と架橋剤を主成分とし、前記塗布層の赤外分光スペクトルにおいて脂肪族系ポリカーボネート成分由来の1460cm-1付近の吸光度(A1460)とウレタン成分由来の1530cm-1付近の吸光度(A1530)との比率(A1460/A1530)が0.40~1.55であることを特徴とする易接着性ポリエステルフィルム。
(2)前記架橋剤が、メラミン系架橋剤、イソシアネート系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤から選ばれた少なくとも1種の架橋剤である、前記易接着性ポリエステルフィルム。
(3)前記塗布層中の脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂と架橋剤の質量比(ウレタン樹脂/架橋剤)が1/9~9/1である、前記易接着性ポリエステルフィルム。
(5)前記易接着性ポリエステルフィルムの前記塗布層に、ハードコート層、光拡散層、レンズ層、電磁波吸収層、近赤外線遮断層、透明導電層から選択される少なくとも1層の光学機能層を積層してなる積層ポリエステルフィルム。
(6)前記光学用易接着性ポリエステルフィルムを巻き取ってなる易接着性ポリエステルフィルムロール。
本発明で基材を構成するポリエステル樹脂は、ポリエチ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-2,6-ナフタレート、ポリメチレンテレフタレート、および共重合成分として、例えば、ジエチレングリコール、ネオペンチルグリコール、ポリアルキレングリコールなどのジオール成分や、アジピン酸、セバチン酸、フタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸などのジカルボン酸成分などを共重合したポリエステル樹脂などを用いることができる。
本発明の易接着性ポリエステルフィルムには、脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂と架橋剤を主成分とした塗布層が形成され、赤外分光法による測定で、前記塗布層の脂肪族系ポリカーボネート成分由来の1460cm-1付近の吸光度(A1460)とウレタン成分由来の1530cm-1付近の吸光度(A1530)の比率(A1460/A1530)が0.40~1.55であることが重要である。ここで、「主成分」とは、塗布層に含まれる全固形成分中として50質量%以上、より好ましくは70質量%以上含有することを意味する。
本発明のウレタン樹脂は、構成成分として、少なくともポリオール成分、ポリイソシアネート成分を含み、さらに必要に応じて鎖延長剤を含む。本発明のウレタン樹脂は、これら構成成分が主としてウレタン結合により共重合された高分子化合物である。本発明では、ウレタン樹脂の構成成分として脂肪族系ポリカーボネートポリオールを有することを特徴とする。本発明の塗布層に脂肪族系ポリカーボネートを構成成分とするウレタン樹脂を含有させることで、耐湿熱性を向上させることができる。なお、これらウレタン樹脂の構成成分は、核磁気共鳴分析などにより特定することが可能である。
本発明において、塗布層中に架橋剤を含有させる必要がある。架橋剤を含有させることにより、高温高湿下での密着性を更に向上させることが可能になる。架橋剤としては、カルボン酸基、水酸基、アミノ基などと反応して、アミド結合、ウレタン結合、ウレア結合を形成するものが高温高湿処理で劣化しにくいため好ましい。逆に、エステル結合、エーテル結合を伴う場合は加水分解性を有する場合があり好ましくない。本発明で好適に用いられる架橋剤としては、メラミン系、イソシアネート系、カルボジイミド系、オキサゾリン系等が挙げられる。これらの中で、塗液の経時安定性、高温高湿処理下の密着性向上効果からイソシアネート系、カルボジイミド系、が好ましい。さらに、塗布層に適度な柔軟性を奏し、塗布層の応力緩和作用を好適に付与する点で、イソシアネート系架橋剤を用いることが特に好ましい。また、架橋反応を促進させるため、触媒等を必要に応じて適宜使用される。
本発明において、塗布層中に粒子を含有させることもできる。粒子は(1)シリカ、カオリナイト、タルク、軽質炭酸カルシウム、重質炭酸カルシウム、ゼオライト、アルミナ、硫酸バリウム、カーボンブラック、酸化亜鉛、硫酸亜鉛、炭酸亜鉛、二酸化チタン、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、水酸化アルミニウム、加水ハロイサイト、炭酸マグネシウム、水酸化マグネシウム、等の無機粒子、(2)アクリルあるいはメタアクリル系、塩化ビニル系、酢酸ビニル系、ナイロン、スチレン/アクリル系、スチレン/ブタジエン系、ポリスチレン/アクリル系、ポリスチレン/イソプレン系、ポリスチレン/イソプレン系、メチルメタアクリレート/ブチルメタアクリレート系、メラミン系、ポリカーボネート系、尿素系、エポキシ系、ウレタン系、フェノール系、ジアリルフタレート系、ポリエステル系等の有機粒子が挙げられる。
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は、前述のポリエステルフィルムの塗布層の少なくとも片面に、ハードコート層、光拡散層、レンズ層、電磁波吸収層、近赤外線遮断層、透明導電層から選択される、少なくとも1層の光学機能層を積層することにより得られる。なお、前記レンズ層としては特に形状を問わないが、例えば、プリズム状レンズ、フレネル状レンズ、マイクロレンズなどが好適に適用できる。
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。
JIS K7121に準拠し、示差走査熱量計(セイコーインスツルメンツ株式会社製、DSC6200)を使用して、DSC曲線からガラス転移開始温度を求めた。
得られた易接着性ポリエステルフィルムについて塗布層を削り取り、約1mgの試料を採取した。採取した試料に圧力をかけ、厚み約1μmのフィルム状に成型した塗布層試料片(大きさ:約50μm×約50μm)を作成した。さらに、ブランク試料として基材フィルムと同質のPET樹脂についても前記手順と同様にして試料片(ブランク試料片)を作成した。
作成した試料片をKBr板上に載せ、下記条件の顕微透過法により赤外吸収スペクトルを測定した。塗布層の赤外分光スペクトルは、塗布層試料片から得た赤外分光スペクトルとブランク試料片のスペクトルとの差スペクトルとして求めた。
脂肪族系ポリカーボネート成分由来の1460cm-1付近の吸光度(A1460)は1460±10cm-1の領域に吸収極大をもつ吸収ピーク高さの値とし、ウレタン成分由来の1530cm-1付近の吸光度(A1530)は1530±10cm-1の領域に吸収極大をもつ吸収ピーク高さの値とした。なお、ベースラインはそれぞれの極大吸収のピークの両側の裾を結ぶ線とした。得られた吸光度から下記式により吸光度比率を求めた。
(吸光度比率)=A1460/A1530
装置:FT-IR分析装置SPECTRA
TECH社製 IRμs/SIRM
検出器:MCT
分解能:4cm-1
積算回数:128回
得られた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に準拠し、濁度計(日本電色製、NDH2000)を用いて測定した。
得られた易接着性ポリエステルフィルムのヘイズはJIS K 7136に準拠し、濁度計(日本電色製、NDH2000)を用いて測定した。
得られた光学用積層ポリエステルフィルムの光硬化型ハードコート層または光硬化型アクリル層または光硬化型ウレタン/アクリル層面(以下、光学機能層)に、隙間間隔2mmのカッターガイドを用いて、光学機能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つける。次いで、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光学機能層面から引き剥がす作業を5回行った後、光学用積層ポリエステルフィルムの光学機能層面から剥がれたマス目の数を目視で数え、下記の式から光学機能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%、または、光学機能層の材破
○:99~90%
△:89~70%
×:69~0%
得られた光学用積層ポリエステルフィルムを、高温高湿槽中で80℃、95%RHの環境下48時間放置した。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(6)と同様の方法で光学機能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%、または、光学機能層の材破
○:99~90%
△:89~70%
×:69~0%
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、4,4-ジフェニルメタンジイソシアネート43.75質量部、ジメチロールブタン酸12.85質量部、数平均分子量2000のポリヘキサメチレンカーボネートジオール153.41質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン8.77質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min-1で攪拌混合しながら、ポリウレタンプレポリマー溶液を添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分35%の水溶性ポリウレタン樹脂(A-1)を調製した。得られたポリウレタン樹脂(A-1)のガラス転移点温度は-30℃であった。
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、4,4-ジフェニルメタンジイソシアネート29.14質量部、ジメチロールブタン酸7.57質量部、数平均分子量3000のポリヘキサメチレンカーボネートジオール173.29質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン5.17質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min-1で攪拌混合しながら、ポリウレタンプレポリマー溶液を添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分35%の水溶性ポリウレタン樹脂(A-2)を調製した。
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、4,4-ジフェニルメタンジイソシアネート43.75質量部、ジメチロールブタン酸11.12質量部、ヘキサンジオール1.97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143.40質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン8.77質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min-1で攪拌混合しながら、ポリウレタンプレポリマー溶液を添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分35%の水溶性ポリウレタン樹脂(A-3)を調製した。
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、イソホロンジイソシアネート38.41質量部、ジメチロールプロパン酸6.95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158.99質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン4.37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γ―(アミノエチル)アミノプロピルトリエトキシシラン3.84質量部、2-[(2-アミノエチル)アミノ]エタノール1.80質量部と水450gを添加して、ポリウレタンプレポリマー溶液を滴下して水分散した。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30%の水溶性シラノール基含有ポリウレタン樹脂(A-4)を調製した。
水溶性ポリウレタン樹脂(A-1)の数平均分子量2000のポリヘキサメチレンカーボネートジオールを数平均分子量1000のポリヘキサメチレンカーボネートジオールに変更した以外は、同様の方法で固形分35%の水溶性ポリウレタン樹脂(A-5)を得た。
水溶性ポリウレタン樹脂(A-1)の数平均分子量2000のポリヘキサメチレンカーボネートジオールを数平均分子量5000のポリヘキサメチレンカーボネートジオールに変更した以外は、同様の方法で固形分35%の水溶性ポリウレタン樹脂(A-6)を得た。
水溶性ポリウレタン樹脂(A-1)の数平均分子量2000のポリヘキサメチレンカーボネートジオールを数平均分子量2000のポリエステルジオールに変更した以外は、同様の方法で固形分35%の水溶性ポリウレタン樹脂(A-7)を得た。
水溶性ポリウレタン樹脂(A-1)の数平均分子量2000のポリヘキサメチレンカーボネートジオールを数平均分子量2000のポリエーテルジオールに変更した以外は、同様の方法で固形分35%の水溶性ポリウレタン樹脂(A-8)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(B)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ー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(C)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−メチルー−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(D)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。
水 55.62質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂(A-1) 11.29質量%
ブロックポリイソシアネート水分散液(B) 2.26質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
粒子 0.07質量%
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.05質量%
(シリコン系、固形分濃度100質量%)
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急冷密着固化させ、未延伸PETシートを得た。
(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)
前記の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(E)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。
ハードコート層形成用塗布液(E)
メチルエチルケトン 65.00質量%
ジペンタエリスリトールヘキサアクリレート 27.20質量%
(新中村化学製A-DPH)
ポリエチレンジアクリレート 6.80質量%
(新中村化学製A-400)
光重合開始剤 1.00質量%
(チバスペシャリティーケミカルズ社製イルガキュア184)
清浄に保った厚さ1mmのSUS板上(SUS304)に、下記光硬化型アクリル系塗布液を約5gのせ、フィルム試料の塗布層面と光硬化型アクリル系塗布液が接するように重ね合わせ、フィルム試料の上から幅10cm、直径4cmの手動式荷重ゴムローラーで光硬化型ウレタン/アクリル系塗布液(F)を引き延ばすように圧着した。次いで、フィルム面側から、高圧水銀灯を用いて500mJ/cm2の紫外線を照射し、光硬化型ウレタン/アクリル樹脂を硬化させた。厚み20μmの光硬化型ウレタン/アクリル層を有するフィルム試料をSUS板から剥離し、光学用積層ポリエステルフィルムを得た。
光硬化型ウレタン/アクリル系塗布液(F)
光硬化型アクリル樹脂 67.00質量%
(新中村化学製A-BPE-4)
光硬化型アクリル樹脂 15.00質量%
(新中村化学製AMP-10G)
光硬化型ウレタン/アクリル樹脂 15.00質量%
(新中村化学製U-6HA)
光重合開始剤 3.00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)
光硬化型ウレタン/アクリル層を有する光学用積層ポリエステルフィルムの光硬化型ウレタン/アクリル系塗布液(F)を光硬化型アクリル系塗布液(G)に変更した以外は同様にして、光学用積層ポリエステルフィルムを得た。
光硬化型アクリル系塗布液(G)
光硬化型アクリル樹脂 67.00質量%
(新中村化学製A-BPE-4)
光硬化型アクリル樹脂 30.00質量%
(新中村化学製AMP-10G)
光重合開始剤 3.00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)
ポリウレタン樹脂をポリウレタン樹脂(A-5)に変更した以外は実施例1と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
ポリウレタン樹脂をポリウレタン樹脂(A-6)に変更した以外は実施例1と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
ポリウレタン樹脂をポリウレタン樹脂(A-7)に変更した以外は実施例1と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
ポリウレタン樹脂をポリウレタン樹脂(A-8)に変更した以外は実施例1と同様にして易接着性ポリエステルフィルムおよび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と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
水 53.04質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂(A-1) 16.13質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
粒子 0.07質量%
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.05質量%
(シリコン系、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と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
水 53.91質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂(A-1) 14.51質量%
ブロックポリイソシアネート水分散液(B) 0.75質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
粒子 0.07質量%
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.05質量%
(シリコン系、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と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
水 54.76質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂(A-1) 12.90質量%
ブロックポリイソシアネート水分散液(B) 1.51質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
粒子 0.07質量%
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.05質量%
(シリコン系、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と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
水 57.35質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂(A-1) 8.06質量%
ブロックポリイソシアネート水分散液(B) 3.76質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
粒子 0.07質量%
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.05質量%
(シリコン系、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と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
水 59.92質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂(A-1) 3.23質量%
ブロックポリイソシアネート水分散液(B) 6.02質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
粒子 0.07質量%
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.05質量%
(シリコン系、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と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
水 60.79質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂(A-1) 1.61質量%
ブロックポリイソシアネート水分散液(B) 6.77質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
粒子 0.07質量%
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.05質量%
(シリコン系、固形分濃度100質量%)
ポリウレタン樹脂をポリウレタン樹脂(A-2)に変更した以外は実施例1と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
ポリウレタン樹脂をポリウレタン樹脂(A-3)に変更した以外は実施例1と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
ポリウレタン樹脂をシラノール基含有ポリウレタン樹脂(A-4)に変更した以外は実施例1と同様にして易接着性ポリエステルフィルムおよび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(B)をオキサゾリン基を有する水溶性樹脂(C)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(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)をイミノ・メチロールメラミン(固形分濃度70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。
塗布液を下記に変更したこと以外は実施例1と同様にして易接着性ポリエステルフィルムおよび光学用積層ポリエステルフィルムを得た。
水 62.82質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂(A-1) 5.64質量%
ブロックポリイソシアネート水分散液(B) 1.13質量%
粒子 0.35質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
粒子 0.04質量%
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.02質量%
(シリコン系、固形分濃度100質量%)
Claims (6)
- 少なくとも片面に塗布層を有するポリエステルフィルムであって、
前記塗布層が、脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂と架橋剤を主成分とし、
前記塗布層の赤外分光スペクトルにおいて脂肪族系ポリカーボネート成分由来の1460cm-1付近の吸光度(A1460)とウレタン成分由来の1530cm-1付近の吸光度(A1530)との比率(A1460/A1530)が0.40~1.55であることを特徴とする易接着性ポリエステルフィルム。 - 前記架橋剤が、メラミン系架橋剤、イソシアネート系架橋剤、カルボジイミド系架橋剤、オキサゾリン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1に記載の易接着性ポリエステルフィルム。
- 前記塗布層中の脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂と架橋剤の質量比(ウレタン樹脂/架橋剤)が1/9~9/1である、請求項1または2に記載の易接着性ポリエステルフィルム。
- ポリエステルフィルムのヘイズが2.5%以下である、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。
- 請求項1~3のいずれかに記載する易接着性ポリエステルフィルムの前記塗布層に、ハードコート層、光拡散層、レンズ層、電磁波吸収層、近赤外線遮断層、透明導電層から選択される少なくとも1層の光学機能層を積層してなる積層ポリエステルフィルム。
- 請求項1~4のいずれかに記載の易接着性ポリエステルフィルムを巻き取ってなる光学用易接着性ポリエステルフィルムロール。
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CN113544200B (zh) * | 2019-06-03 | 2023-09-12 | 东洋纺株式会社 | 覆金属聚酯薄膜 |
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KR101685733B1 (ko) | 2016-12-12 |
CN102497985B (zh) | 2015-06-17 |
JP4770971B2 (ja) | 2011-09-14 |
TWI411634B (zh) | 2013-10-11 |
KR20120051043A (ko) | 2012-05-21 |
CN102497985A (zh) | 2012-06-13 |
TW201111422A (en) | 2011-04-01 |
JP2011031561A (ja) | 2011-02-17 |
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