WO2011040160A1 - 積層フィルム - Google Patents
積層フィルム Download PDFInfo
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- WO2011040160A1 WO2011040160A1 PCT/JP2010/064668 JP2010064668W WO2011040160A1 WO 2011040160 A1 WO2011040160 A1 WO 2011040160A1 JP 2010064668 W JP2010064668 W JP 2010064668W WO 2011040160 A1 WO2011040160 A1 WO 2011040160A1
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- layer
- mass
- coating
- film
- resin
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping 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
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
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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
- B32B2375/00—Polyureas; Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/204—Plasma displays
Definitions
- the present invention relates to a laminated film having excellent adhesion and moisture and heat resistance. Specifically, it is suitable as a base film 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. It relates to an easily adhesive film.
- the base material of an optical functional film used in a liquid crystal display is a transparent thermoplastic made of polyethylene terephthalate (PET), acrylic, polycarbonate (PC), triacetyl cellulose (TAC), polyolefin, polyamide, or the like.
- PET polyethylene terephthalate
- PC polycarbonate
- TAC triacetyl cellulose
- polyolefin polyamide
- polyamide polyamide
- thermoplastic resin film When using the thermoplastic resin film as a base material for various optical functional films, optical 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 external light from being reflected, and a lens layer that is used to collect and diffuse light And an optical functional layer such as a light diffusion layer for improving luminance.
- a protective film hard coat layer
- AR layer antireflection layer
- lens layer that is used to collect and diffuse light
- an optical 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.
- a method of imparting 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 thermoplastic resin film of the base Is generally known.
- an aqueous coating solution containing the resin solution or a dispersion in which the resin is dispersed in a dispersion medium is applied to a base film with a thermoplastic resin film before crystal orientation is completed in a stretched film.
- thermoplastic resin film stretched at least in a uniaxial direction and then subjected to heat treatment to complete the orientation of the thermoplastic resin film (so-called in-line coating method), or after the production of the thermoplastic resin film,
- in-line coating method a method of drying after applying a solvent-based coating solution (so-called off-line coating method) has been 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 bathrooms, high-temperature and high-humidity areas, etc. in addition to high transparency.
- the laminated film used for such applications requires high adhesion even under high temperature and high humidity. Therefore, as exemplified below, by adding a cross-linking agent to the coating liquid, a highly adhesive thermoplastic that has given heat and moisture resistance by forming a cross-linked structure in the coating layer when the coating layer is laminated by the in-line coating method.
- a resin film is disclosed. *
- Patent Document 1 one kind of resin selected from an acrylic resin, a polyester resin, and a urethane resin in the laminated film, and a melamine-based crosslinking agent, an oxazoline-based crosslinking agent, an isocyanate-based crosslinking agent, an aziridine-based crosslinking agent,
- a lens sheet that includes a cross-linking agent selected from at least one of epoxy-based cross-linking agents and is provided with a laminated film containing at least one of amide ester bond, urethane bond, amide bond, and urea bond
- a film is disclosed, and specifically, urethane resin and melamine crosslinking agent, polyester resin and melamine crosslinking agent and oxazoline crosslinking agent, acrylic resin, polyester resin and oxazoline crosslinking agent and the like are exemplified.
- Patent Document 2 exemplifies an optically easy-adhesive polyester film provided with a coating layer containing a polyester resin and an acrylic resin having an oxazoline group and a polyalkylene oxide chain.
- Patent Document 3 exemplifies an easily adhesive film in which a polyester-based polyurethane and an oxazoline-containing polymer are applied.
- Patent Document 4 exemplifies a polycarbonate-based polyurethane having an anionic group and a melamine-based crosslinking agent or an epoxy-based crosslinking agent.
- Patent Document 5 the present applicant exemplifies an easily adhesive film for optics in which a coating layer composed of a copolyester resin, a polyurethane resin, and an oxazoline-based crosslinking agent is laminated.
- JP 2000-141574 A Japanese Patent No. 3773738 JP 2000-355086 A Japanese Patent No. 2544792 Japanese Patent No. 3900191
- the present invention hardly deteriorates the coating layer in a high temperature and high humidity environment, which has been considered to be unavoidable in the past, in other words, almost no decrease in adhesion (moisture heat resistance) in a high temperature and high humidity environment. It is intended to provide a laminated film that does not cause.
- the adhesion (wet heat resistance) under high temperature and high humidity referred to in the present invention is a layer of a photocurable acrylic layer, and then placed in an environment of 80 ° C., 95% RH, 48 hours, with a gap interval of 2 mm.
- 100 square cuts that penetrate the photocurable acrylic resin layer and reach the base film are made on the photocurable acrylic layer surface, and then cellophane adhesive tape is applied to the square cut surface.
- Attaching and rubbing with an eraser means complete adhesion, meaning adhesion when the same part is peeled off 5 times vigorously, and adherence according to criteria more stringent than the evaluation method described in JIS K5600-5-6 It is based on sex evaluation.
- An object of the present invention is to provide a laminated film that retains not only the initial adhesiveness (initial adhesiveness) but also excellent adhesiveness even under such high temperature and high humidity.
- the present inventor has found not only initial adhesion but also moisture resistance by a coating layer containing polycarbonate urethane resin as a main component and 1.0 to 4.0 mmol / g of oxazoline group.
- the inventors have found the surprising effect that the heat is improved, and have reached the present invention. That is, the coating layer contains a polycarbonate-based urethane resin and a compound having an oxazoline group, but these have substantially no cross-linked structure or have a low degree of cross-linking so that the oxazoline group remains in the coating layer.
- the present inventors have found the fact that overturns the conventional common sense that high adhesion is maintained even under high temperature and high humidity, and the present invention has been achieved.
- a crosslinking agent and a resin having a functional group capable of reacting with it are mixed to form a highly crosslinked structure when the coating layer is laminated. It has been considered desirable.
- the present invention uses a polycarbonate urethane resin and an oxazoline-based cross-linking agent that have few or substantially no carboxyl groups or salts thereof, which are functional groups having high reactivity with oxazoline groups.
- the oxazoline group remains in a specific range in the coating layer.
- An oxazoline-based cross-linking agent having high reactivity with a carboxyl group is applied in combination with a resin having a functional group such as a carboxyl group from the technical common sense, and is combined with a resin having substantially no carboxyl group.
- the content of the oxazoline group in the coating layer can be determined by total reflection absorption infrared spectroscopy.
- 1st invention of this application is a laminated
- the said coating layer has polycarbonate type urethane resin as a main component, Furthermore, the oxazoline group is 0 in the said coating layer.
- a laminated film containing 5 to 4.0 mmol / g. 2nd invention of this application is the said laminated
- the base film has a layered structure of A layer / B layer / A layer, the layer A contains inorganic particles, and the layer B contains substantially no particles. It is.
- 4th invention of this application is the said laminated
- 5th invention of this application is the said laminated
- the laminated film of the invention of the present application is extremely excellent in initial adhesion and adhesion under high temperature and high humidity (moisture heat resistance).
- the adhesiveness with an optical functional layer at high temperature and high humidity is excellent.
- the functional layer laminated on the coating layer, such as a lens sheet has a very thin portion, and is particularly useful for applications where the coating layer is susceptible to deterioration under high temperature and high humidity.
- it is excellent in initial adhesiveness and heat-and-moisture resistance, and can aim at coexistence with high transparency and handling property.
- the thermoplastic resin constituting the base film of the present invention includes polyolefin resins such as polyethylene and polypropylene, polyamide resins such as nylon 6 and nylon 66, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and polymethylene terephthalate. And a copolymer component such as diol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. Polyester resins such as those obtained by copolymerization can be used. Of these, polyester resins are preferred from the viewpoint of mechanical strength and chemical resistance.
- 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 base film of the present invention preferably contains inorganic particles in order to improve handling properties.
- a preferred embodiment of the base film is a base film composed of at least three layers.
- the layer structure in the three-layer structure the structure of the outermost layer on the front and back may be the same composition or different composition, but the two kinds of three layers (A layer / B layer / A layer) are flat. From the point of view, it is preferable.
- the outermost layer (A layer / B layer / A layer in the case of A layer) contains particles
- the center layer (B layer) contains substantially no particles.
- the reason why the layer A contains particles is that the contact area between the base film and the coating layer interface can be increased by setting the surface roughness to an appropriate level, and an effect of obtaining higher adhesion can be obtained. This is to improve handling properties such as slipping property, winding property and blocking resistance, and wear properties such as wear resistance and scratch resistance.
- the characteristics can be evaluated by a coefficient of static friction ( ⁇ s) between the laminated film surfaces. In this case, the static friction coefficient ( ⁇ s) is preferably 0.7 or less.
- the reason why the layer B does not substantially contain particles is to maintain high transparency.
- the thickness ratio of each layer is arbitrary without limitation, and the total thickness of both outermost layers is preferably 100 ⁇ m, and the upper limit is preferably 80 ⁇ m. Particularly preferred. If it exceeds 100 ⁇ m, the transparency is lowered, which may not be preferable.
- substantially free of 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, it is less than 50 ppm, preferably less than 10 ppm, most preferably detected The content is below the limit. This means that even if particles are not actively added to the base film, contaminants derived from foreign substances and raw material resin or dirt adhering to the line or equipment in the film manufacturing process will be peeled off and mixed into the film. It is because there is a case to do.
- the thickness of the base film used in the present invention is not particularly limited, but can be arbitrarily determined in the range of 30 to 500 ⁇ m according to the standard to be used.
- the upper limit of the thickness of the base film is preferably 350 ⁇ m, particularly preferably 250 ⁇ m.
- the lower limit of the film thickness is preferably 50 ⁇ m, more preferably 75 ⁇ m, and particularly preferably 100 ⁇ m.
- the film thickness is less than the lower limit, rigidity and mechanical strength tend to be insufficient.
- the film thickness exceeds the upper limit the cost may increase.
- These layers can contain various additives in the polyester, if necessary.
- 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 type and content of the particles contained in the outermost layer may be inorganic particles or organic particles, and are not particularly limited, but include metal oxidation such as silica, titanium dioxide, talc, and kaolinite.
- metal oxidation such as silica, titanium dioxide, talc, and kaolinite.
- examples thereof include inorganic particles that are inert to polyesters such as products, calcium carbonate, calcium phosphate, and barium sulfate. Any one of these inert inorganic particles may be used alone, or two or more thereof may be used in combination.
- the above particles preferably have an average particle size of 0.1 to 3.5 ⁇ m.
- the lower limit of the average particle diameter is more preferably 0.5 ⁇ m, further preferably 0.8 ⁇ m, and still more preferably 1.0 ⁇ m.
- the upper limit of the average particle is more preferably 3.0 ⁇ m, still more preferably 2.8 ⁇ m. If the average particle size is less than the lower limit, sufficient handling properties may not be obtained. If the upper limit is exceeded, the transparency may decrease.
- These particles are preferably porous particles, particularly porous silica. Porous particles are easily deformed into a flat shape during stretching in the film forming process, and voids are not easily generated around the particles during stretching, and high transparency is easily obtained.
- the content of the inorganic particles in the outermost layer is preferably 0.01 to 0.20% by mass with respect to the polyester constituting the outermost layer.
- the lower limit of the concentration is more preferably 0.02% by mass, and further preferably 0.03% by mass.
- the upper limit of the concentration is more preferably 0.15% by mass, and further preferably 0.10% by mass. If it is less than the lower limit, sufficient handling properties cannot be obtained. When the upper limit is exceeded, the transparency decreases.
- the average particle size of the particles can be measured by the following method. Take a photograph of the particles with an electron microscope or an optical microscope and at a magnification such that the size of one smallest particle is 2 to 5 mm, the maximum diameter of 300 to 500 particles (in the case of porous silica, Particle diameter) is measured, and the average value is defined as the average particle diameter. Moreover, when calculating
- TEM transmission electron microscope
- a known method can be adopted.
- it can be added at any stage for producing the polyester, but it is preferably added as a slurry dispersed in ethylene glycol or the like at the stage of esterification or after the end of the ester exchange reaction and before the start of the polycondensation reaction.
- the polycondensation reaction may proceed.
- a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material or a method of blending dried particles and a polyester raw material using a kneading extruder It can be carried out.
- the surface of the substrate film such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, etc., is within the range not impairing the object of the present invention.
- An activation process may be performed.
- the coating layer of the present invention will be described.
- the oxazoline group is left in a specific range with a polycarbonate urethane resin as a main component.
- the “main component” means containing 30% by mass or more as the total solid component contained in the coating layer.
- the polycarbonate polyurethane resin and the compound having an oxazoline group have substantially no crosslinked structure or have a low degree of crosslinking.
- the coating layer of the present invention does not contain a carboxyl group or a salt thereof, which is a functional group having high reactivity with the oxazoline group, or its salt is very small, so that there are many unreacted oxazoline groups in the coating layer. .
- a functional group such as a carboxyl group is present in a resin used for a functional layer to be laminated, such as a photocurable acrylic resin and an unreacted product.
- a functional group exists also in the thermoplastic resin which is a base film. It is presumed that in a high-temperature and high-humidity environment, the interaction between the functional group and / or the oxazoline group present in these functional layers and / or the substrate film proceeds, and strong adhesion can be obtained.
- the lower limit of the concentration of the oxazoline group in the coating layer is 0.5 mmol / g, preferably 0.7 mmol / g, more preferably 1.0 mmol / g, and the upper limit is 4.0 mmol / g, preferably 3 0.8 mmol / g, more preferably 3.5 mmol / g. If the amount is less than the above lower limit, sufficient adhesiveness at high temperature and high humidity may not be obtained. When the above upper limit is exceeded, the ratio of the polycarbonate-based urethane resin becomes relatively small, and the adhesiveness, particularly the initial adhesiveness, may be lowered.
- the adhesiveness (humidity and heat resistance) with an optical functional layer such as a lens layer, a hard coat layer, a light diffusion layer, an electromagnetic wave absorption layer, a near infrared ray blocking layer, and a transparent conductive layer under high temperature and high humidity.
- an optical functional layer such as a lens layer, a hard coat layer, a light diffusion layer, an electromagnetic wave absorption layer, a near infrared ray blocking layer, and a transparent conductive layer under high temperature and high humidity.
- 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.
- a water-soluble urethane resin is used, compatibility with a resin having an oxazoline group increases, and transparency can be improved.
- 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 into the urethane molecular skeleton.
- the sulfonic acid (salt) group is strongly acidic and it may be difficult to maintain heat and moisture resistance due to its hygroscopic performance, it is common to introduce a carboxylic acid (salt) group that is weakly acidic. is there.
- the coating layer has substantially no carboxyl group. Therefore, in order to impart water solubility to the urethane resin, it is a preferred embodiment of the present invention to introduce a polyoxyalkylene group instead of a carboxyl group.
- the polycarbonate urethane resin used in the coating solution of the present invention will be described in more detail.
- it has a polycarbonate polyol as a structural component of a polycarbonate-type urethane resin, ie, a urethane resin, It is characterized by the above-mentioned.
- Urethane resins are broadly classified into polyester-based urethane resins, polyether-based urethane resins, and polycarbonate-based urethane resins.
- Polyester-based urethane resins are easily hydrolyzed at high temperatures and high humidity, and polyether-based urethane resins are highly hygroscopic. For this reason, the film strength of the coating layer tends to decrease, and the adhesion is insufficient.
- polycarbonate urethane resin has excellent moisture and heat resistance. This is the reason why the polycarbonate urethane resin is used in the present invention.
- the moisture and heat resistance can be improved by adding a urethane resin containing polycarbonate as a constituent component to the coating layer of the present invention.
- the polycarbonate urethane resin of the present invention contains at least a polyol component and a polyisocyanate component as constituent components, and further contains a chain extender as necessary.
- the polycarbonate urethane resin of the present invention is a polymer compound in which these constituent components are mainly copolymerized by urethane bonds.
- the structural component of these polycarbonate-type urethane resins can be specified by nuclear magnetic resonance analysis (NMR) etc.
- a polycarbonate diol obtained by reacting one or more diols such as bisphenol-A with carbonates such
- the composition molar ratio of the polycarbonate polyol which is a constituent component of the urethane resin, is preferably 3 to 100 mol% when the total polyisocyanate component of the urethane resin is 100 mol%, preferably 5 to 50 mol%. More preferably, it is 6 to 20 mol%.
- the composition molar ratio is low, the durability effect by the polycarbonate polyol may not be obtained.
- the said composition molar ratio is high, initial adhesiveness may fall.
- polyisocyanates examples include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, 1 Alicyclic diisocyanates such as 1,3-cyclohexanebismethylisocyanate, hexamethylene diisocyanate, and aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, or trimethylolpropane containing one or more of these compounds. And polyisocyanates added in advance.
- Chain extenders include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol, ethylenediamine, hexamethylene Examples thereof include diamines and diamines such as piperazine, amino alcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol, and water.
- glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol
- polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol
- ethylenediamine hexamethylene
- diamines and diamines such as piperazine
- amino alcohols such as monoethanolamine and diethanolamine
- the polycarbonate polyurethane used in the present invention preferably has a structure having a polyoxyethylene chain in the side chain of the urethane resin.
- Examples of the polyoxyalkylene group introduced into the urethane resin include a polyoxyethylene group, a polyoxypropylene group, and a polytetramethylene glycol chain, and these can be used alone or in combination of two or more. Among these, a polyoxyethylene group can be preferably used.
- polyisocyanate and one-end blocked polyoxyethylene glycol (alkoxyethylene glycol whose one end is blocked with an alkyl group having 1 to 20 carbon atoms) are blocked at one end.
- the polyoxyethylene chain-containing monoisocyanate was obtained by removing the unreacted polyisocyanate if necessary. Then, the obtained polyoxyethylene chain-containing monoisocyanate and diisocyanate can be obtained by an allophanatization reaction.
- the composition molar ratio of the polyoxyethylene groups in the urethane resin is 100 mol% of the total polyisocyanate component of the urethane resin. It is preferably 3 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. If the composition molar ratio is less than 3 mol%, water dispersibility may be difficult.
- the polycarbonate-based urethane resin obtained by the above method has substantially or little carboxyl groups or salts thereof which are functional groups with oxazoline groups.
- the polycarbonate-based urethane resin is preferably contained in the coating layer in an amount of 30% by mass to 90% by mass.
- it is more preferably 40% by mass or more and 80% by mass or less.
- the content of the urethane resin is large, the content of the compound having an oxazoline group is relatively small, so that the adhesiveness under high temperature and high humidity decreases, and conversely, the content of the urethane resin is small. In this case, not only the initial adhesiveness is lowered, but the coating layer may be peeled off during the coating process, which may be a drawback.
- a resin other than the polycarbonate-based urethane resin may be included to improve adhesion.
- an acrylic resin, a polyester resin, etc. are mentioned. Those having a low content of carboxyl groups or salts thereof are preferable, and those having no carboxyl group or salts thereof are more preferable.
- carboxyl groups or salts thereof reacts with the oxazoline group, and the oxazoline group that reacts with a functional group such as a carboxyl group contained in the base film or optical function layer under high temperature and high humidity decreases. It is not preferable.
- the coating layer contains a compound having an oxazoline group.
- the compound having an oxazoline group is preferably water-soluble because it has good compatibility with other water-soluble resins and improves the transparency of the coating layer.
- hydrophilic monomers include 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and monomers having a polyethylene glycol chain such as a monoester compound of (meth) acrylic acid and polyethylene glycol, (Meth) acrylic acid 2-aminoethyl and its salts, (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, (meth) acrylonitrile, sodium styrenesulfonate, etc. Can be mentioned.
- the monomer which has polyethyleneglycol chains such as (meth) acrylic-acid methoxypolyethylene glycol with high solubility to water, and the monoester compound of (meth) acrylic acid and polyethyleneglycol.
- the oxazoline value of the compound having an oxazoline group used in the present invention is not particularly limited, but specifically, for example, 1000 g-solid / eq. Or less, more preferably 500 g-solid / eq. Hereinafter, even more preferably 300 g-solid / eq. It is as follows.
- the oxazoline value (g-solid / eq.) Is the weight of the polymer per 1 mol of the oxazoline group. Therefore, the smaller the value of the oxazoline value, the larger the amount of oxazoline groups in the polymer, and the larger the value, the smaller the amount of oxazoline groups in the polymer.
- the compound having an oxazoline group used in the present invention may be commercially available.
- examples of commercially available compounds having a water-soluble or water-dispersible oxazoline group include Epocros WS-300, Epocros WS-500, Epocros WS-700, and Epocros K-2010E manufactured by Nippon Shokubai Co., Ltd.
- the compound having an oxazoline group is preferably contained in the coating layer in an amount of 10% by mass to 70% by mass.
- it is more preferably 30% by mass or more and 70% by mass or less.
- the presence / absence and content of the oxazoline group in the coating layer can be determined by a known method. For example, a method of detecting by infrared spectroscopy as described below, or scraping off the coating layer, dissolving the scraped material in methyl ethyl ketone, chloroform or dimethylformamide, and using a nuclear magnetic resonance analyzer (NMR), from its integration ratio Examples thereof include a method of determining a mole% ratio of each composition.
- the 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, Inorganic particles such as diatomaceous earth, calcium silicate, aluminum hydroxide, hydrous halloysite, magnesium carbonate, magnesium hydroxide, (2) acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / Butadiene, polystyrene / acrylic, polystyrene / isoprene, polystyrene / isoprene, methyl methacrylate / butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, Allyl phthalate
- 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.
- 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 surface roughness (Ra) of the coating layer is preferably 2 to 25 nm. More preferably, it is 5 to 20 nm. If it is less than 2 nm, the blocking resistance is lowered, and if it exceeds 25 nm, the transparency 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 haze is preferably 3.0% or less, more preferably 2.5% or less, and further preferably 2.0% or less.
- Such a laminated film can be improved in compatibility with other resins by preferably making the compound having an oxazoline group contained in the coating layer described above water-soluble.
- additives may be contained within a range that does not impair adhesion with the optical functional layer.
- the additive include fluorescent dyes, fluorescent brighteners, plasticizers, ultraviolet absorbers, pigment dispersants, foam suppressors, antifoaming agents, preservatives, and antistatic agents.
- a method of coating a polyester film with a coating solution containing a solvent, particles, and a resin and drying the coating solution may be mentioned.
- the solvent include organic solvents such as toluene, water, and a mixed system of water and a water-soluble organic solvent.
- water alone or a mixture of a water-soluble organic solvent and water is used from the viewpoint of environmental burden. preferable.
- any known method can be used as a method for applying the coating solution for forming the coating layer to the base 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 coating the coating solution on an unstretched or uniaxially stretched film, drying it, stretching it at least in a uniaxial direction, and then performing a heat treatment.
- the coating amount after drying of the finally obtained coating layer is preferably 0.02 to 0.5 g / m 2 . If the coating amount of the coating layer is less than 0.02 g / m 2 , the effect on adhesiveness may be reduced. On the other hand, if the coating amount exceeds 0.5 g / m 2 , blocking resistance may be lowered.
- the laminated film of the present invention has at least one optical layer 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 the coating layer surface of the base film described above.
- a functional layer can be laminated and used.
- 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 coated layer of the laminated film obtained in the present invention has good adhesion to the hard coat layer, the light diffusion layer, the prismatic lens layer, the electromagnetic wave absorption layer, the near infrared ray blocking layer, and the transparent conductive layer. Furthermore, good adhesive strength can be obtained even for applications other than optical applications. Specifically, 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 absorbance derived from the oxazoline group is the value of the height of the absorption peak having an absorption maximum in the region of 1655 ⁇ 10 cm ⁇ 1 (A 1655 ), and the absorbance derived from PET has the absorption maximum in the region of 1340 ⁇ 10 cm ⁇ 1.
- the height of the absorption peak (A 1340 ) was used.
- the base line was a line connecting the sleeves on both sides of each maximum absorption peak.
- the thickness of the coating layer was determined with a transmission electron microscope.
- a sample of the laminated film was embedded in a visible light curable resin (D-800 manufactured by Nippon Shin-EM Co., Ltd.) and cured by exposure to visible light at room temperature.
- an ultrathin section having a thickness of about 70 to 100 nm was prepared using an ultramicrotome equipped with a diamond knife, and stained in ruthenium tetroxide vapor for 30 minutes. Furthermore, after performing carbon vapor deposition, the cross section was observed using the transmission electron microscope (the JEOL Co., Ltd. make, TEM2010), the photograph was image
- the concentration of the oxazoline group in the coating layer was determined using a calibration curve prepared from a standard sample that had been coated with a coating solution with a known oxazoline concentration and air-dried in advance. Asked.
- the mixture was adjusted so that the fixed component concentration was 30% by mass), and the coating layer after drying was applied so that the thickness of the coating layer was 50 nm, 100 nm, and 200 nm.
- the infrared absorbance ratio A 1655 / A 1340 was measured by external spectroscopy, and the following primary formula consisting of three variables of the oxazoline group concentration, coating layer thickness, and infrared absorbance ratio A 1655 / A 1340 was obtained from the obtained results. This was used as a calibration curve.
- (Oxazoline concentration) A ⁇ (Infrared absorbance ratio A 1655 / A 1340 ) / (Coating layer thickness) + B (Here, A and B are constants obtained from the data obtained by creating the calibration curve)
- Adhesiveness (%) (1 ⁇ number of peeled squares / 100) ⁇ 100 ⁇ : 100% or photocuring acrylic layer material failure ⁇ : 99-90% ⁇ : 89-70% ⁇ : 69 to 0%
- Photo-curing acrylic resin composition 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 acrylic coating solution was pressed from above the sample with a manually loaded rubber roller having a width of 10 cm and a diameter of 4 cm so as to extend. Subsequently, 800 mJ / cm ⁇ 2 > of ultraviolet rays were irradiated from the film surface side using the high pressure mercury lamp, and the photocurable acrylic resin was hardened.
- a film sample having a photocurable acrylic layer having a thickness of 20 ⁇ m was peeled from the SUS plate to obtain an optical functional film.
- Photo-curing acrylic coating solution Photocurable acrylic resin 54.00% by mass (Arakawa Chemical Beam Set 505A-6) Photo-curing acrylic resin 36.00% by mass (Arakawa Chemical Beam Set 550) Photopolymerization initiator 10.00% by mass (Irgacure 184 manufactured by Ciba Specialty Chemicals)
- a sample film was prepared by cutting out an area of 8 cm ⁇ 5 cm from the films obtained in Examples and Comparative Examples. This was fixed to the bottom surface of a metal rectangular parallelepiped having a size of 6 cm ⁇ 5 cm and having a weight of 4.4 kg so that the coating layer surface was on the outside. At this time, the 5 cm width direction of the sample film and the 5 cm width direction of the metal cuboid were matched, one side in the longitudinal direction of the sample film was bent, and fixed to the side surface of the metal cuboid with an adhesive tape.
- a sample film was cut out to an area of 20 cm ⁇ 10 cm from the same laminated film, and the end portion in the longitudinal direction was fixed to a flat metal plate with an adhesive tape with the coating layer surface facing up.
- the measurement surface of the metal rectangular parallelepiped on which the sample film was adhered was placed in contact with this, and the static friction coefficient ( ⁇ s) was measured under the conditions of a pulling speed of 200 mm / min, 23 ° C. and 65% RH.
- RTM-100 manufactured by Toyo BALDWIN Co., Ltd. was used, and the coefficient of static friction ( ⁇ s) was JIS. Calculation was performed according to K-7125. When the static friction coefficient ( ⁇ s) was 0.7 or less, handling property was good ( ⁇ ), and when it exceeded 0.7, handling property was poor (x).
- Oxazoline value A resin containing oxazoline is lyophilized and analyzed by 1 H-NMR, and the oxazoline value is calculated from the absorption peak intensity derived from the oxazoline group and the absorption peak intensity derived from other monomers. did.
- the reaction was carried out to a rate of 99% or more. Subsequently, this was cooled to 30 degreeC and the isocyanate group terminal prepolymer was obtained. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., added with an isocyanate group-terminated prepolymer while stirring and mixing at 2000 min ⁇ 1 to disperse in water. did. Thereafter, a part of acetonitrile and water was removed under reduced pressure to prepare an aqueous solution (A-1) of a polycarbonate urethane resin having a solid content of 35%.
- A-1 aqueous solution of a polycarbonate urethane resin having a solid content of 35%.
- a monomer mixture consisting of 126 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline and 84 parts of methoxypolyethylene glycol acrylate prepared in advance, and ABN-E (manufactured by Nippon Hydrazine Kogyo Co., Ltd.)
- Polymerization initiator An initiator solution consisting of 21 parts of 2,2′-azobis (2-methylbutyronitrile) and 189 parts of isopropyl alcohol was added dropwise over 2 hours using a dropping funnel. During the reaction, nitrogen gas was kept flowing, and the temperature in the flask was kept at 80 ⁇ 1 ° C.
- the obtained oxazoline group-containing resin (B-1) has an oxazoline value of 220 g-solid / eq. Met.
- the obtained polymer was dissolved in ion exchange water to obtain an aqueous solution (B-1) having a solid content concentration of 25% by mass.
- a monomer mixture consisting of 213 parts of methyl methacrylate, 58 parts of 2-isopropenyl-2-oxazoline and 123 parts of methoxypolyethylene glycol acrylate prepared in advance, and ABN-E (manufactured by Nippon Hydrazine Kogyo Co., Ltd.)
- Polymerization initiator An initiator solution consisting of 21 parts of 2,2′-azobis (2-methylbutyronitrile) and 189 parts of isopropyl alcohol was added dropwise over 2 hours using a dropping funnel. During the reaction, nitrogen gas was kept flowing, and the temperature in the flask was kept at 80 ⁇ 1 ° C.
- the obtained resin (B-3) having an oxazoline group had an oxazoline value of 550 g-solid / eq. Met.
- the obtained polymer was dissolved in ion-exchanged water to obtain an aqueous solution (B-3) having a solid content concentration of 25% by mass.
- the polycondensation reaction was carried out to obtain a copolymerized polyester resin (A) having a number average molecular weight of 19,500 and a glass transition temperature of 62 ° C. 300 parts by mass of the obtained copolyester resin and 140 parts by mass of butyl cellosolve were stirred at 160 ° C. for 3 hours to obtain a viscous melt, water was gradually added to the melt, and a uniform light white color was added after 1 hour. An aqueous dispersion (C-1) having a solid concentration of 35% was obtained.
- Example 1 Preparation of coating solution (A) The following coating agent was mixed to prepare a coating solution (A).
- Fluorosurfactant solid content concentration 10% by mass
- polyester resins are filtered through a filter medium made of a sintered stainless steel (nominal filtration accuracy of 10 ⁇ m particles, 95% cut), laminated in a three-layer confluence block, extruded into a sheet form from a die, and then electrostatically
- the film was wound around a casting drum having a surface temperature of 30 ° C. using an applied casting method, and solidified by cooling to obtain an unstretched film.
- the discharge amount of each extruder was adjusted so that the ratio of the thicknesses of the A layer, the B layer, and the A layer was 1.5: 7: 1.5.
- this unstretched film 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 oriented PET film.
- Example 2 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (B) in Example 1. (Preparation of coating solution (B)) The following coating agent was mixed and the coating liquid (B) was produced.
- Fluorosurfactant solid content concentration 10% by mass
- Example 3 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (C) in Example 1. (Preparation of coating solution (C)) The following coating agent was mixed and the coating liquid (C) was produced.
- Example 4 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (D) in Example 1. (Preparation of coating liquid (D)) The following coating agent was mixed and the coating liquid (D) was produced.
- Example 5 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (E) in Example 1. (Preparation of coating liquid (E)) The following coating agent was mixed and the coating liquid (E) was produced.
- Fluorosurfactant solid content concentration 10% by mass) 1 part by mass
- Example 6 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (F) in Example 1. (Preparation of coating solution (F)) The following coating agent was mixed and the coating liquid (F) was produced.
- a laminated film was obtained in the same manner as in Example 2 except that PET (C) containing 0.035% by mass of 5 ⁇ m silica particles was supplied to the extruder 1 (for outer layer A layer).
- a laminated film was obtained in the same manner as in Example 2 except that PET (C) containing 0.010% by mass of 5 ⁇ m silica particles was supplied to the extruder 1 (for outer layer A layer).
- a laminated film was obtained in the same manner as in Example 2 except that PET (C) containing 0.025% by mass of 4 ⁇ m silica particles was supplied to the extruder 1 (for outer layer A layer).
- Example 10 In the same manner as in Example 2 except that PET (B) containing 0.025% by mass of silica particles having an average particle diameter of 2.5 ⁇ m was used for the B layer as the raw material polymer without providing the A layer. A laminated film was obtained.
- Example 11 A laminated film was obtained in the same manner as in Example 2 except that the thickness of the base film was 100 ⁇ m.
- Example 12 Example 2 except that the A layer was not provided and the polyethylene terephthalate (PET) resin pellet having an intrinsic viscosity of 0.62 dl / g and not containing particles for the B layer was used as the raw material polymer. 2 was used to obtain a laminated film.
- PET polyethylene terephthalate
- Comparative Example 1 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (G) in Example 1. (Preparation of coating solution (G)) The following coating agent was mixed and the coating liquid (G) was produced.
- Water 50 parts by weight Isopropanol 31 parts by weight Polycarbonate polyurethane resin aqueous solution (A-1) 17 parts by weight Particles 1 part by weight (silica sol having an average particle size of 40 nm, solid content concentration 40% by weight) Fluorosurfactant (solid content concentration 10% by mass) 1 part by mass
- Comparative Example 2 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (H) in Example 1. (Preparation of coating solution (H)) The following coating agent was mixed and the coating liquid (H) was produced.
- Comparative Example 3 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (I) in Example 1. (Preparation of coating liquid (I)) The following coating agent was mixed to prepare a coating liquid (I).
- Polyether-based polyurethane resin aqueous solution (A-4) 10 parts by weight
- Resin-containing oxazoline group aqueous solution (B-1) 7 parts by weight particles 1 part by weight (silica sol having an average particle size of 40 nm, Solid content concentration 40% by mass)
- Fluorosurfactant solid content concentration 10% by mass
- Comparative Example 4 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (J) in Example 1. (Preparation of coating solution (J)) The following coating agent was mixed to prepare a coating solution (J).
- Comparative Example 5 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (K) in Example 1. (Preparation of coating solution (K)) The following coating agent was mixed to prepare a coating solution (K).
- Comparative Example 6 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (L) in Example 1. (Preparation of coating solution (L)) The following coating agent was mixed and the coating liquid (L) was produced.
- Comparative Example 7 A laminated film was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (M) in Example 1. (Preparation of coating solution (M)) The following coating agent was mixed and the coating liquid (M) was produced.
- Water 45 parts by weight Isopropanol 27 parts by weight Polycarbonate-based polyurethane resin aqueous solution (A-1) 1 part by weight Resin aqueous solution having an oxazoline group (B-1) 25 parts by weight particles 1 part by weight (silica sol having an average particle size of 40 nm, solid (Concentration 40% by mass) Fluorosurfactant (solid content concentration 10% by mass) 1 part by mass
- Comparative Example 8 The same as in Example 2 except that the coating solution (N) in which the water-soluble resin (B-1) having an oxazoline group was changed to an epoxy compound (Denacol EX-521, solid content concentration 100%, manufactured by Nagase ChemteX Corporation) was used. By the method, a laminated film was obtained.
- Comparative Example 9 In the same manner as in Example 2 except that the coating solution (O) in which the water-soluble resin (B) having an oxazoline group was changed to a melamine compound (Becamine M-3 solid content concentration: 60% by DIC) was used. A film was obtained.
- the laminated film of the present invention is excellent in initial adhesion and moisture and heat resistance.
- it since it has excellent initial adhesion to the optical functional layer and heat and heat resistance, it is mainly used in displays and the like, and is used as a hard coat film, an antireflection film using the film, a light diffusion sheet, a prismatic lens sheet, and a near infrared shielding film.
- It is suitable as a base film for optical functional films such as transparent conductive films and antiglare films.
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JP5342632B2 (ja) * | 2011-06-30 | 2013-11-13 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
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EP2796291B1 (en) * | 2011-12-21 | 2016-10-05 | Toray Industries, Inc. | Laminated film |
US9878523B2 (en) | 2013-03-29 | 2018-01-30 | Toray Industries, Inc. | Laminated film |
JPWO2021166881A1 (zh) * | 2020-02-20 | 2021-08-26 | ||
CN112250818A (zh) * | 2020-09-27 | 2021-01-22 | 长春一汽富维东阳汽车塑料零部件有限公司 | 一种可重复利用水性聚氨酯遮蔽材料及其制备方法 |
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JPH10237384A (ja) * | 1997-02-27 | 1998-09-08 | Sanyo Chem Ind Ltd | 金属蒸着用下塗り剤組成物 |
JP2005082671A (ja) * | 2003-09-08 | 2005-03-31 | Toppan Printing Co Ltd | 塗工フィルム及び反射用シート |
WO2006057382A1 (ja) * | 2004-11-29 | 2006-06-01 | Toyo Boseki Kabushiki Kaisha | 積層熱可塑性樹脂フィルムおよび積層熱可塑性樹脂フィルムロール |
JP2009143226A (ja) * | 2007-11-22 | 2009-07-02 | Toyobo Co Ltd | 光学用易接着性ポリエステルフィルム及び光学用積層ポリエステルフィルム |
WO2010001750A1 (ja) * | 2008-07-03 | 2010-01-07 | 東洋紡績株式会社 | 光学用易接着性ポリエステルフィルム |
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JP2011136481A (ja) * | 2009-12-28 | 2011-07-14 | Toyobo Co Ltd | 易接着性熱可塑性樹脂フィルム |
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JP4623239B1 (ja) | 2011-02-02 |
KR101699997B1 (ko) | 2017-01-25 |
TW201129473A (en) | 2011-09-01 |
TWI399291B (zh) | 2013-06-21 |
CN102725336A (zh) | 2012-10-10 |
KR20120080194A (ko) | 2012-07-16 |
JP2011093301A (ja) | 2011-05-12 |
CN102725336B (zh) | 2014-01-08 |
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