WO2013058316A1 - 塗布フィルム - Google Patents
塗布フィルム Download PDFInfo
- Publication number
- WO2013058316A1 WO2013058316A1 PCT/JP2012/076947 JP2012076947W WO2013058316A1 WO 2013058316 A1 WO2013058316 A1 WO 2013058316A1 JP 2012076947 W JP2012076947 W JP 2012076947W WO 2013058316 A1 WO2013058316 A1 WO 2013058316A1
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- WO
- WIPO (PCT)
- Prior art keywords
- film
- polyester
- coated
- thickness
- coating
- Prior art date
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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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- 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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- 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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
Definitions
- the present invention relates to a coated film, such as a long-time heat treatment at 180 ° C., a sputtering process under a high tension condition, and a durability test in a high-temperature and high-humidity atmosphere.
- the present invention relates to a coated film having a characteristic that the increase in film haze is as small as possible even after undergoing a process under various conditions, and having excellent optical characteristics and visibility even after being processed as a product for an optical member.
- the present invention relates to a coating film suitable for optical applications where high transparency is required with emphasis on so-called visibility, which is transmitted through light, for example, for touch panels.
- capacitive touch panels there are two types: surface type and projection type.
- the surface type consists of three layers: a cover, a transparent conductive layer, and a glass substrate.
- the projection type consists of a glass or plastic film, a transparent electrode layer, and a substrate layer equipped with an IC that performs arithmetic processing. Is done.
- the transparent conductive laminate In the manufacturing process of the transparent conductive laminate, it is generally heat processed.
- an ITO film is formed by a sputtering method, and then heat treatment is performed at 150 ° C. for crystallization (Patent Document 1), or in the production of a conductive laminated film.
- Patent Document 2 When it is allowed to stand at 150 ° C. for 1 hour for low heat shrinkage treatment (Patent Document 2), or when processing a transparent conductive film, heat treatment at about 150 ° C. may be required to print a silver paste or the like. Yes (Patent Document 3).
- Patent Document 4 a technique for suppressing oligomer precipitation by applying a coating layer on a polyester film substrate has been proposed (Patent Document 4).
- problems such as peeling of the coating layer may occur due to contact, rubbing, etc. between the conveying guide roll and the polyester film surface in the processing step.
- the oligomer precipitation of the part cannot be suppressed, and when the oligomer precipitation amount itself of the polyester base material is reduced, the oligomer precipitation amount is further increased in combination with a coating layer having a function of suppressing oligomer precipitation.
- a technique for suppressing oligomer precipitation of the polyester film base material itself is strongly demanded because it can be reduced.
- the present invention has been made in view of the above circumstances, and its solution is to provide a coated film that is excellent in optical properties and visibility even after being processed as a product for optical members, and is particularly suitable for optical applications. Specifically, for example, harsh conditions such as a long-time heat treatment at 180 ° C., a sputtering process under a high tension condition, and a durability test in a high-temperature and high-humidity atmosphere.
- An object of the present invention is to provide a coated film that can suppress an increase in film haze even after undergoing the steps below and is excellent in optical characteristics and visibility even after being processed as a product for an optical member.
- the gist of the present invention is a coated film in which a coated layer is provided on one side of a polyester film having a thickness of 10 to 200 ⁇ m, and the above polyester film has a laminated structure of at least three layers, and both outermost layers. Is a layer having a thickness of 4 ⁇ m or more and comprising 80% by weight or more of polyester having an oligomer content of 0.5% by weight or less.
- the effect that the film haze difference before and after heat treatment (180 ° C., 90 minutes) is 0.4% or less can be obtained.
- the effect that the amount of oligomer (cyclic trimer) extracted from the surface of the coating layer after heat treatment (180 ° C., 150 minutes) is 3.0 mg / m 2 or less is also obtained. Therefore, for example, after passing through a process under harsh conditions such as a long-time heat treatment at 180 ° C., a sputtering process under a high tension condition, and a durability test under a high temperature and high humidity atmosphere. Even so, it is possible to provide a coated film having a small film haze and excellent optical characteristics and visibility.
- the coated film of the present invention has a configuration in which a coated layer is provided on one side of a polyester film.
- the above-mentioned polyester film is a polyester film extruded by a so-called extrusion method that is melt-extruded from an extrusion die, and is a film oriented in the biaxial directions of the vertical direction and the horizontal direction as necessary.
- Polyester can be obtained by polycondensation of aromatic dicarboxylic acid and aliphatic glycol.
- aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid
- aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
- Typical polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalene dicarboxylate (PEN) and the like.
- the polyester may be a homopolyester or a copolyester.
- a copolyester it is a copolymer containing 30 mol% or less of the third component.
- the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and a kind of oxycarboxylic acid (for example, P-oxybenzoic acid).
- glycol component examples include one or more types such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanone neopentyl glycol.
- the thickness of the polyester film is 10 to 200 ⁇ m.
- the thickness is less than 10 ⁇ m, when forming an ITO film by a sputtering method in order to form a transparent conductive film, the film strength is lost to the processing tension, wrinkles occur, and a normal transparent conductive film may not be formed. is there.
- it exceeds 200 ⁇ m the film becomes too stiff and the writing effect due to the cushioning effect of the adhesive layered on the coating film when finished into the final touch panel product is reduced, or the responsiveness of the touch panel is reduced. Such a problem may occur.
- the sheet flexibility of the sheet forming the transparent conductive film sheet (laminated transparent conductive film) formed by bonding the film-film after forming the transparent conductive film on the coated film is impaired.
- the thickness of the reester film is preferably 10 to 80 ⁇ m, more preferably 10 to 60 ⁇ m.
- the above polyester film has a laminated structure of at least three layers, and both outermost layers are composed of 80% by weight or more of polyester having an oligomer (cyclic trimer) content of 0.5% by weight or less. If the above conditions are not satisfied, under severe conditions such as long-time heat treatment at 150 ° C, sputtering process under high tension, durability test under high temperature and high humidity atmosphere, etc. When a coated film is used in this processing step, the film haze increases greatly, and after processing, it may become unsuitable for an optical member in terms of optical characteristics or visibility.
- the thickness of the polyester layers of both outer layers is 4 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 6 ⁇ m or more.
- the thickness of the polyester layer constituting both outer layers is less than 4 ⁇ m, the desired oligomer precipitation sealing effect may not be obtained.
- the polyester having a low oligomer content when used, particularly when the polyester layer is laminated with a thickness of 4 ⁇ m or more, the film haze of the obtained film itself can be suppressed to a lower level, which is highly transparent. Suitable for optical applications where a film is required.
- particles may be blended mainly for the purpose of imparting slipperiness and preventing the occurrence of scratches in each step.
- the kind of the particle to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness.
- Specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid.
- Examples of the particles include magnesium, kaolin, aluminum oxide, and titanium oxide.
- the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used.
- thermosetting urea resins examples include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, benzoguanamine resins, and the like.
- precipitated particles in which a part of a metal compound such as a catalyst is precipitated and finely dispersed during the polyester production process.
- the shape of the particles is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Further, the hardness, specific gravity, color and the like are not particularly limited. These series of particles may be used in combination of two or more as required.
- the average particle diameter of the particles is not particularly limited, but is usually 0.02 ⁇ m to 3 ⁇ m, preferably 0.02 ⁇ m to 2.5 ⁇ m, and more preferably 0.02 ⁇ m to 2 ⁇ m.
- the average particle diameter exceeds 3 ⁇ m, the degree of roughening of the film surface becomes too large and the film may become hazy.
- the particle content is usually 0.0005 to 0.5% by weight, preferably 0.001 to 0.3% by weight.
- the slipperiness of the film may be insufficient, resulting in poor appearance such as scratches during film processing.
- the transparency of a film may be inadequate.
- the method of blending the particles with the polyester is not particularly limited, and a known method can be adopted.
- it can be added at any stage of producing the polyester, but it is preferably added as a slurry dispersed in ethylene glycol or the like at the stage of esterification or before the start of the polycondensation reaction after completion of the transesterification 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 blending of dried particles and a polyester raw material using a kneading extruder is done by methods.
- the coating layer of the coating film of the present invention is provided for the purpose of improving the adhesion with the layer processed on it, improving the slipping property during processing, and the like.
- the coating layer may be provided by in-line coating, which treats the film surface during the process of forming the polyester film, or may employ offline coating which is applied outside the system on the film once produced. Since the coating can be performed simultaneously with the film formation, the production can be handled at a low cost, and therefore in-line coating is preferably used.
- the polyester film may be subjected to surface treatment such as corona treatment or plasma treatment in advance. The surface treatment may be single-sided or double-sided.
- the in-line coating is not limited to the following, but for example, in the sequential biaxial stretching, the coating treatment can be performed particularly before the lateral stretching after the longitudinal stretching is finished.
- the coating layer can be applied simultaneously with the film formation, and the coating layer can be processed at a high temperature in the heat treatment step of the stretched polyester film, so various surface functions that can be formed on the coating layer. Performances such as adhesion to the layer and heat and humidity resistance can be improved.
- the thickness of an application layer can also be changed with a draw ratio, and uniform coating can be performed with a thin film. That is, a suitable coated film can be produced by in-line coating, particularly coating before stretching.
- Coating layer is additive such as surfactant, antifoaming agent, coatability improver, thickener, organic lubricant, organic particles, inorganic particles, antioxidant, UV absorber, foaming agent, dye, pigment, etc. May be contained. These additives may be used alone or in combination of two or more as necessary.
- the coating liquid may contain a small amount of an organic solvent for the purpose of improving dispersion in water or improving the film-forming performance. It is necessary to use the organic solvent as long as it is soluble in water.
- the organic solvent include aliphatic or alicyclic alcohols such as n-butyl alcohol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol and methyl alcohol, glycols such as propylene glycol, ethylene glycol and diethylene glycol, n-butyl cellosolve, Glycol derivatives such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate and amyl acetate, ketones such as methyl ethyl ketone and acetone, and amides such as N-methylpyrrolidone Can be mentioned.
- heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination as necessary.
- the coating material may be either water-based and / or solvent-based for offline coating, but is preferably water-based or water-dispersed for in-line coating.
- the solid content concentration of the coating solution is not particularly limited, but is usually 0.3 to 65% by weight, preferably 0.5 to 30% by weight, and more preferably 1 to 20% by weight. When the concentration is too high or too low than these ranges, it may be difficult to provide a coating layer having a thickness necessary for sufficiently expressing the function.
- the thickness of the coating layer (after drying) is usually 0.003 to 1.5 ⁇ m, preferably 0.01 to 0.5 ⁇ m, and more preferably 0.01 to 0.3 ⁇ m. If the thickness of the coating layer is less than 0.003 ⁇ m, sufficient performance may not be obtained. On the other hand, if the thickness exceeds 1.5 ⁇ m, blocking between films may occur easily.
- Examples of the method of applying the coating solution to the polyester film include a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, or these as shown in “Coating Method” by Yuji Harasaki, Tsuji Shoten, published in 1979. Other coating devices can be used.
- the blending amount of the particles in the coating solution is usually 0.5 to 10% by weight, preferably 1 to 5% by weight.
- the blending amount is less than 0.5% by weight, the blocking resistance may be insufficient.
- the blending amount exceeds 10% by weight, the transparency of the film is hindered and the image sharpness tends to decrease.
- inorganic particles examples include silicon dioxide, alumina, zirconium oxide, kaolin, talc, calcium carbonate, titanium oxide, barium oxide, carbon black, molybdenum sulfide, and antimony oxide.
- silicon dioxide is easy to use because it is inexpensive and has various particle sizes.
- organic particles examples include polystyrene or polyacrylate polymethacrylate in which a crosslinked structure is achieved by a compound containing two or more carbon-carbon double bonds in one molecule (for example, divinylbenzene).
- the above inorganic particles and organic particles may be surface-treated.
- the surface treatment agent include a surfactant, a polymer as a dispersant, a silane coupling agent, a titanium coupling agent, and the like.
- the content of the particles in the coating layer is usually 10% by weight or less, preferably 5% by weight or less, from the viewpoint of not inhibiting the transparency.
- the coating layer may contain an antifoaming agent, a coating property improver, a thickener, an antioxidant, an ultraviolet absorber, a foaming agent, a dye, a pigment and the like.
- the film haze of the coated film of the present invention is usually 1.3% or less, preferably 1.1% or less, and more preferably 1.0% or less.
- the film haze exceeds 1.3%, the transparency is lowered.
- the film haze is used as an optical display member, there may be a problem that the visibility is lowered.
- the coated film of the present invention has an effect that the film haze change rate ( ⁇ H) before and after heat treatment (180 ° C., 90 minutes) is 0.4% or less.
- the amount of oligomer (cyclic trimer) extracted from the surface of the coating layer after heat treatment (180 ° C., 150 minutes) is 3.0 mg / m 2 or less.
- Such an effect is particularly important when a high degree of transparency is required even after being exposed to a high temperature atmosphere for a long time, such as for a touch panel. Therefore, the coated film of the present invention is suitable for applications that require high visibility, such as for touch panels.
- a colorant, a conductive material, etc. may be added within a range that does not impair the gist of the present invention. May form a functional multilayer thin film for the purpose of electromagnetic shielding.
- thermoplastic resins such as polyethylene naphthalate, polytrimethylene terephthalate, etc. can be mixed within a range that does not impair the gist of the present invention.
- Average particle diameter (d50) The particle size was measured by a sedimentation method based on Stokes' resistance law using a centrifugal sedimentation type particle size distribution analyzer “SA-CP3 type” manufactured by Shimadzu Corporation.
- Preparation of the standard sample was performed by accurately weighing the preliminarily collected oligomer (cyclic trimer) and dissolving it in the accurately weighed DMF.
- concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg / ml.
- Polyester layer thickness on coated film The film piece was fixed with an epoxy resin and then cut with a microtome, and the cross section of the film was observed with a transmission electron micrograph. Two of the cross-sections are observed in parallel with the film surface, and the interface is observed by light and dark. The distance between the two interfaces and the film surface was measured from 10 photographs, and the average value was taken as the thickness.
- Rate of change in film haze before and after heat treatment ( ⁇ H):
- a coating solution having the following coating solution composition is applied to the surface opposite to the surface provided with the coating layer.
- the obtained film was treated under predetermined heat treatment conditions (180 ° C., 90 minutes), and then the film haze was measured in the same manner as in the item (5).
- the film haze change rate ( ⁇ H) before and after the heat treatment was determined by the following formula.
- Film haze change rate (.H:%) (film haze after heat treatment) ⁇ (film haze before heat treatment)
- SRa Surface roughness of coated film:
- a non-contact surface measurement system (“Micromap 512” manufactured by Micromap) using direct phase detection interferometry, a so-called two-beam interference method utilizing Michelson's interference, a coated surface and a non-coated surface (coated layer)
- the surface roughness (SRa) of the film surface on which no is provided is measured.
- the measurement wavelength was 554 nm
- the objective lens was 20 ⁇
- the 20 ° field of view was measured, and the average value was adopted.
- Amount of ester cyclic trimer extracted from the coating layer surface of the coating film after the heat treatment The coating film is heated in air at 180 ° C. for 150 minutes. Thereafter, the heat-treated coated film is brought into close contact as much as possible with the inner surface of a box having a top and width of 10 cm and a height of 3 cm to open a box shape. At this time, the coating layer surface is set inside. Next, 4 ml of DMF (dimethylformamide) is placed in the box prepared by the above method and left for 3 minutes, and then DMF is recovered.
- DMF dimethylformamide
- the recovered DMF is supplied to liquid chromatography (“LC-7A” manufactured by Shimadzu Corporation) to determine the amount of oligomer (cyclic trimer) in DMF, and this value is divided by the film area in contact with DMF.
- the amount of the film surface ester cyclic trimer (mg / m 2 ).
- the amount of oligomer (cyclic trimer) in DMF was determined from the peak area ratio between the standard sample peak area and the measured sample peak area (absolute calibration curve method).
- the standard sample preparation method and the liquid chromatograph conditions were the same as in item (3).
- Film-film adhesion evaluation (practical property substitution evaluation): The following acrylic pressure-sensitive adhesive composition was applied on a coating layer of a sample film heated at 150 ° C. for 2 hours, and after heat treatment at 100 ° C. for 5 minutes, a pressure-sensitive adhesive layer having a thickness of 150 ⁇ m was obtained. Next, the film was reciprocated once by using a 2 kg metal roller on the exposed pressure-sensitive adhesive layer side, and after bonding, the workability was determined according to the following criteria.
- ⁇ Acrylic adhesive composition> (Monomer composition) 2-ethylhexyl acrylate 70% by weight 2-methoxyethyl acrylate 29% by weight 4-hydroxybutyl acrylate 1% by weight
- To 100 parts by weight of the monomer composition 0.1 part of “Coronate L” manufactured by Nippon Polyurethane was added to obtain an acrylic pressure-sensitive adhesive layer forming composition.
- Film-film sheet flexibility evaluation (practical property substitution evaluation): Using a sample film of A4 cut size, it was folded in a loop shape so that the film surface provided with the coating layer was the outer surface, and the film was crushed by applying a load from directly above the obtained loop-shaped film. Using the repulsive force, the firmness of the film was determined according to the following criteria. ⁇ Criteria> A: The stiffness of the film is weak and the sheet flexibility is good (a level that causes no problem in practical use). B: The film is strong and the sheet flexibility is poor (practically problematic level).
- the obtained polyester (A) had an intrinsic viscosity of 0.65 and an oligomer (cyclic trimer) content of 0.97% by weight.
- Polyester (A) is pre-crystallized at 160 ° C. in advance, and then solid-phase polymerized in a nitrogen atmosphere at a temperature of 220 ° C., limiting viscosity 0.75, oligomer (cyclic trimer) content 0.46% by weight. Polyester (B) was obtained.
- polyester (C) In the method for producing polyester (A), after adding 0.04 part of ethyl acid phosphate, 0.2 part of silica particles dispersed in ethylene glycol having an average particle diameter of 1.6 ⁇ m and 0.04 part of antimony trioxide are added. In addition, polyester (C) was obtained using the same method as the production method of polyester (A) except that the polycondensation reaction was stopped at the time corresponding to the intrinsic viscosity of 0.65. The obtained polyester (C) had an intrinsic viscosity of 0.65 and an oligomer (cyclic trimer) content of 0.82% by weight.
- the film was stretched 3.4 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then this longitudinally stretched film was guided to a tenter and stretched 4.3 times at 120 ° C. in the transverse direction.
- the film is rolled up on a roll and coated on one side with the coating solution prepared by the preparation method described below so that the film thickness is 0.1 ⁇ m after drying to obtain a coated film.
- a coated film having a thickness of 23 ⁇ m was obtained.
- the properties of the obtained coated film are shown in Table 1 below.
- Example 2 In Example 1, a coated film was obtained in the same manner as in Example 1 except that the thickness component ratio was changed to 4: 15: 4. The properties of the obtained coated film are shown in Table 1 below.
- Example 1 In Example 1, a coated film was obtained in the same manner as in Example 1 except that the thickness component ratio was changed to 3: 17: 3. The properties of the obtained coated film are shown in Table 1 below.
- Example 2 In Example 1, a coated film was obtained in the same manner as in Example 1 except that polyesters (B) and (C) were mixed in proportions of 70% and 30% as raw materials for the A layer, respectively. The properties of the obtained coated film are shown in Table 1 below.
- Example 4 In Example 1, a coated film was obtained in the same manner as in Example 1 except that 100% of polyester (C) was mixed as a raw material for the A layer. The properties of the obtained coated film are shown in Table 1 below.
- the coated film was obtained in the same manner as in Example 1 except that the thickness of the polyester film was changed to 5: 45: 2.5 and the thickness of the polyester film was changed to 50 ⁇ m.
- the characteristics of the obtained coated film are shown in Tables 2 and 3 below.
- the coated film of the present invention for example, a severe condition such as a long-time heat treatment at 180 ° C., a sputtering process under a high tension condition, a durability test in a high-temperature and high-humidity atmosphere, etc. Even after going through the steps below, the increase in film haze is as small as possible. Therefore, according to the present invention, it is possible to provide a coated film that is excellent in optical properties and visibility, and particularly suitable for optical applications, and its industrial value is high.
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Abstract
Description
ポリエステルに非相溶な他のポリマー成分および顔料を除去したポリエステル1gを精秤し、フェノール/テトラクロロエタン=50/50(重量比)の混合溶媒100mlを加えて溶解させ、30℃で測定した。
(株)島津製作所社製遠心沈降式粒度分布測定装置「SA-CP3型」を用いてストークスの抵抗則にもとづく沈降法によって粒子の大きさを測定した。
ポリエステル原料を約200mg秤量し、クロロホルム/HFIP(ヘキサフルオロ-2-イソプロパノル)の比率3:2の混合溶媒2mlに溶解させる。溶解後、クロロホルム20mlを追加した後、メタノール10mlを少しずつ加える。沈殿物を濾過により除去し、更に、沈殿物をクロロホルム/メタノールの比率2:1の混合溶媒で洗浄し、濾液・洗浄液を回収し、エバポレーターにより濃縮、その後、乾固させる。乾固物をDMF(ジメチルホルムアミド)25mlに溶解後、この溶液を液体クロマトグラフィー(島津製作所製「LC-7A」)に供給して、DMF中のオリゴマー量を求め、この値をクロロホルム/HFIP混合溶媒に溶解させたポリエステル原料量で割って、含有オリゴマー量(重量%)とする。DMF中のオリゴマー量は、標準試料ピーク面積と測定試料ピーク面積のピーク面積比より求めた(絶対検量線法)。
移動相A:アセトニトリル
移動相B:2%酢酸水溶液
カラム:三菱化学(株)製「MCI GEL ODS 1HU」
カラム温度:40℃
流速:1ml/分
検出波長:254nm
フィルム小片をエポキシ樹脂にて固定成形した後、ミクロトームで切断し、フィルムの断面を透過型電子顕微鏡写真にて観察した。その断面のうちフィルム表面とほぼ平行に2本、明暗によって界面が観察される。その2本の界面とフィルム表面までの距離を10枚の写真から測定し、平均値を厚みとした。
試料フィルムをJIS-K-7136に準じ、村上色彩技術研究所製ヘーズメーター「HM-150」により、フィルムヘーズ(%)を測定した。
試料フィルムにおいて、下記塗布液組成からなる塗布液を塗布層が設けられた面とは反対側の面に塗布する。その後、得られたフィルムを所定の熱処理条件(180℃、90分)で処理した後、(5)項と同様にして、フィルムヘーズを測定した。
<塗布液組成>
コルコート社製「コルコートP」
使用バー:♯3バー
乾燥条件:100℃ 1分間
その後、下記式により、熱処理前後におけるフィルムヘーズ変化率(・H)を求めた。
フィルムヘーズ変化率(・H:%)=(熱処理後のフィルムヘーズ)-(熱処理前のフィルムヘーズ)
直接位相検出干渉法、いわゆるマイケルソンの干渉を利用した2光束干渉法を用いた、非接触表面計測システム(マイクロマップ社製「Micromap512)」により、試料フィルムの塗布面および反塗布面(塗布層が設けられていないフィルム面)の表面粗さ(SRa)を計測した。なお、測定波長は554nmとし、対物レンズは20倍を用いて、20°視野計測し、その平均値を採用した。
塗布フィルムにおいて、塗布層とは反対側の面に、アルゴンガス95%と酸素ガス5%とからなる0.4Paの雰囲気下で、酸化インジウム95重量%、酸化スズ5重量%の焼結体材料を用いた反応性スパッタリング法により、厚み25nmのITO膜(透明導電性薄膜)を形成した。また、ITO膜は180℃×1時間の加熱処理により結晶化させた。得られたフィルムの透明性・視認性について、下記判定基準により、判定を行った。
<判定基準>
A:透明性・視認性、特に良好(実用上、問題ないレベル)
B:透明性・視認性良好(実用上、問題ないレベル)
C:透明性・視認性不良(実用上、問題あるレベル)
D:透明性・視認性が特に不良(実用上、問題あるレベル)
上記(8)項記載の方法により、スパッタリング加工時に、加工部分のフィルムの平面性を目視による官能評価を行い、下記判定基準により、判定を行なった。
<判定基準>
A:フィルムの加工部分が幅方向全体にわたりうねり、シワの発生なく良好に加工できている(実用上、問題ないレベル)。
B:フィルムの加工部分にうねり、シワ等の発生し、幅方向で均一に加工できていない(実用上、問題あるレベル)。
新タック化成社のノンキャリアフィルム「KF4#50」の軽剥離側セパを剥がし、塗布フィルムの塗布層面に貼り合わせた。次に重剥離側セパを剥がし、日本板硝子社製板ガラス(「フロート板ガラス(5mm厚み)」)に貼り合せ塗布フィルム/粘着層/ガラス構成体を作成した。得られた構成体を塗布フィルム側からボールペンのペン先を接触させ、その粘着剤のクッション効果について、下記判定基準により、判定を行った。
<判定基準>
A:ペンを接触している間、接触した箇所に粘着層が追従する。接触をやめると粘着層の追従変形が元に戻る(クッション効果を感じることができる)。
B:ペンを接触させても粘着層が変形せず、クッション効果が感じることができない
Aは、実用上、問題ないレベルである。
DMF中のオリゴマー(環状三量体)量は、標準試料ピーク面積と測定試料ピーク面積のピーク面積比より求めた(絶対検量線法)。なお、標準試料の作成方法および液体クロマトグラフの条件は(3)項と同様に行なった。
上記(8)項記載の方法において、ITO膜の加熱処理条件を150℃×2時間に変更し、判定基準を下記のように変更したこと以外は、上記(8)項と同様に行った。
150℃、2時間加熱した試料フィルムの塗布層上に下記アクリル系粘着剤組成物を塗布し、100℃、5分間熱処理した後、厚みが150μmの粘着剤層を得た。次に露出している粘着剤層側にフィルムを2kgの金属ローラーを用いて、1往復させ、貼り合わせた後、作業性に関して下記判定基準により、判定を行った。
<アクリル系粘着剤組成物>
(モノマー配合組成)
アクリル酸2-エチルヘキシル 70重量%
アクリル酸2-メトキシエチル 29重量%
アクリル酸4-ヒドロキシブチル 1重量%
上記モノマー組成100重量部に対して、日本ポリウレタン製「コロネートL」を0.1部添加し、アクリル系粘着剤層形成用組成物を得た。
<判定基準>
A:シワが入らず特に良好(実用上、問題ないレベル)。
B:シワが入り不良(実用上、問題あるレベル)。
A4カット判サイズの試料フィルムを用いて、塗布層が設けられたフィルム面が外面になるようにループ状に折り曲げ、得られたループ状フィルムの真上から荷重を加えて押しつぶした際のフィルムの反発力を用いて、フィルムのコシの強弱に関して、下記判定基準により判定を行った。
<判定基準>
A:フィルムのコシが弱くシート柔軟性が良好(実用上、問題ないレベル)。
B:・フィルムのコシが強くシート柔軟性が不良(実用上、問題あるレベル)。
[ポリエステル(A)の製造方法]
テレフタル酸ジメチル100重量部とエチレングリコール60重量部とを出発原料とし、触媒として酢酸マグネシウム・四水塩0.09重量部を反応器にとり、反応開始温度を150℃とし、メタノールの留去と共に徐々に反応温度を上昇させ、3時間後に230℃とした。4時間後、実質的にエステル交換反応を終了させた。この反応混合物にエチルアシッドフォスフェート0.04部を添加した後、三酸化アンチモン0.04部を加えて、4時間重縮合反応を行った。すなわち、温度を230℃から徐々に昇温し280℃とした。一方、圧力は常圧より徐々に減じ、最終的には0.3mmHgとした。反応開始後、反応槽の攪拌動力の変化により、極限粘度0.63に相当する時点で反応を停止し、窒素加圧下ポリマーを吐出させた。得られたポリエステル(A)の極限粘度は0.65、オリゴマー(環状三量体)の含有量は0.97重量%であった。
ポリエステル(A)を、予め160℃で予備結晶化させた後、温度220℃の窒素雰囲気下で固相重合し、極限粘度0.75、オリゴマー(環状三量体)含有量0.46重量%のポリエステル(B)を得た。
ポリエステル(A)の製造方法において、エチルアシッドフォスフェート0.04部を添加後、平均粒子径1.6μmのエチレングリコールに分散させたシリカ粒子を0.2部、三酸化アンチモン0.04部を加えて、極限粘度0.65に相当する時点で重縮合反応を停止した以外は、ポリエステル(A)の製造方法と同様の方法を用いてポリエステル(C)を得た。得られたポリエステル(C)は、極限粘度0.65、オリゴマー(環状三量体)含有量0.82重量%であった。
ポリエステル(B)、(C)を、それぞれ85%、15%の割合で混合した混合原料をA層の原料とし、ポリエステル(A)100%の原料をB層の原料として、2台の押出機に各々を供給し、各々285℃で溶融した後、A層を最外層(表層)、B層を中間層として、40℃に冷却したキャスティングドラム上に、2種3層(A/B/A)で、厚み構成比がA:B:A=6:11:6になるように共押出し冷却固化させて無配向シートを得た。
次いで、ロール周速差を利用してフィルム温度85℃で縦方向に3.4倍延伸した後、この縦延伸フィルムをテンターに導き、横方向に120℃で4.3倍延伸し、225℃で熱処理を行った後、フィルムをロール上に巻き上げ片面に下記に記載の調製法で作成した塗布液を乾燥後膜厚で0.1μmとなるように塗布し、塗布フィルムとした際のポリエステルフィルムの厚みが23μmの塗布フィルムを得た。得られた塗布フィルムの特性を下記表1に示す。
以下のA、B、C、D、Eの化合物をそれぞれ30、10、40、10、10重量部となるように混合した。
・4級アンモニウム塩基含有ポリマー(A):
2-ヒドロキシ3-メタクリルオキシプロピルトリメチルアンモニウム塩ポリマー
対イオン:メチルスルホネート 数平均分子量:30000
・ポリエチレングリコール含有アクリレートポリマー(B):
ポリエチレングリコール含有モノアクリレートポリマー 数平均分子量:20000
・架橋剤(C):
メラミン架橋剤(DIC社製:ベッカミン「MAS」)
・粒子(D):
アルミナ表面変性コロイダルシリカ(平均粒径:50nm)
・バインダー(E):
ポリビニルアルコール(けん化度88モル%、重合度500)
実施例1において、厚み構成比を4:15:4に変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表1に示す。
実施例1において、厚み構成比を3:17:3に変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表1に示す。
実施例1において、A層の原料としてポリエステル(B)、(C)を、それぞれ70%、30%の割合で混合したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表1に示す。
実施例1において、厚み構成比をA:B:A=4:1:4にし、塗布フィルムとした際のポリエステルフィルムの厚みを9μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表1に示す。
実施例1において、A層の原料としてポリエステル(C)を100%の割合で混合したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表1に示す。
実施例1において、厚み構成比をA:B:A=7.0:36:7.0にし、塗布フィルムとした際のポリエステルフィルムの厚みを50μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
実施例1において、厚み構成比をA:B:A=6.0:38:6.0にし、塗布フィルムとした際のポリエステルフィルムの厚みを50μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
実施例1において、厚み構成比をA:B:A=4.0:42:4.0にし、塗布フィルムとした際のポリエステルフィルムの厚みを50μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
実施例1において、厚み構成比をA:B:A=7.0:86:7.0にし、塗布フィルムとした際のポリエステルフィルムの厚みを100μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
実施例1において、厚み構成比をA:B:A=7.0:111:7.0にし、塗布フィルムとした際のポリエステルフィルムの厚みを125μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
実施例1において、厚み構成比をA:B:A=7.0:174:7.0にし、塗布フィルムとした際のポリエステルフィルムの厚みを188μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
実施例1において、厚み構成比をA:B:A=2.5:45:2.5にし、塗布フィルムとした際のポリエステルフィルムの厚みを50μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
実施例1において、上記ポリエステル(A)、(C)を、それぞれ84重量%、16重量%の割合で混合した混合原料をA層の原料とし、厚み構成比をA:B:A=2.5:45:2.5にし、塗布フィルムとした際のポリエステルフィルムの厚みを50μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
実施例1において、厚み構成比をA:B:A=7.0:236:7.0にし、塗布フィルムとした際のポリエステルフィルムの厚みを250μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
実施例1において、(A)層のポリエステルを(C)=100%にし、塗布フィルムとした際のポリエステルフィルムの厚みを50μmに変更したこと以外は、実施例1と同様の方法で塗布フィルムを得た。得られた塗布フィルムの特性を下記表2及び3に示す。
Claims (3)
- 厚み10~200μmのポリエステルフィルムの片面に塗布層が設けられた塗布フィルムであって、上記のポリエステルフィルムは、少なくとも3層以上の積層構造を有し、両最表層がオリゴマー含有量0.5重量%以下のポリエステル80重量%以上から構成された、厚み4μm以上の層であることを特徴とする塗布フィルム。
- 塗布層がフィルム製膜工程中に塗設されたものである請求項1記載の塗布フィルム。
- 光学用途に使用される請求項1又は2に記載の塗布フィルム。
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JPH11300918A (ja) * | 1998-04-24 | 1999-11-02 | Toray Ind Inc | 易接着性ポリエステルフィルム |
JP2009269173A (ja) * | 2008-04-30 | 2009-11-19 | Toyobo Co Ltd | 接着性改質基材フィルムおよびハードコートフィルム |
JP2010234673A (ja) * | 2009-03-31 | 2010-10-21 | Toray Ind Inc | ポリエステルフィルム |
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