WO2012081438A1 - Film de polyester feuilleté - Google Patents

Film de polyester feuilleté Download PDF

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Publication number
WO2012081438A1
WO2012081438A1 PCT/JP2011/078075 JP2011078075W WO2012081438A1 WO 2012081438 A1 WO2012081438 A1 WO 2012081438A1 JP 2011078075 W JP2011078075 W JP 2011078075W WO 2012081438 A1 WO2012081438 A1 WO 2012081438A1
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WO
WIPO (PCT)
Prior art keywords
polyester film
coating layer
coating
acid
polyester
Prior art date
Application number
PCT/JP2011/078075
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English (en)
Japanese (ja)
Inventor
加藤雄三
川崎泰史
藤田真人
Original Assignee
三菱樹脂株式会社
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Filing date
Publication date
Priority claimed from JP2010278881A external-priority patent/JP5489972B2/ja
Priority claimed from JP2010278880A external-priority patent/JP5489971B2/ja
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Publication of WO2012081438A1 publication Critical patent/WO2012081438A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a laminated polyester film, for example, a laminated polyester film that needs to reduce interference unevenness due to reflection of external light, such as a liquid crystal display, a plasma display panel, and organic electroluminescence.
  • polyester films have been used for touch panels, antireflection films, prism sheets, light diffusion sheets, electromagnetic wave shielding films, and the like, which are members of liquid crystal displays and plasma display panels.
  • the base film used for these members is required to have excellent transparency and visibility.
  • the polyester film excellent in transparency and a mechanical characteristic is generally used as a base material.
  • an easy-adhesion coating layer is generally provided as an intermediate layer, but the reflected light at the interface between the hard coat layer and the coating layer, and the coating layer When the reflected light at the interface between the polyester film and the polyester film interferes, rainbow pattern unevenness (interference unevenness) may occur.
  • the refractive index of the coating layer for reducing the interference unevenness is considered to be around the geometric mean of the refractive index of the biaxially stretched polyester film of the base material and the refractive index of the hard coat layer, and the refractive index around this can be adjusted. Ideal. Since the refractive index of the polyester film is high, it is generally necessary to design the coating layer with a high refractive index.
  • An example of improving interference unevenness by increasing the refractive index of the coating layer includes, for example, a method of blending a metal chelate compound or metal fine particles having a high refractive index in the coating layer.
  • the stability of the coating solution may not be sufficient depending on the combination due to the instability of the metal chelate in the aqueous solution, and there is a possibility of increasing the liquid replacement work when producing for a long time.
  • Patent Document 1 an example in which the refractive index is increased by a combination of a polyester resin and metal fine particles is also known, but in this case, there is a case where it is not possible to sufficiently exhibit the strict moist heat-resistant adhesion demanded in recent years (Patent Document). 2, 3).
  • the present case has been made in view of the above circumstances, and the problem to be solved is to reduce interference unevenness when various surface functional layers such as a hard coat are provided, and to have good visibility and surface function. It is providing the laminated polyester film excellent in adhesiveness with a layer.
  • the gist of the present invention is a laminated polyester film having a coating layer formed from a coating solution containing a polyester resin, titanium oxide particles, and an epoxy compound or an isocyanate compound on at least one surface of the polyester film.
  • the laminated polyester film of the present invention when various surface functional layers such as a hard coat are laminated, visibility is hardly impaired due to interference unevenness and the like, and a film having excellent adhesion to various surface functional layers is provided. And its industrial value is high.
  • the polyester film constituting the laminated polyester film in the present invention may have a single layer structure or a multilayer structure, and may have four or more layers as long as it does not exceed the gist of the present invention other than a two-layer or three-layer structure. It may be a multilayer, and is not particularly limited.
  • the polyester used in the present invention may be a homopolyester or a copolyester.
  • a homopolyester those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred.
  • the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid
  • examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
  • Typical polyester includes polyethylene terephthalate and the like.
  • examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (for example, p-oxybenzoic acid).
  • 1 type or 2 types or more are mentioned,
  • a glycol component 1 type or 2 types or more, such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexane dimethanol, neopentyl glycol, is mentioned.
  • the polyester polymerization catalyst is not particularly limited, and a conventionally known compound can be used. Examples thereof include an antimony compound, a titanium compound, a germanium compound, a manganese compound, an aluminum compound, a magnesium compound, and a calcium compound. Among these, a titanium compound is particularly preferable from the viewpoint of increasing the brightness of the film.
  • an ultraviolet absorber can be contained in order to improve the weather resistance of the film and prevent deterioration of the liquid crystal.
  • the ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays and can withstand the heat applied in the production process of the polyester film.
  • an organic ultraviolet absorber there are an organic ultraviolet absorber and an inorganic ultraviolet absorber, and an organic ultraviolet absorber is preferable from the viewpoint of transparency.
  • an organic type ultraviolet absorber For example, a cyclic imino ester type, a benzotriazole type, a benzophenone type etc. are mentioned. From the viewpoint of durability, a cyclic imino ester type and a benzotriazole type are more preferable. It is also possible to use two or more ultraviolet absorbers in combination.
  • particles can 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 include inorganic particles such as magnesium, kaolin, aluminum oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin.
  • precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process can also be used.
  • the shape of the particles to be used 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. Moreover, there is no restriction
  • the average particle size of the particles used is usually in the range of 0.01 to 3 ⁇ m. If the average particle size is less than 0.01 ⁇ m, the slipperiness may not be sufficiently imparted, or the particles may be aggregated to make the dispersibility insufficient, thereby reducing the transparency of the film. On the other hand, when the thickness exceeds 5 ⁇ m, the surface roughness of the film becomes too rough, which may cause problems when various surface functional layers such as a hard coat layer are formed in a subsequent process.
  • the particle content in the polyester layer is less than 5% by weight, preferably in the range of 0.0005 to 3% by weight.
  • the transparency of the film becomes high and the film becomes a good film, but the slipperiness may be insufficient. There are cases where improvement is required. Further, when the particle content exceeds 5% by weight, the transparency of the film may be insufficient.
  • the method for adding particles to the polyester layer is not particularly limited, and a conventionally known method can be adopted.
  • it can be added at any stage for producing the polyester constituting each layer, but it is preferably added after completion of esterification or transesterification.
  • 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.
  • antioxidants In addition to the above-mentioned particles, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments, and the like can be added to the polyester film in the present invention as necessary. .
  • the thickness of the polyester film in the present invention is not particularly limited as long as it can be formed as a film, but is usually in the range of 10 to 350 ⁇ m, preferably 25 to 250 ⁇ m.
  • a production example of the polyester film in the present invention will be specifically described, but is not limited to the following production examples. That is, a method of using the polyester raw material described above and cooling and solidifying a molten sheet extruded from a die with a cooling roll to obtain an unstretched sheet is preferable. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method and / or a liquid application adhesion method is preferably employed. Next, the obtained unstretched sheet is stretched in the biaxial direction. In that case, first, the unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine.
  • the stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times.
  • the film is stretched in the direction perpendicular to the first stretching direction.
  • the stretching temperature is usually 70 to 170 ° C.
  • the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. is there.
  • heat treatment is performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a biaxially oriented film.
  • a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.
  • the simultaneous biaxial stretching method can be adopted for the production of the polyester film constituting the laminated polyester film.
  • the simultaneous biaxial stretching method is a method in which the above-mentioned unstretched sheet is stretched and oriented simultaneously in the machine direction and the width direction in a state where the temperature is usually controlled at 70 to 120 ° C., preferably 80 to 110 ° C. Is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times in terms of area magnification. Subsequently, heat treatment is performed at a temperature of 170 to 250 ° C. under tension or under relaxation within 30% to obtain a stretched oriented film.
  • a conventionally known stretching method such as a screw method, a pantograph method, or a linear driving method can be employed.
  • the coating layer constituting the laminated polyester film in the present invention
  • it may be provided by in-line coating which treats the film surface during the process of forming a polyester film, or offline coating which is applied outside the system on a once produced film may be adopted. 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 in-line coating is not limited to the following, for example, in the sequential biaxial stretching, a coating treatment can be performed particularly before the lateral stretching after the longitudinal stretching is finished.
  • a coating treatment can be performed particularly before the lateral stretching after the longitudinal stretching is finished.
  • the coating layer is provided on the polyester film by in-line coating, it is possible to apply at the same time as the film formation, and the coating layer can be processed at a high temperature in the heat treatment process of the polyester film after stretching. Performances such as adhesion to various surface functional layers that can be formed on the layer and heat-and-moisture resistance can be improved.
  • the thickness of an application layer can also be changed with a draw ratio, and compared with offline coating, thin film coating can be performed more easily. That is, a film suitable as a polyester film can be produced by in-line coating, particularly coating before stretching.
  • a coating layer formed of a coating solution containing a polyester resin, titanium oxide particles, and an epoxy compound or an isocyanate compound on at least one surface of the polyester film.
  • the coating layer of the present invention is obtained by setting the refractive index of the surface functional layer such as the hard coat layer and the refractive index of the coating layer to the biaxially stretched polyester. It is designed to be close to the refractive index of the film. When these refractive indexes are in the vicinity of the same, reflection at each interface can be suppressed, so that interference unevenness is extremely reduced.
  • the polyester resin used for forming the coating layer of the present invention includes, for example, the following polyvalent carboxylic acid and polyvalent hydroxy compound as main components. That is, as the polyvalent carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutar Acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride,
  • the coating layer has a higher refractive index and hard coating.
  • Surface functional layer such as a layer, and since the interference unevenness can highly inhibited by adjusting the near equivalent polyester film substrate preferably has a naphthalene structure.
  • the polyvalent hydroxy compound include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2- Methyl-1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, ethylene glycol modified bisphenol A, diethylene glycol modified bisphenol A, diethylene glycol, triethylene glycol, polyethylene Glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylol
  • a polymer other than the above-described polyester resin is used in order to improve the adhesion with the surface functional layer, the coated surface, and the visibility and transparency when the surface functional layer is formed. It can also be used in combination.
  • polymer examples include acrylic resin, urethane resin, polyvinyl (polyvinyl alcohol, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches and the like. It is done.
  • Titanium oxide has a high refractive index and can increase the refractive index of the coating layer without impairing the transparency of the film.
  • the refractive index of the resin used in the coating layer is low, it is preferable to use titanium oxide particles having a high refractive index, and in order to obtain a coating layer having a refractive index close to that of the polyester film, refraction is required. It is preferable to use a rate of 1.7 or more. If necessary, two or more types of titanium oxide particles may be used in combination.
  • the average particle size of the titanium oxide particles used for forming the coating layer of the present invention is preferably 100 nm or less, more preferably 50 nm or less, still more preferably 25 nm or less, and particularly preferably 15 nm or less.
  • particles other than titanium oxide particles may be used in combination for forming the coating layer.
  • the epoxy compound used for the formation of the coating layer of the present invention is a compound having an epoxy group in the molecule.
  • epichlorohydrin and ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A and other hydroxyl groups such as Examples include condensates with amino groups, such as polyepoxy compounds, diepoxy compounds, monoepoxy compounds, and glycidylamine compounds.
  • polyepoxy compound examples include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane.
  • polyglycidyl ether and diepoxy compound examples include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether.
  • Polypropylene glycol diglycidyl ether polypropylene glycol diglycidyl ether, poly Examples of tetramethylene glycol diglycidyl ether and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N ′,-tetraglycidyl-m-. Examples include xylylenediamine, 1,3-bis (N, N-diglycidylamino) cyclohexane, and the reactants thereof. These may be used alone or in combination of two or more.
  • the isocyanate compound used for forming the coating layer of the present invention is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate.
  • isocyanates include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate.
  • Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate
  • Alicyclic isocyanates such as bets are exemplified.
  • polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination.
  • isocyanates aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.
  • the blocking agent When used in the state of blocked isocyanate, the blocking agent includes, for example, bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcohols such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol.
  • active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ⁇ -caprolactam and ⁇ -valerolactam , Amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, formaldehyde, acetal Examples include oxime compounds such as dooxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more.
  • the isocyanate compound in the present invention may be used alone or as a mixture or combination with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.
  • cross-linking agents other than the epoxy compound and the isocyanate compound can be used in combination in forming the coating layer of the present invention within a range not impairing the gist of the invention.
  • a crosslinking agent other than the epoxy compound and the isocyanate compound a known crosslinking agent can be used, and examples thereof include oxazoline compounds, melamine compounds, carbodiimide compounds, and silane coupling compounds.
  • the oxazoline compound used in the formation of the coating layer of the present invention is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferred, and an addition-polymerizable oxazoline group-containing monomer alone or another monomer Can be made by polymerization with.
  • Addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like, and one or a mixture of two or more thereof can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
  • the other monomer is not particularly limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer.
  • alkyl (meth) acrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, (Meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene
  • Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alky
  • the melamine compound used for forming the coating layer of the present invention is a compound having a melamine structure in the compound.
  • an alcohol is reacted with an alkylolated melamine derivative or an alkylolated melamine derivative to partially Alternatively, fully etherified compounds and mixtures thereof can be used.
  • alcohol used for etherification methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used.
  • a melamine compound either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used.
  • a product obtained by co-condensing urea or the like with a part of melamine can be used, and a catalyst can be used to increase the reactivity of the melamine compound.
  • the carbodiimide compound used for the formation of the coating layer of the present invention is a compound having a carbodiimide structure, and is a compound having one or more carbodiimide structures in the molecule, for better adhesion and the like. Further, a polycarbodiimide compound having two or more in the molecule is more preferable.
  • the carbodiimide compound can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used.
  • the diisocyanate compound is not particularly limited, and any of aromatic and aliphatic compounds can be used.
  • tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexa examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.
  • cross-linking agents are used in a design that improves the performance of the coating layer by reacting in the drying process or film forming process. It can be inferred that unreacted products of these crosslinking agents, compounds after the reaction, or mixtures thereof exist in the finished coating layer.
  • the coating layer has an antifoaming agent, a coating property improving agent, a thickener, an organic lubricant, an antistatic agent, an ultraviolet absorber, an antioxidant, foaming as necessary. Agents, dyes, pigments and the like may be contained.
  • the ratio of the polyester resin is usually in the range of 10 to 90% by weight, more preferably in the range of 40 to 85% by weight, based on the total amount of non-volatile components in the coating solution forming the coating layer constituting the laminated polyester film in the present invention. .
  • the refractive index of the coating layer can be easily adjusted, and interference unevenness can be easily suppressed when a surface functional layer such as a hard coat layer is provided.
  • adhesiveness with a surface functional layer may fall.
  • the content of titanium oxide particles is usually 5 to 60% by weight, preferably 8 to 50% by weight, and more preferably, as a ratio to the total nonvolatile components in the coating solution forming the coating layer constituting the laminated polyester film. It is in the range of 20 to 40% by weight.
  • the content of the titanium oxide particles is less than 5% by weight, the refractive index of the coating layer does not increase, so that interference unevenness may not be reduced, and when it exceeds 60% by weight, the haze of the coating layer may deteriorate.
  • the content of the epoxy compound is usually in the range of 1 to 50% by weight, preferably in the range of 5 to 30% by weight. More preferably, it is in the range of 10 to 20% by weight.
  • the amount is less than 1% by weight, there is a concern that the adhesion to a surface functional layer such as a hard coat layer may be lowered.
  • the amount exceeds 50% by weight, the haze of the coating layer may be deteriorated.
  • the content of the compound derived from the isocyanate compound is usually in the range of 1 to 50% by weight, preferably 5 to 30% by weight, based on the total amount of non-volatile components in the coating solution forming the coating layer constituting the laminated polyester film. More preferably, it is in the range of 10 to 20% by weight.
  • the amount is less than 1% by weight, there is a concern that the adhesion to a surface functional layer such as a hard coat layer may be lowered.
  • the amount exceeds 50% by weight the haze of the coating layer may be deteriorated.
  • the analysis of various components in the coating layer can be performed by analysis of TOF-SIMS, ESCA, fluorescent X-rays, and the like.
  • a coating layer When providing a coating layer by in-line coating, apply the above-mentioned series of compounds as an aqueous solution or water dispersion on a polyester film with a coating solution adjusted to a solid content concentration of about 0.1 to 50% by weight. It is preferable to produce a laminated polyester film. Moreover, in the range which does not impair the main point of this invention, a small amount of organic solvents may be contained in the coating liquid for the purpose of improving dispersibility in water, improving film-forming properties, and the like. Only one type of organic solvent may be used, or two or more types may be used as appropriate.
  • the thickness of the coating layer provided on the polyester film is in the range of 0.01 to 0.20 ⁇ m, more preferably 0.02 to 0.10 ⁇ m. If the coating amount is less than 0.01 ⁇ m, sufficient adhesion may not be obtained, and if it exceeds 0.20 ⁇ m, the appearance, transparency, and film blocking properties may be deteriorated.
  • a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating or the like can be used.
  • the drying and curing conditions for forming the coating layer on the polyester film are not particularly limited.
  • the coating layer is provided by off-line coating, usually at 80 to 200 ° C. for 3 to 40 seconds.
  • the heat treatment is preferably performed at 100 to 180 ° C. for 3 to 40 seconds as a guide.
  • the coating layer is provided by in-line coating, it is usually preferable to perform heat treatment at 70 to 280 ° C. for 3 to 200 seconds as a guide.
  • polyester film constituting the laminated polyester film in the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.
  • the coating layer in the present invention has a refractive index adjusted to be around the same as that of the base polyester film in order to suppress interference unevenness to a higher degree.
  • the absolute reflectance of the coating layer is in the range of 5.5 to 6.5%, preferably in the range of 5.6 to 6.4%, more preferably 5.7 at an arbitrary wavelength of 400 to 800 nm. It is in the range of ⁇ 6.3%. When the reflectance is out of this range, interference unevenness is increased when a surface functional layer such as a hard coat is provided on the coating layer, and the visibility may be lowered.
  • the polyester film of the present invention is generally provided with a surface functional layer such as a hard coat layer on the coating layer.
  • a surface functional layer such as a hard coat layer on the coating layer.
  • cured materials such as reactive silicon compounds, such as monofunctional (meth) acrylate, polyfunctional (meth) acrylate, and tetraethoxysilane.
  • reactive silicon compounds such as monofunctional (meth) acrylate, polyfunctional (meth) acrylate, and tetraethoxysilane.
  • a polymerization cured product of a composition containing an ultraviolet curable polyfunctional (meth) acrylate is particularly preferable.
  • composition containing an ultraviolet curable polyfunctional (meth) acrylate is not particularly limited.
  • the UV-curable polyfunctional (meth) acrylate is not particularly limited.
  • composition containing an ultraviolet curable polyfunctional (meth) acrylate are not particularly limited. Examples thereof include inorganic or organic fine particles, polymerization initiators, polymerization inhibitors, antioxidants, antistatic agents, dispersants, surfactants, light stabilizers and leveling agents. Moreover, when making it dry after film forming in the wet-coating method, arbitrary amounts of solvents can be added.
  • the hard coat layer when an organic material is used, a general wet coat method such as a roll coat method or a die coat method is employed.
  • the formed hard coat layer can be subjected to a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams as necessary.
  • the obtained film is visually observed under the three-wavelength type fluorescent lamp for interference unevenness on the coating layer side, ⁇ when the interference unevenness cannot be confirmed, ⁇ when thin and sparse interference unevenness is confirmed ⁇ , thin Indicates that a linear interference unevenness can be confirmed, and ⁇ indicates that a clear interference unevenness is confirmed.
  • the obtained film was subjected to 10 ⁇ 10 cross-cut after 100 hours in an environment of 60 ° C. and 90% RH, and a 18 mm wide tape (Cello Tape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) was used.
  • a 18 mm wide tape (Cello Tape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) was used.
  • the polyester used in the examples and comparative examples was prepared as follows.
  • polyester (A) 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, 30 ppm of ethyl acid phosphate with respect to the produced polyester, and 100 ppm with respect to the produced polyester of magnesium acetate tetrahydrate as the catalyst at 260 ° C. in a nitrogen atmosphere. The reaction was allowed to proceed. Subsequently, 50 ppm of tetrabutyl titanate was added to the resulting polyester, the temperature was raised to 280 ° C. over 2 hours and 30 minutes, the pressure was reduced to an absolute pressure of 0.3 kPa, and melt polycondensation was further carried out for 80 minutes. 0.63 polyester (A) was obtained.
  • the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.63 due to a change in stirring power of the reaction tank, and the polymer was discharged under nitrogen pressure.
  • the obtained chip was preliminarily crystallized at 160 ° C., and then solid-phase polymerized in a nitrogen atmosphere at a temperature of 220 ° C. to obtain a polyester (C) having an intrinsic viscosity of 0.85.
  • polyester (D) is obtained using the same method as the production method of polyester (A) except that 0.3 part by weight of silica particles having an average particle diameter of 2 ⁇ m is added before melt polymerization. It was.
  • Isocyanate compounds Obtained by blocking 200 parts of a polyester having an average molecular weight of 1000 consisting of an ethylene oxide 2 mol adduct of bisphenol A and maleic acid, and 84 parts of sodium bisulfite with a polyisocyanate consisting of 33.6 parts of hexamethylene diisocyanate, Polyester resin-containing blocked isocyanate compound.
  • Isocyanate compounds (C2B) A blocked isocyanate obtained by blocking an isocyanate group of polyisocyanate comprising 158 parts of hexamethylene diisocyanate trimer and 26 parts of methoxypolyethylene glycol having a number average molecular weight of 1400 with 66 parts of methyl ethyl ketone oxime, 1,6-hexanediol and diethyl carbonate A urethane obtained by neutralizing a prepolymer comprising 115 parts of a polycarbonate polyol having a number average molecular weight of 2000, 1 part of trimethylolpropane, 40 parts of isophorone diisocyanate and 8 parts of dimethylolpropionic acid with triethylamine and extending the chain with diethylenetriamine. An aqueous blocked isocyanate compound containing a resin.
  • Oxazoline compounds (C3) Acrylic polymer having oxazoline group and polyalkylene oxide chain, Epocros WS-500 (manufactured by Nippon Shokubai Co., Ltd., containing about 38% 1-methoxy-2-propanol solvent)
  • the film was stretched 3.4 times in the longitudinal direction at a film temperature of 85 ° C. using the difference in peripheral speed of the roll, and then the coating liquid 1 shown in Table 1 below was applied to both sides of the longitudinally stretched film, and led to a tenter. Thickness having a coating layer in which the film is stretched 4.0 times at 120 ° C. in the transverse direction and heat-treated at 225 ° C. and then relaxed by 2% in the transverse direction and the coating layer thickness (after drying) is 0.10 ⁇ m. A 125 ⁇ m polyester film was obtained.
  • the minimum reflectance at an arbitrary wavelength of 400 to 800 nm of the coating layer was 5.5%. Clear interference unevenness was observed on the film after laminating the hard coat layer. The adhesion was also good. Also, the haze was low and the transparency was good. The properties of this film are shown in Table 2 below.
  • Example 1 In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film.
  • the finished polyester film had a high reflectance as shown in Table 2, and had good interference unevenness and adhesion.
  • Comparative Examples 1-7 In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition of an application layer into the coating agent composition shown in Table 1, and obtained the polyester film. As shown in Table 3, the finished laminated polyester film had poor interference unevenness and poor adhesion to the hard coat.
  • Comparative Example 8 In Example 1, it manufactured similarly to Example 1 except having not provided the application layer, and obtained the polyester film. The finished laminated polyester film was inferior in adhesion to the hard coat as shown in Table 3.
  • the film of the present invention can be suitably used for, for example, various optical films that are members of liquid crystals, plasma displays, and the like, and applications that place importance on adhesion and visibility with a surface functional layer such as a hard coat layer. .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film de polyester feuilleté lequel, lorsque diverses couches de surface fonctionnelles comprenant, par exemple, un revêtement dur, sont superposées sur celui-ci, diminue une irrégularité due à une interférence ou similaire pour parvenir à une visibilité satisfaisante et a une excellente adhérence aux couches de surface fonctionnelles. Le film de polyester feuilleté comprend un film de polyester et une couche de revêtement formée sur au moins une surface de celui-ci à partir d'un fluide de revêtement qui comprend une résine de polyester, des particules d'oxyde de titane et un composé époxy ou composé isocyanate.
PCT/JP2011/078075 2010-12-15 2011-12-05 Film de polyester feuilleté WO2012081438A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2010-278880 2010-12-15
JP2010-278881 2010-12-15
JP2010278881A JP5489972B2 (ja) 2010-12-15 2010-12-15 積層ポリエステルフィルム
JP2010278880A JP5489971B2 (ja) 2010-12-15 2010-12-15 積層ポリエステルフィルム

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014024896A (ja) * 2012-07-25 2014-02-06 Mitsubishi Plastics Inc 積層ポリエステルフィルム
CN110128915A (zh) * 2019-05-29 2019-08-16 无锡卡秀堡辉涂料有限公司 一种指纹识别素材emc材料的涂料及其制备方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004054161A (ja) * 2002-07-24 2004-02-19 Teijin Dupont Films Japan Ltd 光学用易接着性ポリエステルフィルム
JP2006123498A (ja) * 2004-09-30 2006-05-18 Dainippon Printing Co Ltd 光学積層体
JP2007203712A (ja) * 2006-02-06 2007-08-16 Fujifilm Corp 積層フィルム及びその製造方法、並びに積層フィルムを用いた光学シート及び表示装置
JP2007237720A (ja) * 2006-03-13 2007-09-20 Mitsubishi Polyester Film Copp 光学用積層ポリエステルフィルム
JP2008169277A (ja) * 2007-01-10 2008-07-24 Teijin Dupont Films Japan Ltd 光学用易接着性ポリエステルフィルム
JP2008170490A (ja) * 2007-01-09 2008-07-24 Konica Minolta Opto Inc 反射防止フィルム、それを用いた表示装置、プラズマディスプレイ用前面板フィルター、及びプラズマディスプレイ
JP2008183882A (ja) * 2007-01-31 2008-08-14 Fujifilm Corp 光学用積層フィルム及びその製造方法、反射防止フィルム並びに画像表示装置
JP2008183760A (ja) * 2007-01-29 2008-08-14 Teijin Dupont Films Japan Ltd 光学用易接着性ポリエステルフィルム
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
WO2010134416A1 (fr) * 2009-05-22 2010-11-25 東洋紡績株式会社 Film polyester hautement adhésif à usage optique
WO2011145405A1 (fr) * 2010-05-15 2011-11-24 三菱樹脂株式会社 Film de polyester stratifié

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004054161A (ja) * 2002-07-24 2004-02-19 Teijin Dupont Films Japan Ltd 光学用易接着性ポリエステルフィルム
JP2006123498A (ja) * 2004-09-30 2006-05-18 Dainippon Printing Co Ltd 光学積層体
JP2007203712A (ja) * 2006-02-06 2007-08-16 Fujifilm Corp 積層フィルム及びその製造方法、並びに積層フィルムを用いた光学シート及び表示装置
JP2007237720A (ja) * 2006-03-13 2007-09-20 Mitsubishi Polyester Film Copp 光学用積層ポリエステルフィルム
JP2008170490A (ja) * 2007-01-09 2008-07-24 Konica Minolta Opto Inc 反射防止フィルム、それを用いた表示装置、プラズマディスプレイ用前面板フィルター、及びプラズマディスプレイ
JP2008169277A (ja) * 2007-01-10 2008-07-24 Teijin Dupont Films Japan Ltd 光学用易接着性ポリエステルフィルム
JP2008183760A (ja) * 2007-01-29 2008-08-14 Teijin Dupont Films Japan Ltd 光学用易接着性ポリエステルフィルム
JP2008183882A (ja) * 2007-01-31 2008-08-14 Fujifilm Corp 光学用積層フィルム及びその製造方法、反射防止フィルム並びに画像表示装置
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
WO2010134416A1 (fr) * 2009-05-22 2010-11-25 東洋紡績株式会社 Film polyester hautement adhésif à usage optique
WO2011145405A1 (fr) * 2010-05-15 2011-11-24 三菱樹脂株式会社 Film de polyester stratifié

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014024896A (ja) * 2012-07-25 2014-02-06 Mitsubishi Plastics Inc 積層ポリエステルフィルム
CN110128915A (zh) * 2019-05-29 2019-08-16 无锡卡秀堡辉涂料有限公司 一种指纹识别素材emc材料的涂料及其制备方法

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