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WO2002000772A1 - Biaxially oriented polyester film, adhesive film, and laminated film - Google Patents

Biaxially oriented polyester film, adhesive film, and laminated film Download PDF

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Publication number
WO2002000772A1
WO2002000772A1 PCT/JP2001/005464 JP0105464W WO0200772A1 WO 2002000772 A1 WO2002000772 A1 WO 2002000772A1 JP 0105464 W JP0105464 W JP 0105464W WO 0200772 A1 WO0200772 A1 WO 0200772A1
Authority
WO
WIPO (PCT)
Prior art keywords
biaxially oriented
film
oriented polyester
polyester film
adhesive
Prior art date
Application number
PCT/JP2001/005464
Other languages
French (fr)
Japanese (ja)
Inventor
Taro Oya
Masayuki Fukuda
Original Assignee
Teijin Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2000194440A external-priority patent/JP2004149548A/en
Priority claimed from JP2000317667A external-priority patent/JP2004149551A/en
Application filed by Teijin Limited filed Critical Teijin Limited
Publication of WO2002000772A1 publication Critical patent/WO2002000772A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/25Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255Polyesters

Definitions

  • the present invention relates to a biaxially oriented polyester film, an adhesive film, and a laminated film. More specifically, the invention relates to a biaxially oriented polyester film suitable for use by bonding to an image display surface, an adhesive film and a laminated film using the same.
  • TVs and personal computer CRT displays emit images by displaying three lights, blue light, green light and red light, but also emit the intermediate colors of blue light and green light or green light and red light. Therefore, there is a problem that the hue contrast of the image is blurred by the light of these intermediate colors. And this problem has been strongly desired to be improved because personal computers are rapidly spreading and the situation of watching it for a long time is increasing.
  • Japanese Patent Application Laid-Open No. H11-333556 discloses that when attaching a protective film consisting of a protective layer and an adhesive layer to the image display surface, the adhesive layer is mixed with a carbon black. No. 39 proposes this.
  • the carbon black of the pressure-sensitive adhesive layer increases the average absorbance over each wavelength in the visible light band, so that the transmission of blue light and green light, and the transmission of intermediate colors of green light and red light respectively. It is disclosed that the contrast can be suppressed and the hue contrast of the image becomes clear.
  • Means for increasing the absorbance of the protective film of the publication include increasing the concentration of the light absorbing agent in the pressure-sensitive adhesive layer and increasing the thickness of the pressure-sensitive adhesive layer.
  • the addition concentration is naturally limited because it causes a decrease in the bonding strength of the adhesive layer and a decrease in handleability.
  • the latter may be appropriately selected according to the type of the adhesive and the surface roughness of the surface to be bonded, and the thickness of the adhesive layer such as a CRT display is preferably in the range of 5 to 40 m. No more adhesive layer thickness Does not function as an adhesive, but rather reduces the ease of handling in the processing and bonding processes.
  • the protective layer is composed of a base film or a hard coat layer serving as a base material.
  • a pigment is mixed with a binder resin, and the mixture is cured and laminated on the base film as a hard coat layer or a new layer. And dyeing the base film with a dye.
  • the layer to which the colorant is added is as thin as 6 to 10 m except for the base film.
  • the addition concentration is high when the hard coat layer is colored, so that the abrasion resistance and the abrasion resistance of the hard coat decrease.
  • providing a new binder layer on the colored layer also has the problem of complicating the process.
  • the method of dyeing the base film with a dye requires a separate dyeing step for dyeing, which causes a problem that the production process becomes complicated and the production cost increases.
  • the film provided with the adhesive layer at the time of forming the base film is:
  • the dyeing process has a problem that the adhesion of the adhesive layer to the hard coat layer and the pressure-sensitive adhesive layer is impaired.
  • adhesion between the base film and the adhesive layer is poor.
  • An object of the present invention is to solve the above-mentioned problems and to improve the handleability and hue contrast.
  • An object of the present invention is to provide a biaxially oriented polyester film having the same function.
  • Another object of the present invention is to provide a laminated film having improved transparency, visibility by external light, and abrasion resistance.
  • the average value (T av) of light transmittance at a wavelength of 450 to 65 nm is 40 to 80%
  • a biaxially oriented polyester film which is a base film for a laminated film for bonding an image display surface.
  • an adhesive film comprising the biaxially oriented polyester film of the present invention and a first adhesive layer provided on at least one surface of the film. Achieved.
  • the above objects and advantages of the present invention are: Thirdly, the biaxially oriented polyester film of the present invention, a first adhesive layer provided on both sides of the film, and a first adhesive layer on one side. A surface different from the surface in contact with the biaxially oriented polyester film of the hard coat layer and the other first adhesive layer provided on the surface different from the surface in contact with the biaxially oriented polyester film This is achieved by a laminated film for bonding a video display surface, comprising a second adhesive layer provided thereon.
  • a dye is added to the biaxially oriented film itself in order to remove or weaken these intermediate colors, and the light transmittance of the biaxially oriented film over the entire wavelength region is appropriately reduced, so that the above-mentioned three primary colors are removed.
  • the biaxially oriented polyester film of the present invention will be described in detail.
  • the biaxially oriented polyester film of the present invention has an average transmittance (Tav) in the wavelength range of 450 to 650 nm in the range of 40 to 80% in order not to transmit the overlapping portion of the three primary colors. It is necessary. If Tav exceeds 80%, the effect of enhancing contrast cannot be sufficiently exhibited, while if Tav is less than 40%, the entire area of the screen becomes longer and visibility deteriorates.
  • the preferred lower limit of Tav is 50%, and the preferred upper limit of TaV is 70%.
  • Tav may be hereinafter referred to as an average transmittance.
  • the ratio (T i ZT a V) between the transmittance (T i) of the light beam at each wavelength in the wavelength range and the average value (T aV) of the transmittance in the wavelength range is 0.7 to 1.3.
  • the upper limit of T i / Tav is preferably 1.2, and more preferably 1.10.
  • the lower limit of TiZTaV is preferably 0.8, and more preferably 0.9.
  • the biaxially oriented polyester film of the present invention needs to have a haze value of 5% or less. If the haze value is larger than 5%, the hue of the image becomes cloudy, and the visibility deteriorates due to lack of sharpness.
  • Means for reducing the Haze of the biaxially oriented film to 5% or less and the T aV to 80% or less include, for example, using a pigment having a particle size of 500 nm or less or a dye as a pigment.
  • the haze value of the biaxially oriented polyester film is preferably 3% or less, particularly preferably 2% or less.
  • the amount of the dye added is preferably in the range of 0.02 to 0.42 g per unit area (m 2 ) of the surface perpendicular to the thickness direction of the biaxially oriented polyester film.
  • Dyes used in the present invention include organic dyes and pigments. Generally, organic dyes have lower weather resistance than pigments. The haze goes up.
  • the pigment blended in the biaxially oriented polyester film of the present invention has good dispersibility in the polyester constituting the biaxially oriented polyester film to prevent a decrease in the haze value. It is preferable to use a material having an appropriate particle size distribution and reducing the absorbance at each wavelength on average for the same reason as the dye. Specifically, the average particle size after dispersion is preferably from 10 to 50 O nm from the viewpoint of dispersibility in polyester. Particularly preferable amount of the case of the pigment unit area in a plane perpendicular to the thickness direction of the biaxially Oriented polyester film (m 2) per 0 2 7 ⁇ 0.
  • the pigment is preferably a black car pump rack or cobalt oxide.
  • a mixture of colored pigments so that the hue becomes black may be used.
  • colored pigments include phthalocyanine pigments, quinacdrine pigments, perylene pigments, and indanthrene blue pigments.
  • Organic dyes generally have poorer heat stability and weatherability than pigments. However, in the present invention, since the organic dye is added to the polyester, most of the ultraviolet light is absorbed by the polyester. Is possible. Further, in the present invention, the organic dye to be blended into the biaxially oriented polyester film is preferably one that hardly undergoes deterioration or deterioration at a temperature of 330 ° C. or lower in consideration of the heat history up to the final product. Specific examples include anthraquinone dyes, quinacdrine dyes, and pyrinone dyes. Further, when the selective transmittance is further developed by the dye, the transmitted light is biased and colored. Therefore, it is preferable to use a mixture of at least two types of organic dyes to reduce the absorbance at each wavelength on average.
  • Examples of the organic dye preferably used in the present invention include a perinone dye represented by the following formula (1) and an anthraquinone dye represented by the following formulas (2) to (4).
  • Ri R 16 is each independently a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, an aromatic group having 6 to 14 carbon atoms, an aromatic group having 14 carbon atoms, aromatic alkyl group, a heterocyclic group having 4 to 12 carbon atoms, a halogen atom, Shiano group, a nitro group, one CO R 17, one COOR 17, one NR 17 R 18, one NR 18 C_ ⁇ _R 19, one NR 18 S_ ⁇ 9 R 19, one CONR 17 R ls, _S0 2 NR 17 R 18, -COR 19, one S_ ⁇ 2 R 19, one COR 19, one NR 17 CONR 18 R 19, one C_ ⁇ _NR 18 S_ ⁇ represents 2 R 19 or a S0 2 NR 18 C oR 19, R 17 and R 18
  • the organic dye in which at least two kinds of the above organic dyes are mixed absorbs evenly over the entire visible light range and does not shift in hue.
  • Particularly preferred combinations of organic dyes are The ratio of each of the four dyes represented by the formulas (1) to (4) in the organic dye mixture is 20 to 60 mol% of the verinone dye represented by the formula (1), and the formula (2) Of the anthraquinone dye of the formula (3), from 10 to 40 mol% of the anthraquinone dye of the formula (3) and from 10 to 30 mol% of the anthraquinone dye of the formula (4). It was done.
  • Such a mixture of organic dyes expresses a clear hue contrast with little transmission of the above-mentioned superimposed portion of the light of the three primary colors.
  • the most preferred combinations of organic dyes are 30 to 50 mol% of the perinone dye of the formula (1), 10 to 20 mol% of the anthraquinone dye of the formula (2), and 25 to 50 mol% of the anthraquinone dye of the formula (3). ⁇ 35 mol% and an anthraquinone dye of the formula (4) in an amount of from 10 to 20 mol%.
  • a particularly preferred addition amount is from 0.021 to 0.214 g per unit area (m 2 ) of a plane perpendicular to the thickness direction of the biaxially oriented polyester film.
  • the pigment may be dispersed and dissolved in ethylene glycol or the like and added at the polymerization stage of the polyester.
  • the film A method is preferred in which pellets of a polyester resin to which a dye is added at a higher concentration than the addition concentration or a pellet obtained by melting and solidifying the dye itself are mixed and added. In melting and solidifying the dye, a binder may be appropriately added.
  • a method of adding with a small feeder is preferable because mechanical properties are different from pellets of polyester resin.
  • the addition amount by the feeder varies depending on the capacity and the addition amount of the extruder, but is preferably 0.2 to 20 kgZh force on the equipment.
  • the properties of the dye to be added to the polyester from the viewpoint of productivity, a dye which causes little decrease in the viscosity of the polyester resin during extrusion of the polyester is preferable.
  • the residence time is preferably 20 to 400 seconds at a shear deformation rate of the extruder of 0 (1 second). When this value is less than 20, the pigment is not sufficiently kneaded and uneven coloring is observed. On the other hand, when the value is more than 400 seconds, cutting due to a decrease in viscosity is liable to occur.
  • the polyester constituting the biaxially oriented polyester film in the present invention is preferably It is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof, and a diol or an ester-forming derivative thereof.
  • Specific examples of such a polyester include polyethylene terephthalate, polyethylene isophthalate,
  • polyethylene-1,2,6-naphthalene dicarboxylate are used.
  • those comprising at least 70% by weight of ethylene based on the weight of the polyester are preferably made of ethylene terephthalate or ethylene 1,6-naphthalenedicarboxylate.
  • the processability of a biaxially oriented polyester film is preferred. From the viewpoint of transparency and transparency, polyester having ethylene terephthalate as a main repeating unit is preferable.
  • Copolysynthetic components of polyesters whose main repeating unit is ethylene terephthalate include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, azelaic acid, and Examples thereof include aliphatic dicarboxylic acids such as basic acid and decane dicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
  • diol component examples include alicyclic diols such as 1,4-butanediol, 1,6-hexanediol, aliphatic diols such as diethylene glycol, and 1,4-cyclohexanedimethanol, and bis-diols.
  • Aromatic diols such as phenol A can be exemplified.
  • copolymer components may be used alone or in combination of two or more. Among these copolymer components, isophthalic acid is particularly preferred from the viewpoint of processability and transparency.
  • the proportion of the copolymer component depends on the type thereof, but is preferably a proportion that results in a melting point of the polymer of 230 to 258 ° C. If the melting point is lower than 230 ° C, heat resistance and mechanical strength may be poor.
  • the ratio of azophthalic acid is set to 12 mol 1% or less based on the number of moles of the acid component. Good.
  • the melting point of the polyester is measured by a method in which a melting peak is obtained at a heating rate of 20 / min using DuPont Instrument 910 DSC. The sample amount is 2 O mg.
  • the intrinsic viscosity (orthochlorophenol, 35 ° C.) of the polyester constituting the biaxially oriented polyester film of the present invention is preferably 0.52 to 1.5, more preferably 0.57. ⁇ : L.0.0, particularly preferably 0.60 to 0.80. If the intrinsic viscosity is less than 0.52, the film-forming properties may be poor, which is not preferable. On the other hand, if the intrinsic viscosity exceeds 1.50, the molding processability may be impaired, the extruder may be overloaded, or the intrinsic viscosity may decrease significantly due to an excessive rise in the resin temperature. Not preferred.
  • the polyesters described above can be produced by a method known per se, for example, by subjecting terephthalic acid, ethylene glycol and, if necessary, a copolymerization component (eg, isophthalic acid) to an esterification reaction, and then subjecting the resulting reaction product to To obtain a polyester by a polycondensation reaction until the degree of polymerization reaches a desired degree of polymerization, or a transesterification reaction of dimethyl ester terephthalate, ethylene glycol and, if necessary, a copolymer component (eg, dimethyl isophthalate).
  • a copolymerization component eg, isophthalic acid
  • a method in which the obtained reaction product is subjected to a polycondensation reaction until a desired degree of polymerization is obtained to obtain a polyester can be preferably exemplified.
  • 2,6-naphthylenedicarboxylic acid for the acid component or 1,4-cyclohexanedimethanol for the glycol component can be used.
  • the polyester obtained by the above method (melt polymerization) can be converted into a polymer having a higher degree of polymerization by a polymerization method in a solid state (solid state polymerization), if necessary.
  • the polyester thus obtained is subjected to a film-forming method known per se, that is, a method in which the polyester is melted and then extruded from a linear die to form an unstretched film, which is stretched and heat-treated. It can be a biaxially oriented polyester film.
  • the biaxially oriented polyester film of the present invention can contain an ultraviolet absorber.
  • R Q2 and R ° 3 are the same or different and are monovalent hydrocarbon residues;
  • X Q 2 is a tetravalent aromatic residue, which further contains a heteroatom. May be contained.
  • Such a cyclic imino ester is a compound known as an ultraviolet absorber, and is described, for example, in JP-A-59-12952.
  • X Q1 is a divalent aromatic residue in which the two bonds from X Q1 represented by the formula (5) are in the first and second positions; n Is 1, 2 or 3;
  • X 01 is preferably, for example, 1,2-phenylene, 1,2-naphthylene,
  • R one O-, one CO-, - S-, one S0 2 -, one CH 2 _, - (CH 2 ) 2 - or a C (CH 3) 2 - and it is.
  • 1,2-phenylene is particularly preferred.
  • X Q1 The aromatic residues exemplified for X Q1, for example an alkyl example when methyl having 1 to 10 carbon atoms, Echiru, propyl, hexyl, decyl and the like; Ari Le e.g. phenyl carbon number 6-12, naphthyl; number of carbon atoms 5 to 12 cycloalkyl such as pentyl pentyl, cyclohexyl and the like; aralkyl having 8 to 20 carbon atoms such as phenylethyl and the like; alkoxy having 1 to 10 carbon atoms such as methoxy, X toxic, decyloxy and the like; nitro; halogen such as It may be substituted with a substituent such as chlorine, bromine or the like; an acyl having 2 to 10 carbon atoms such as acetyl, proponyl, zenzyl, decanoyl and the like.
  • Ari Le e.g. phenyl
  • R 01 can be an n-valent (where n is 1, 2 or 3) hydrocarbon residue, or can be a direct bond only when n is 2.
  • Unsubstituted aliphatic groups having L0 include, for example, methyl, ethyl, propyl, hexyl, decyl and the like; unsubstituted aromatic groups having 6-12 carbons include, for example, phenyl, naphthyl, Examples of the unsubstituted alicyclic group having 5 to 12 carbon atoms include cyclopentyl and cyclohexyl.
  • R Q4 is alkylene, phenylene, or naphthylene having 2 to 10 carbon atoms.
  • a group represented by the following formula (11) (In the formula, 1 ⁇ 5 is an alkyl group having 1 to 0 carbon atoms, a phenyl group or a naphthyl group.)
  • R Q4 and R Q5 are as defined above, R Q6 is any of the groups defined for hydrogen atom or R 0 5.
  • R Q4 and R G6 are the same as above, and 1 ⁇ 7 is either a hydrogen atom or a group defined as 1 ⁇ 5.
  • 1 ⁇ 7 is either a hydrogen atom or a group defined as 1 ⁇ 5.
  • the monovalent hydrocarbon residue in the third, is substituted by the same substituents as the aromatic residue of the unsubstituted, for example, exemplified as the substituent of the aromatic residues representing said X 01 Can be mentioned. Therefore, examples of substitution with such a substituent include, for example, tolyl, methylnaphthyl, nitrophenyl, nitronaphthyl, chlorophenyl, benzoylphenyl, acetylphenyl or acetylnaphthyl.
  • the monovalent hydrocarbon residue a group represented by the above formula (10), (11), (12) or (13), that is, a substituted aliphatic residue or aromatic residue, Preferred are aromatic residues.
  • Examples of the divalent unsubstituted aliphatic group having 2 to 10 carbon atoms include ethylene, trimethylene, tetramethylene, and decamethylene.
  • Examples of the unsubstituted aromatic residue having 2 to 6 carbon atoms include divalent unsubstituted aromatic groups. Examples include phenylene, naphthylene, P, P'-biphenylene, and the like.
  • Examples of the divalent unsubstituted alicyclic group having 5 to 12 carbon atoms include, for example, cyclopentylene, cyclohexylene, and the like. .
  • R Q8 is any of the groups defined for R Q4 .
  • R Q 8 is the same as above, and R Q9 is any of the groups defined for R Q4 And R. 1Q is any of the groups defined in RQ6 . )
  • divalent hydrocarbon residue a third, a divalent aromatic residue of the non-substituted, for example by the same substituents as exemplified as the substituent for the aromatic group represented by the X 01 Substituted ones can be mentioned.
  • R fll is preferably a direct bond or an unsubstituted or substituted divalent aromatic hydrocarbon residue of the above-described first to third groups.
  • Unsubstituted or substituted aromatic hydrocarbon residues of the first or third group in which the bond comes from the furthest position are preferred, especially p-phenylene, p, p, -biphenyl Rene or 2,6-naphthylene is preferred.
  • trivalent hydrocarbon residue examples include, for example, a trivalent aromatic residue having 6 to 6 carbon atoms: L 2.
  • Such an aromatic residue may be substituted with the same substituent as exemplified as the substituent for the monovalent aromatic residue.
  • R 02 and R 03 are the same or different and are monovalent hydrocarbon residues, and X 02 is a tetravalent aromatic hydrocarbon residue.
  • the tetravalent aromatic residue may be substituted with the same substituent as that exemplified for the trivalent aromatic residue representing the length in the description of the above formula (5).
  • cyclic iminoester represented by the above formulas (5) and (6) used in the present invention include the following compounds.
  • R Q 11 is a divalent aromatic hydrocarbon residue.
  • the compound represented by is advantageously used.
  • the compounds of the formula (18) are, among others, 2,2′-p-phenylenebis (3,11-benzoxazine-14-one), 2,2 ′ — (4,4,1-diphenylene) bis ( Preferred are 3,1 benzoxazine and 4-one) and 2,2 '-(2,6-naphthylene) bis (3,1 benzoxazine).
  • the UV-absorbing properties of these cyclic imino esters are described in, for example, JP-A-59-12952, which are representative compounds thereof, which are incorporated herein by reference.
  • the cyclic imino ester has excellent compatibility with the polyester, but has the ability to react with the terminal hydroxyl group of the polyester as described in JP-A-59-12952 and US Pat. No. 4,291,152. Having. Therefore, it is necessary to carefully mix the cyclic imino ester and the polyester so that the cyclic imino ester is contained in a substantially unreacted state.
  • the main proportion of the terminal group is a carboxyl group polyester or the terminal hydroxyl group is blocked with a terminal blocking agent that is not reactive with the cyclic imino ester.
  • a terminal blocking agent that is not reactive with the cyclic imino ester.
  • T is the melt mixing temperature CO and Tm are the polyester melting temperatures (° C).
  • the cyclic imino ester and the polyester may react at a small ratio.However, this reaction increases the molecular weight of the polyester.According to this ratio, it is possible to prevent a decrease in the molecular weight due to the deterioration of the polyester due to the light absorbing agent. Is possible.
  • the ultraviolet absorption wavelength region When the cyclic iminoester reacts with the polyester, the ultraviolet absorption wavelength region generally shows a tendency to shift to a lower wavelength side than the unreacted ultraviolet absorption wavelength region, and therefore transmits the higher wavelength ultraviolet light. Have a tendency to
  • the cyclic imino ester When the cyclic imino ester is added in an appropriate amount, there is almost no sublimation, so that the periphery of the die is not stained by the film formation, and it absorbs the light near the wavelength of about 180 nm from ultraviolet rays, so that the film is not colored and visible light Excellent in preventing deterioration of absorbents and films.
  • the amount of the ultraviolet absorber added is preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, based on the polyester. If the amount is less than 0.1%, the effect of preventing ultraviolet light deterioration is small, while if it exceeds 5% by weight, the film-forming properties of the polyester deteriorate, which is not preferable.
  • the above-mentioned ultraviolet absorber is preferably added at the time of polymerization of polyester or at the time of melt extrusion, and it is particularly preferable to add the ultraviolet absorber in the form of master pellets.
  • an antioxidant if necessary, further, an antioxidant, a heat stabilizer, a viscosity adjuster, a plasticizer, a hue improver, Additives such as lubricants, nucleating agents, antistatic agents, antioxidants, and catalysts can be added. Suitable lubricants for the above polyester Such a roughening substance (filament) can be contained.
  • those conventionally known as a slipperiness imparting agent for a polyester film are used.
  • examples include calcium carbonate, calcium oxide, aluminum oxide, aluminum oxide, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles.
  • cross-linked silicone resin particles are used.
  • porous silica having an average particle size of l to 3 / m is preferred because it is easy to obtain slipperiness while maintaining transparency.
  • the addition amount of the porous silica is preferably from 0.01 to 0.005% by weight from the viewpoint of transparency and slipperiness.
  • the thickness of the biaxially oriented polyester film of the present invention is preferably 50 m or more because the scattering of glass can be easily suppressed in the event that the CRT is imploded.
  • the upper limit of the thickness of the biaxially oriented polyester film is preferably 250 or less because the haze value is easily maintained at 5% or less and the productivity of the film is good.
  • the biaxially oriented polyester film of the present invention preferably has a heat shrinkage in the longitudinal direction and width direction of 2% or less, respectively, when treated at 150 ° C. for 30 minutes, more preferably.
  • the heat shrinkage is 0 to: 0.5%. If the above heat shrinkage exceeds 2%, it is not preferable because flattening is likely to occur due to thermal deformation in the vapor deposition process when forming the optical laminate, particularly when forming the antireflection layer.
  • the biaxially oriented polyester film of the present invention is a base film for a laminated film for laminating an image display surface.
  • the adhesive film of the present invention can be positioned as an intermediate product for producing a laminated film for laminating an image display surface.
  • the laminated film for bonding the image display surface will be described later.
  • the adhesive layer constituting the adhesive film of the present invention is preferably composed of a composition mainly composed of an aqueous polyester and an amide of a fatty acid and Z or a bisamide of a fatty acid.
  • the glass transition point (Tg) of the aqueous polyester forming the adhesive layer is preferably from 40 to 85 ° C, more preferably from 45 to 80 ° C.
  • Water-based polyester When the glass transition point (Tg) is less than 40 ° C, the obtained film tends to have low heat resistance and low blocking resistance. On the other hand, when the Tg of the water-based polyester exceeds 85 ° C, the effect of improving the adhesiveness becomes poor.
  • the aqueous polyester referred to here is a polyester soluble or dispersible in water.
  • terephthalic acid isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, 4,4-diphenyldicarboxylic acid, phenylindanedicarboxylic acid, adipic acid, sebacin Acids, 5-Na sulfoisophthalic acid, trimellitic acid, dimethylol propionic acid, etc., and sulfonic acid components and ethylene glycol, diethylene glycol, neopentyl diol, 1,4-butanediol, 1,6- Polyesters produced from hydroxy compound components such as hexanediol, 1,4-six-mouth hexanedimethanol, glycerin, trimethylolpropane, and alkylene oxide adducts of bisphenol A can be mentioned. Further, the aqueous Polje ester further if it is necessary to impart affinity for water may be introduced
  • the diamine is preferably a diamine having 1 to 15 carbon atoms, particularly an alkylenediamine.
  • Preferred is N, N'-alkylenebisamide having a molecular weight of 200 to 800.
  • N, N'-methylenebisstearic acid amide, N, N'-ethylenebispalmitic acid amide, N, N, -methylene Bislauric acid amide, linoleic acid amide, caprylic acid amide, stearic acid amide and the like can be exemplified, and among these, the bisamide represented by the following formula is particularly preferable.
  • fatty acid amides and z or fatty acid bisamides are preferably contained in the composition for forming a coating film in an amount of 3 to 10% by weight.
  • the content of fatty acid amide and / or Z or fatty acid bisamide is too small, sufficient adhesive strength cannot be obtained, and slipperiness and blocking resistance tend to be reduced.
  • the adhesiveness between the coating film and the adhesive for glass decreases, the coating film becomes brittle, and the haze tends to increase.
  • the coefficient of friction of the adhesive layer in the present invention is preferably 0.8 or less, and more preferably 0.6% or less. If the friction coefficient of the adhesive layer exceeds 0.8, the winding property and the workability are poor, and it is difficult to perform a smooth film formation and processing.
  • the surface roughening substance examples include calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, silicon oxide, sodium silicate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, Inorganic fine particles such as tin oxide, antimony trioxide, force pump rack, molybdenum disulfide, etc., acrylic cross-linked polymer, styrene cross-linked polymer, cross-linked silicone resin, fluoro resin, benzoguanamine resin, phenol resin, nylon resin, Organic fine particles such as polyethylene wax can be used. Among these, it is preferable to select ultrafine particles having a specific gravity of not more than 3 in order to avoid sedimentation of the water-insoluble solid substance in the aqueous dispersion.
  • the preferable addition amount of the surface roughening material is 5 to 30% by weight in the composition for forming a coating film.
  • the range is 5 to 10% by weight.
  • particles having an average particle size of 0.01 to 0.1 m are used, 8 to 3% by weight is used. It is preferable to select from the range of 0% by weight.
  • the center line surface roughness (R a) of the slippery adhesive layer to which is added is preferably 2 to 10 nm. If Ra is less than 2 nm, it is difficult to attain the above-mentioned coefficient of friction, and the winding form becomes poor due to insufficient slippage during winding of the laminate, which hinders subsequent operations. On the other hand, if the Ra of the adhesive layer exceeds 1 O nm, the transparency deteriorates, and the haze tends to exceed 5%.
  • the adhesive layer in the present invention may be formed by applying an aqueous solution, an aqueous dispersion or an emulsion of the composition comprising the above-mentioned aqueous polyester and fatty acid amide and / or fatty acid bisamide to a roll coating method, a gravure coating method, a mouth-to-brush method, It can be preferably formed by a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, or the like. Further, in order to form a coating film, a resin other than the aqueous polyester, a surface roughening substance, an antistatic agent, a surfactant, an ultraviolet absorber, and the like can be added as necessary.
  • the application of the coating solution to the biaxially oriented polyester film can be performed at any stage, and is preferably performed during the film forming process of the biaxially oriented polyester film. It is preferable to apply at the stage until completion.
  • the stage until the completion of the crystal orientation means the unstretched film, the uniaxially oriented film in which the unrolled intermediate film is oriented in either the longitudinal direction or the lateral direction, and furthermore, the two directions of the longitudinal and lateral directions.
  • Orientation-oriented low-magnification orientation (biaxially oriented film before it is finally re-stretched longitudinally or laterally to complete oriented crystallization).
  • the coating solution of the above composition it is preferable to apply to a uniaxially oriented film that has been oriented in one direction, and then to carry out lateral stretching and heat fixing as it is, and to obtain the slipperiness thus obtained.
  • the adhesive layer exhibits strong bonding strength with the biaxially oriented polyester film of the base film.
  • the coating film may be formed on only one side of the film, or may be formed on both sides.
  • the coating amount of the coating solution is preferably 70 to 100 It is preferred that the amount be in the range of nm, more preferably in the range of 75-95 nm. If the thickness of the coating film is less than 70 nm, the adhesive strength tends to be insufficient, and if it is too thick and exceeds 10 O nm, blocking may occur or the haze value may increase.
  • the coating solution when applying the coating solution to the film, take preparatory steps to improve coatability. It is preferable to apply a physical treatment such as a corona surface treatment, a flame treatment, or a plasma treatment to the coated surface in advance, or to use a chemically inert surfactant together with the coating composition. This surfactant promotes wetting of the aqueous coating liquid on the polyester film.
  • polyoxyethylene alkyl phenyl ether polyoxyethylene monofatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal stone, alkyl sulfate, alkyl sulfonate, alkyl sulfonate, etc., nonionic, nonionic Surfactants.
  • the coating liquid may contain an ionic low molecular compound depending on the presence of impurities in the raw material.
  • the ionic low molecular compound referred to here is one S ⁇ 3
  • X 1, -coox 1, - substances having a PO 4 X one NO- X 1 (X 1 represents an alkali metal or Anmoniumu groups in formula) Molecular weight 1 0 0 0
  • the following ionic functional group represented by like It is. If the ionic low-molecular compound is present in the adhesive layer in excess of 1000 ppm, the coating liquid wets the biaxially oriented polyester film when the aforementioned coating liquid is applied to the biaxially oriented polyester film. In addition, it is difficult to obtain a coating film having a constant thickness, and the adhesiveness to the adhesive is apt to decrease.
  • the detection of the zwitterionic low-molecular compound can be performed by forming a coating film on the film surface and analyzing the surface of the coating film by XPS (X-ray photoelectron spectroscopy).
  • the adhesive film of the present invention uses the adhesive layer as the back surface (in the case of double-sided application, any single surface), and transmits light in the visible light region from the side of the biaxially oriented polyester film at an angle of 45 degrees to the surface.
  • the reflectance at the interface between the adhesive layer and the biaxially oriented polyester film (hereinafter sometimes referred to as the back surface reflectance) is preferably 0.4% or less.
  • the backside reflectance exceeds 0.4%, the effect on frontside reflection cannot be ignored, and when used as an optical laminate for antiglare films for displays, the reflection of extraneous light is caused by interference between frontside reflection and backside reflection. It becomes obscured with a rainbow pattern, which easily impairs visibility.
  • the refractive index (nz) in the thickness direction of the coating film is preferably set to 1.50 to: L.60. If nz deviates from the above range, the backside reflection in the visible light region tends to exceed 0.4%. Also, the refractive index is If the ratio exceeds the range, the effect of back surface reflection becomes apparent, and in the case where an anti-reflection layer described later is provided, there may be a problem that it becomes difficult to prevent reflection.
  • the easy-adhesive film thus obtained has excellent surface slipperiness and adhesiveness, but also has a clear hue contrast and is excellent in transparency.
  • a second adhesive film is formed on one surface of the adhesive film of the present invention having the first adhesive layer formed on both surfaces. And a hard coat layer laminated on the other surface.
  • the laminated film of the present invention will be described in detail below.
  • the laminated film of the present invention is obtained by laminating a hard coat layer on the first adhesive layer, whereby the abrasion resistance of the laminated film of the present invention can be improved.
  • a radiation-curable or silane-based resin can be used as the node coat layer.
  • a hard coat layer using a radiation-curable resin is preferable, and among them, an ultraviolet (UV) A hard coat layer using a resin is preferable.
  • UV curable composition used for forming the hard coat layer include UV curable compositions such as urethane acrylate, epoxy acrylate, and polyester acrylate.
  • the composition is applied on the adhesive layer, and the composition is cured by heating, irradiation with radiation (for example, ultraviolet rays), or the like. Good.
  • the thickness of the hard coat layer is not particularly limited, but is preferably in the range of 1 to 15 m.
  • the laminated film of the present invention it is preferable to further form a multiple antireflection layer on the hard coat layer thus formed.
  • the multiple anti-reflection layer is formed by alternately laminating a plurality of layers having different refractive indexes, and the configuration is generally well known.
  • One low refractive index layer (S i ⁇ 2 , 2 O nm)- Layer (IT_ ⁇ , 93 nm) such as
  • the anti-reflection layer As a method for forming the anti-reflection layer, any method can be adopted, and for example, the layers may be laminated by sputtering. With the multiple anti-reflection layer, the laminated film of the present invention can suppress the reflection of extraneous light that hinders the visibility of the display.
  • the anti-reflection layer includes a single-layer film which mainly prevents yellow light from being mainly reflected, but a multilayer anti-reflection film is more suitable for preventing reflection of a display.
  • the second adhesive layer is laminated on a surface different from the side on which the hard coat layer is formed.
  • a biaxially oriented polyester film is also used. In order to improve the adhesiveness of these, it is preferable to laminate them via a first adhesive layer.
  • the haze value was measured using a haze meter (NDH-20) manufactured by Nippon Denshoku Industries Co., Ltd. The haze value was evaluated according to the following criteria.
  • the transmittance of visible light having a wavelength of 450 to 650 ⁇ m was measured using a spectrophotometer MP C3100 manufactured by Shimadzu Corporation.
  • Average transmittance (Tav) of wavelength 450-65011111 is 0.40 or more and 0.50 or less Full or 0.70 to 0.80 or less,
  • Average absorbance (Aav) at a wavelength of 400 to 750 nm is less than 0.40 or more than 0.80
  • the transmittance (T i) at each wavelength i from 450 to 650 nm was measured according to the above-mentioned method for measuring absorbance. The obtained results were evaluated by the following methods.
  • the test CRT is illuminated with a 30W fluorescent lamp from above 45 °, and the maximum and minimum luminance on the screen is measured with a luminance meter (Minol Yu) at 30 ° above horizontal, where specular light is not directly incident. , Contrast 1 (highest luminance, lowest luminance).
  • the test sample was attached to a CRT with an adhesive, and the highest luminance and the lowest luminance were measured again, and the contrast 2 was obtained.
  • a value of 100% was evaluated in the following categories. X 100% is 120% or more, ⁇ : (Contrast 2 Z Contrast 1) X 100% is 100% or more and less than 120%,
  • L *, a *, and b * in the L * a * b * color system were determined from the transmission spectrum of the test film with respect to the standard light A in accordance with JIS Z 8729.
  • the chroma deviation from the achromatic color was evaluated using the ab chroma (C * ab) obtained from the following equation.
  • the surface of the adhesive layer of the adhesive film is the back side (or one side in the case of double-sided application)
  • a point light source is irradiated at an angle of 45 ° from the film surface, and the film thickness is d from the main reflection
  • the reflected light separated by dZO. 707 is defined as the backside reflection, and this is divided by the amount of light from the point light source to obtain the reflectance. This was evaluated according to the following criteria.
  • a hard coat layer with a thickness of 5 m is formed on the adhesive layer of the adhesive film, cross-cut in a grid (1), 100 squares of 11111, and a 24-mm cellophane tape (Nichiban) (Manufactured by the company) and abruptly peeled off at a peeling angle of 180 °.
  • the peeled surface was observed and evaluated according to the following criteria.
  • the surface of the adhesive layer of the adhesive film is analyzed by XPS (X-ray photoelectron spectroscopy). According to the result, it is displayed as follows.
  • The content of ionic low-molecular compounds is 1000 ppm or less
  • the thread placed on the upper film used at that time has a lower surface area of 50 cm 2 (8 OmmX 62.5 mm), and the surface that contacts the film is neoprene rubber with a hardness of 80 ° and its weight. (W) shall be 1.2 kg.
  • the static friction coefficient (iS) is calculated by the following equation.
  • the measurement was performed using an Abbe refractometer with sodium D line as a light source.
  • the mounting solution was methylene iodide, and the measurement atmosphere was 25 ° C and 65% RH.
  • ⁇ : ⁇ haze is less than 10
  • ⁇ : ⁇ haze is 10 or more and less than 20
  • the film is kept in hot air of 150 ° C for 30 minutes, and the dimensional change before and after in the longitudinal direction and the width direction of the film is obtained from the following formula.
  • Stylus tip radius 2 shines
  • the flatness of the optical laminate after processing the anti-reflection layer (wrinkles, transfer, scratches due to rubbing, poor flatness of the film) and the presence of poor flatness due to thermal deformation of the optical laminate were evaluated in three steps. .
  • the intrinsic viscosity [77] 0.65) was extruded in a molten state from a die, and cooled by a cooling drum by a conventional method to obtain an unstretched film. Subsequently, the unstretched film is continuously stretched without being wound up, and then stretched at a stretch ratio of 3.5 while heating to 9 O in the longitudinal direction, and stretched at a stretch ratio of 3.5 while heated to 95 ° C in the transverse direction.
  • Example 1 The same operation as in Example 1 was repeated except that the thickness was changed to 200 m, and the amount of the pigment and the amount of addition were changed to 0.03% by weight of kaya set B lack AN (dye) manufactured by Nippon Kayaku. Was. Table 1 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
  • Polyethylene naphthalate containing 0.04% by weight of Dainippon Seika's car pump rack pigment and 0.007% by weight of porous silica with an average particle size of 1.7 m (35 ° C—intrinsic viscosity by orthochlorophenol) [77] 0.62) was extruded in a molten state from a die, and cooled with a cooling drum by a conventional method to obtain an unstretched film. Then, The unstretched film is continuously stretched without being wound, stretched at a stretch ratio of 3.5 while heating to 140 ° C in the longitudinal direction, and stretched to 135 ° C in the transverse direction.
  • Example 3 The same operation as in Example 3 was repeated except that the thickness was changed to 75 m, and the dye and the amount of the dye were changed as shown in Table 1.
  • Table 1 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
  • Example 1 The same operation as in Example 1 was repeated except that the dye and the amount added were changed as shown in Table 1.
  • Table 1 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
  • Example 3 the same operation was repeated except that the thickness and the amount of the dye added were changed as shown in Table 1.
  • Table 1 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
  • Example 1 75 A (0.03) 0.032 ⁇ ⁇ 2 ⁇ ⁇ Example 2 200 B (0.03) 0.084 ⁇ ⁇ 4 ⁇ ⁇ Example 3 50 A (0.04) 0.028 ⁇ ⁇ 3 ⁇ ⁇ Example 4 75 C (0.07) 0.074 ⁇ ⁇ 4 ⁇ ⁇ Comparative Example 1 75 None X ⁇ 'X ⁇ Comparative Example 2 75 D (0.35) 0.368 ⁇ X 4 ⁇ X Comparative Example 3 75 A (0.20) 0.210 X ⁇ 1 ⁇ ⁇ Comparative Example 4 75 B ( 0.02) 0.021 ⁇ ⁇ 4 X ⁇ Comparative Example 5 75 C (0.25) 0.263 ⁇ X 4 ⁇ X Comparative Example 6 200 A (0.10) 0.280 X ⁇ 1 ⁇ ⁇ ⁇
  • a molten polyethylene terephthalate ([77] 0.65) containing 0.007% by weight of silica was extruded from a die, cooled by a cooling drum in a conventional manner to form an unstretched film, and then 90 ° C in the longitudinal direction. After drawing at a draw ratio of 3.5 times at a temperature of 5%, an aqueous liquid having a concentration of 8% of the following coating composition was uniformly applied to both surfaces with a mouth coater, and then continuously at 95 ° C.
  • the acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and 5-sulfoisophthalic acid (4 mol%), and the daricol component is ethylene glycol (95 mol%) and neopentyl diol. (5 mol%) Tg 68 copolymerized polyester
  • a 75 m thick easily adhesive optical film was obtained in the same manner as in Example 6, except that the composition of the coating composition was changed as shown in Table 2.
  • the thickness of the coating is 0.15 m.
  • Table 2 shows the evaluation results of the obtained easily adhesive films.
  • Example 5 ⁇ (80) J (5) ⁇ (10) ⁇ (5) ⁇ 0.70 1.559 10 ⁇ 4
  • Example 7 Q (80) H (5) ⁇ ) ⁇ (5) ⁇ 0.75 1.550 9 ⁇ 5
  • Example 8 Q (80) 1 (5) ⁇ ) ⁇ (5) ⁇ 0.72 1.549 9 ⁇ 5
  • a UV-curable composition having the following composition was uniformly applied on one surface of the easy-adhesive film of Example 5 using a mouth-to-mouth solution so that the film thickness after curing was 5 m. Coated.
  • N-vinyl lipidone 10% by weight
  • a low refractive index layer (S i ⁇ 2 , 30 nm), a high refractive index layer (T i ⁇ 2 , 30 nm), and a low refractive index layer (S i ⁇ 2 , 3 0 nm), by sputtering a high refractive index layer (T I_ ⁇ 2, 1 0 0 nm) and a low refractive index layer (S I_ ⁇ 2, 1 0 0 nm) anti-reflection layer they are laminated in this order Formed.
  • Table 3 shows the evaluation results of the obtained optical laminate.
  • Example 9 the same operation was repeated except that the biaxially oriented film and the stretching temperature and the stretching ratio were changed to those of Examples 2 to 4.
  • Table 3 shows the evaluation results of the obtained optical laminate.
  • Example 9 the biaxially oriented film and the stretching temperature and stretching ratio were changed to those of Comparative Examples 1 to 6, and the coating composition used to form the slippery adhesive layer is shown below. The same operation was repeated except for the above change. Table 3 shows the evaluation results of the obtained optical laminate.
  • the acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and 5-sulfoisophthalic acid (4 mol%), and the dalicol component is ethylene dalicol (95 mol%) and neopentyldaricol. (5 mol%) copolymerized polyester with T g 68 ° C
  • Example 10 Example 2 200 B (0.03) 0.084 4 ⁇ ⁇ ⁇ Good
  • Example 11 Example 3 50 A (0.04) 0.028 3 ⁇ ⁇ ⁇ Good
  • Example 12 Example 4 75 C (0.07) 0.074 4 ⁇ ⁇ ⁇ Good
  • Comparative Example 8 Comparative Example 2 75 D (0.35) 0.368 4 ⁇ X ⁇ Good
  • Comparative Example 9 Comparative Example 3 75 A (0.20) 0.210 1 ⁇ ⁇ ⁇ Good
  • Comparative Example 10 Comparative Example 4 75 B (0.02) 0.021 4 X ⁇ ⁇ Good C Comparative Example 11 Comparative Example 5 75 C (0.25) 0.263 4 ⁇ X ⁇ Good
  • Comparative Example 12 Comparative Example 6 200 A (0.10) 0.280 1 ⁇ ⁇ ⁇ Good
  • the biaxially oriented polyester films of the present invention are excellent in transparency and image contrast.
  • the adhesive films (Examples 5 to 8) obtained by coating the biaxially oriented polyester film of the present invention with the adhesive m (Examples 5 to 8) showed that the adhesive film for glass and the cord coat were clear as shown in Table 2. It has good adhesiveness and does not impair optical properties.
  • the laminated films in which the hard coat layer and the antireflection layer are provided on the adhesive film of the present invention (Examples 9 to 12) not only have an image contrast, but also have abrasion resistance and antireflection ability. It was excellent.
  • the biaxially oriented polyester films of Comparative Examples 1 to 6 and the laminated films of Comparative Examples 7 to 12 which did not satisfy any of the requirements of the present invention, showed only poor optical characteristics.
  • the dyes represented by the following general formulas (1 ′), (2,), (3,) and (4 ′) were converted to 40.6 mol 1%, 16.7 mol%, 26.2 mol% and 16.6 mol 1%, respectively.
  • the dye mixture and the porous silica having an average particle size of 1.7 were mixed into polyethylene terephthalate having an intrinsic viscosity of 0.65 (35.C, o-chlorophenol), respectively. After blending so as to be 08% by weight and 0.007% by weight, the polyethylene terephthalate was extruded in a molten state from a die, and cooled by a cooling drum by a conventional method to obtain an unstretched film.
  • the unstretched film was stretched in the longitudinal direction at a temperature of 90 ° C. at a stretch ratio of 3.5, and an aqueous liquid having a concentration of 8% of the following coating composition was applied to both surfaces thereof. And then dried at 95 ° C, stretched transversely with 12 O at a stretch ratio of 3.8 times, heat-fixed with 23 Ot: and a thickness of 75 Atm. An easily adhesive film was obtained. The thickness of the coating film is 0.15 Was. Table 4 shows the evaluation results of the obtained easily adhesive films.
  • the acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%), and the glycol component is ethylendalicol (95 mol%) and neopentyldaricol ( (5 mol%) copolymerized polyester with Tg of 68 ° C
  • Example 14 The same operation as in Example 13 was repeated except that the thickness, the type of dye and the amount of dye added were changed as shown in Table 4, respectively.
  • Table 4 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
  • Comparative Examples 14, 15 In Example 13, the type of dye and the amount of dye added were changed as shown in Table 4, and 0.07% by weight of porous silica having an average particle size of 4.0 m was added as a lubricant. Other than the above, the same operation was repeated. Table 4 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
  • the dyes represented by the symbols E, F and G in Table 4 are the dyes of (1 ′) (2 ′) (3 ′) (4 ′) represented by the general formula of Example 4, It was mixed in the following ratio.
  • T Natural force Olin particles with an average particle size of 0.9 xm (0.08 Owt)
  • An optically-adhesive film with a thickness of 75 m was obtained in the same manner as in Example 13 except that the composition of the coating composition was changed as shown in Table 5.
  • the thickness of the coating film was 0.15 m.
  • Table 5 shows the evaluation results of the obtained easily adhesive films.
  • Aqueous polyester (wt%) P (80) ⁇ (80) Q (80) Q (80)
  • Example 1 A UV-curable composition having the following composition was uniformly applied on one surface of the easy-adhesive film of Example 3 using a mouth-to-mouth solution so that the film thickness after curing was 5 m. Was applied.
  • a low refractive index layer Si 2 , 30 nm
  • a high refractive index layer Ti 2 , 30 nm
  • a low refractive index layer Sio 2 , 3 0 nm
  • Table 6 shows the evaluation results of the obtained optical laminate.
  • Example 21 The same operation as in Example 21 was repeated except that the stretching temperature and the stretching ratio in the easily adhesive film and the production process thereof were changed to those of Examples 14 to 16.
  • Table 6 shows the evaluation results of the obtained optical laminate.
  • Example 21 the stretching temperature and the stretching ratio in the easy-adhesion film and the manufacturing process thereof were changed to those of Comparative Examples 13 to 15 and used to form an easily-adhesive coating film with respect to the adhesive. The same operation was repeated except that the coating composition was changed as shown below. Table 6 shows the evaluation results of the obtained optical laminate.
  • the acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%), and the glycol component is ethylene glycol (95 mol%) and neopentyl glycol. (5 mol%) copolymerized polyester with T g 68 ° C
  • Example 21 Example 13 75 ⁇ (0.08) 0.084 1.3 ⁇ ⁇ ⁇ Good Example 22
  • Example 4 the adhesive films of the present invention (Examples 13 to 16) are excellent in transparency and image contrast. As is clear from Table 5, these adhesive films of the present invention (Examples 17 to 20) have good adhesiveness to glass adhesives and eighty-one coats while deteriorating optical characteristics. Absent. Moreover, the laminated films (Examples 21 to 22) in which the hard coat layer and the anti-reflection layer are provided on the adhesive film of the present invention have not only the contrast of the B image but also the abrasion resistance and the anti-reflection ability. It was excellent. In contrast, the easily adhesive films of Comparative Examples 13 to 15 and the laminated films of Comparative Examples 16 to 18 which did not satisfy any of the requirements of the present invention showed only poor optical characteristics. Example 25
  • Example 2 is the same as Example 2 except that 0.5% by weight of 2,2′-p-phenylenebis (3,1-benzoxazidinone-141) is added as an ultraviolet absorber in addition to the dye. Operation was repeated.
  • Table 7 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
  • Example 25 the UV absorber was changed to 2,2′-P, p′-diphenylenebis (3.1-benzozozidinone-one), and the added amount was changed to 1.0% by weight. Other than the above, the same operation was repeated. Table 7 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
  • Example 26 the same operation was repeated except that the addition amount of 2,2′-P, p′-diphenylenebis (3,1-benzoxazidinone-one) was changed to 0.5% by weight.
  • Table 7 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
  • Example 25 the same operation was repeated except that the ultraviolet absorbent was changed to 2-p-nitrophenyl-3,1-benzoxazinone-1-one and the added amount was changed to 0.5% by weight.
  • Table 7 shows the evaluation results.
  • the ultraviolet absorbers represented by the symbols U, V and W in Table 7 are as follows.
  • Molten polyethylene terephthalate containing 0.03% by weight of Kaya set B 1 ack AN (dye) manufactured by Nippon Kayaku Co. and 0.007% by weight of porous silica having an average particle diameter of 1.7 / zm ([? 7] 0.65) from a die, cooled with a cooling drum by a conventional method to form an unstretched film, and then stretched in a longitudinal direction at a temperature of 90 at a stretch ratio of 3.5 times.
  • Aqueous liquid with a concentration of 8% of the composition for application is uniformly applied all over a roll, then stretched 3.8 times at 120 ° C in the horizontal direction while drying at 95 ° C, then 230 ° By heat fixing with C, an easily adhesive film having a thickness of 75 / m was obtained. Incidentally, the thickness of the coating film was 0.15 m. Table 8 shows the evaluation results of the obtained easily adhesive film.
  • the acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%), and the daricol component is ethylene dalicol (9 mol%). 5 mol%) and neopentyl glycol (5 mol%), T g 68 ° C copolymerized polyester
  • Example 29 is the same as Example 29 except that 0.5% by weight of 2,2′-p-phenylenebis (3,1-bunzoxazinone-1-one) was added as an ultraviolet absorber in addition to the dye. Operation was repeated. Table 8 shows the evaluation results of the obtained easily adhesive film.
  • Example 31 to 33
  • Example 30 the same operation was repeated except that the ultraviolet absorber and the amount of addition thereof were changed as shown in Table 8.
  • Table 8 shows the evaluation results of the obtained easily adhesive films.
  • the symbols (P, Q, H, I, J, K and Y) of the coating composition in Table 8 are the following polymers or compounds, respectively.
  • Acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%)
  • the acid component is terephthalic acid (85 mol%) and isophthalic acid (15 mol%)
  • a UV curable composition having the following composition was uniformly applied on one surface of the easily adhesive film of Example 29 using a roll coater so that the film thickness after curing was 5 m.
  • ultraviolet rays were irradiated for 30 seconds with a high-pressure mercury lamp having an intensity of 8 OW / cm to cure, thereby forming a hard coat layer.
  • a low refractive index layer (S i 0 2, 30 nm), a high refractive index layer (T I_ ⁇ 2, 30 nm), a low refractive index layer (S I_ ⁇ 2, 30 nm), High refractive index layer (Ti 2 , 100 nm) and low refractive index layer (Si 2 , 100 nm) are stacked in this order.
  • the resulting anti-reflection layer was formed by sputtering.
  • Table 9 shows the evaluation results of the obtained optical laminate.
  • Example 34 the same operation was repeated, except that the easily adhesive film was changed to those of Examples 30 to 33.
  • Table 9 shows the evaluation results of the obtained optical laminate.
  • Example 2 200 4 ⁇ ⁇ ⁇ Good ⁇ Example 3 5
  • Example 2 5 200 U (0.5) 4 ⁇ ⁇ ⁇ Good ⁇
  • Example 3 6 200 W (1.0) 4 ⁇ ⁇ ⁇ Good ⁇
  • Example 3 7 Example 2 7 200 W (0.5 ) 4 ⁇ ⁇ ⁇ Good ⁇
  • Example 3 7 Example 2 8 200 V (0.5) 4 ⁇ ⁇ ⁇ Good ⁇
  • Tables 7 to 9 are considered.
  • the biaxially oriented polyester film of the present invention to which an ultraviolet absorber was added (Examples 25 to 28) had excellent light degradation resistance, and the adhesive of the present invention using them was used.
  • the transparent films (Examples 30 to 33) and the laminated films (Examples 35 to 38) also had excellent light resistance.
  • the present invention it is possible to obtain a biaxially oriented polyester film having high image contrast without impairing transparency and a laminated film thereof. Furthermore, according to the present invention, if the adhesive strength of the laminated film is improved and the back surface reflectance is reduced, the surface hardness / abrasion resistance and the like are good, and sufficient transparency, anti-glare properties and explosion-proof properties are obtained. It can be used as a protective film for personal computer displays. Further, the biaxially oriented polyester film of the present invention and the laminated film thereof may be used in addition to the above-mentioned surface protective plate of a personal computer display, as well as the surface of window glass, showcases, glasses, instruments, photographs, paintings, illustrations, signs, etc. It can be suitably used as a protective sheet and has high industrial value.

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Abstract

A biaxially oriented polyester film for optical use which combines handleability with a hue contrast; an adhesive film; and a laminated film. The biaxially oriented polyester film contains a colorant incorporated therein and has a haze of 5% or lower. In this film, the average light transmittance in the wavelength range of 450 to 650 nm, Tav, is 40 to 80%, and the value obtained by dividing the light transmittance (Ti) at each wavelength, i, within that wavelength range by the Tav is 0.7 to 1.3. The adhesive film and the laminated film are made with the biaxially oriented polyester film.

Description

二軸配向ポリエステルフィルム、 接着性フィルムおよび積層フィルム  Biaxially oriented polyester film, adhesive film and laminated film
技術分野 Technical field
本発明は二軸配向ポリエステルフィルム、 接着性フィルムおよび積層フィルム に関する。 さらに詳しくは映像表示面に貼り合せて使用するのに好適な二軸配向 ポリエステルフィルム、 それを用いた接着性フィルムおよび積層フィルムに関す 明  The present invention relates to a biaxially oriented polyester film, an adhesive film, and a laminated film. More specifically, the invention relates to a biaxially oriented polyester film suitable for use by bonding to an image display surface, an adhesive film and a laminated film using the same.
る。 You.
 Fine
従来の技術  Conventional technology
テレビやパソコンの C R Tディスプレイなどは、 青色光、 緑色光および赤色光 の 3つの光を発光させて映像を表示するが、 青色光と緑色光または緑色光と赤色 光のそれぞれの中間色も発光しており、 これらの中間色の光によって映像の色相 のコントラストがぼやけるという問題があった。 そして、 この問題は、 パ一ソナ ルコンピュータの急速な普及によって、 長時間見続ける状況が多くなつているこ とから、 その改善が強く望まれてきている。  TVs and personal computer CRT displays emit images by displaying three lights, blue light, green light and red light, but also emit the intermediate colors of blue light and green light or green light and red light. Therefore, there is a problem that the hue contrast of the image is blurred by the light of these intermediate colors. And this problem has been strongly desired to be improved because personal computers are rapidly spreading and the situation of watching it for a long time is increasing.
この問題の対策として、 映像表示面に防護層と粘着剤層とからなる保護フィル ムを貼り付ける際に、 粘着剤層に力一ボンブラックを配合させることが特開平 1 1 - 3 3 5 6 3 9号公報で提案されている。 該公報によれば、 粘着剤層のカーボ ンブラックによって、可視光帯の各波長に渡って平均的に吸光度が増加するので、 青色光および緑色光ならびに緑色光および赤色光の中間色の透過をそれぞれ抑制 することができ、映像の色相のコントラストが明瞭になることが開示されている。 また、 該公報の保護フィルムで吸光度を増加させる手段としては、 粘着剤層中の 吸光剤の添加濃度を増やすことと粘着剤層の厚みを増やすこととがある。 前者に ついては、 粘着剤層の接合力の低下や取り扱い性の低下を引き起こすことからそ の添加濃度は自ずと限界がある。 他方、 後者については、 粘着剤の種類や貼り合 せる面の表面粗さなどによつて適宜選択すればよいが、 C R Tデイスプレイなど の粘着剤層の厚みは 5〜4 0 mの範囲が好ましく、 これ以上の粘着剤層の厚み は粘着剤としては機能せず、 むしろ、 加工や貼り合わせの工程における取り扱い 性を低下させる。 As a countermeasure against this problem, Japanese Patent Application Laid-Open No. H11-333556 discloses that when attaching a protective film consisting of a protective layer and an adhesive layer to the image display surface, the adhesive layer is mixed with a carbon black. No. 39 proposes this. According to the publication, the carbon black of the pressure-sensitive adhesive layer increases the average absorbance over each wavelength in the visible light band, so that the transmission of blue light and green light, and the transmission of intermediate colors of green light and red light respectively. It is disclosed that the contrast can be suppressed and the hue contrast of the image becomes clear. Means for increasing the absorbance of the protective film of the publication include increasing the concentration of the light absorbing agent in the pressure-sensitive adhesive layer and increasing the thickness of the pressure-sensitive adhesive layer. In the former case, the addition concentration is naturally limited because it causes a decrease in the bonding strength of the adhesive layer and a decrease in handleability. On the other hand, the latter may be appropriately selected according to the type of the adhesive and the surface roughness of the surface to be bonded, and the thickness of the adhesive layer such as a CRT display is preferably in the range of 5 to 40 m. No more adhesive layer thickness Does not function as an adhesive, but rather reduces the ease of handling in the processing and bonding processes.
一方、 粘着剤層にではなく防護層を着色することは特開平 2 0 0 0 - 5 7 9 7 6号公報で提案されている。 具体的には、 防護層は基材となるベースフィルムや ハードコート層からなり、 該公報では、 バインダー樹脂に顔料を配合しこれを硬 化させてハードコート層もしくは新たな層としてベースフィルムに積層すること およびベースフィルムを染料で染着することが挙げられている。 しかしながら、 該公報によれば、 着色剤を添加する層はベースフィルムを除けばいずれの層も 6 〜1 0 mと薄いため、 バインダー樹脂に顔料を配合する方法では添加濃度が高 くなり工程上の取り扱い性が低く、 また、 ハ一ドコート層を着色した場合は添加 濃度が高いことからハードコートの耐磨耗性ゃ耐擦傷性が低下する問題があった。 加えて着色層に新たにバインダー層を設けることは、 工程を煩雑化させるという 問題もあった。  On the other hand, coloring the protective layer instead of the pressure-sensitive adhesive layer has been proposed in JP-A-2000-57976. Specifically, the protective layer is composed of a base film or a hard coat layer serving as a base material. According to the publication, a pigment is mixed with a binder resin, and the mixture is cured and laminated on the base film as a hard coat layer or a new layer. And dyeing the base film with a dye. However, according to the publication, the layer to which the colorant is added is as thin as 6 to 10 m except for the base film. In addition, when the hard coat layer is colored, the addition concentration is high when the hard coat layer is colored, so that the abrasion resistance and the abrasion resistance of the hard coat decrease. In addition, providing a new binder layer on the colored layer also has the problem of complicating the process.
また、 ベースフィルムを染料で染着する方法では、 染着させるための染色工程 が別に必要となり、 生産工程の煩雑化や生産コストの増加につながるという問題 がある。 加えて、 ベ一スフイルムに他の層を積層する際の接着性を向上させるた めの接着層を設ける場合には、 ベ一スフイルムの製膜時に接着層を設けたフィル ムに対しては、 染色工程を経ることにより、 接着層のハードコート層および粘着 剤層への易接着性が損われるという問題があり、 ベースフィルム製膜して染色ェ 程を経た後接着層を設けたフィルムに対しては、 ベースフィルムと接着層との接 着性が乏しいという問題があつた。  In addition, the method of dyeing the base film with a dye requires a separate dyeing step for dyeing, which causes a problem that the production process becomes complicated and the production cost increases. In addition, when an adhesive layer is provided to improve the adhesiveness when another layer is laminated on the base film, the film provided with the adhesive layer at the time of forming the base film is: The dyeing process has a problem that the adhesion of the adhesive layer to the hard coat layer and the pressure-sensitive adhesive layer is impaired. Thus, there has been a problem that adhesion between the base film and the adhesive layer is poor.
そのため、 以上のような欠点を克服する視認性の良好な光学用の保護フィルム の提供が強く望まれてきていた。 また、 光学用の保護フィルムでは、 上記の映像 表示の色相のコントラスト向上と工程の簡素化および粘着剤層の取り扱い性向上 のほか〖こ、 透明性の向上、 外来光による視認性低下の防止、 耐磨耗性の向上また は保護フィルムを構成する層間の剥離防止も強く望まれていた。  Therefore, it has been strongly desired to provide a protective film for optics having good visibility that overcomes the above-mentioned drawbacks. In addition, in the optical protective film, in addition to improving the hue contrast of the image display and simplifying the process and improving the handleability of the pressure-sensitive adhesive layer, in addition to improving the transparency, improving the visibility due to extraneous light, There has been a strong demand for improvement in abrasion resistance or prevention of delamination between layers constituting the protective film.
発明の開示  Disclosure of the invention
本発明の目的は、 上述の問題を解消し、 取り扱い性と色相のコントラストとを 兼ね備えた二軸配向ポリエステルフィルムを提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to improve the handleability and hue contrast. An object of the present invention is to provide a biaxially oriented polyester film having the same function.
本発明の他の目的は、 透明性、 外来光による視認性および耐磨耗性の向上した 積層フィルムを提供することにある。  Another object of the present invention is to provide a laminated film having improved transparency, visibility by external light, and abrasion resistance.
本発明のさらに他の目的および利点は以下の説明から明らかになろう。  Still other objects and advantages of the present invention will become apparent from the following description.
本発明によれば、 本発明の上記目的および利点は、 第 1に、  According to the present invention, the above objects and advantages of the present invention are:
( 1 ) 色素を含有し、  (1) containing a dye,
( 2 ) ヘーズ値が 5 %以下であり、  (2) Haze value is 5% or less,
( 3 ) 波長 4 5 0〜6 5 0 nmにおける光線の透過率の平均値 (T a v) が 4 0 〜8 0 %であり、  (3) The average value (T av) of light transmittance at a wavelength of 450 to 65 nm is 40 to 80%,
( 4) 波長 4 5 0〜6 5 0 nmにおける各波長 iの光線の透過率 (T i ) を T a Vで割った値が 0 . 7〜1 . 3であり、 そして  (4) The value obtained by dividing the transmittance (T i) of the light beam of each wavelength i at a wavelength of 450-650 nm by T aV is 0.7-1.3, and
( 5 ) 映像表示面貼合せ用積層フィルムのためのベースフィルムである、 ことを特徴とする二軸配向ポリエステルフィルムによつて達成される。  (5) A biaxially oriented polyester film, which is a base film for a laminated film for bonding an image display surface.
本発明によれば、 本発明の上記目的および利点は、 第 2に、 本発明の二軸配向 ポリエステルフィルムおよび上記フィルムの少なくとも片面上に設けられた第 1 接着層からなる接着性フィルムによつて達成される。  According to the present invention, the above objects and advantages of the present invention are secondly achieved by an adhesive film comprising the biaxially oriented polyester film of the present invention and a first adhesive layer provided on at least one surface of the film. Achieved.
また、 本発明によれば、 本発明の上記目的および利点は、 第 3に、 本発明の二 軸配向ポリエステルフィルム、 このフィルムの両面上に設けられた第 1接着層、 一方の第 1接着層の二軸配向ポリエステルフィルムと接触している面とは異なる 面上に設けられたハ一ドコ一ト層および他方の第 1接着層の二軸配向ポリエステ ルフィルムと接触している面とは異なる面上に設けられた第 2接着層からなる映 像表示面貼合せ用積層フィルムによつて達成される。  According to the present invention, the above objects and advantages of the present invention are: Thirdly, the biaxially oriented polyester film of the present invention, a first adhesive layer provided on both sides of the film, and a first adhesive layer on one side. A surface different from the surface in contact with the biaxially oriented polyester film of the hard coat layer and the other first adhesive layer provided on the surface different from the surface in contact with the biaxially oriented polyester film This is achieved by a laminated film for bonding a video display surface, comprising a second adhesive layer provided thereon.
発明の実施の形態  Embodiment of the Invention
C R Tなどの発光色の強さと光の波長の関係を見ると、 短波長側から青、 緑、 赤の三つのピークが存在する。 問題は、 青と緑および緑と赤のピークの裾野が重 畳していることにある。 このため、 青だけあるいは緑だけが発色しても青と緑の 中間色が、 または、 緑だけあるいは赤だけが発色しても赤と緑の中間色すなわち 黄色みがかった色が何がしか発色し、 これらの中間色が、 映像のコントラストを 弱める原因となる。 そこで、 本発明では、 これらの中間色を除去あるいは弱める ために二軸配向フィルム自体に色素を添加して、 二軸配向フィルムの全波長領域 に亘る光線透過率を適度に低下させて前記の三原色の重畳部分を透過させないよ うにして認視性と映像の色相のコントラストの両立を可能としたものである。 以下、 まず本発明の二軸配向ポリエステルフィルムについて詳述する。 Looking at the relationship between the emission color intensity of CRTs and the like and the wavelength of light, there are three peaks, blue, green, and red, from the short wavelength side. The problem is that the tails of the blue and green and green and red peaks overlap. For this reason, even if only blue or green is developed, the intermediate color between blue and green is formed, or if only green or only red is developed, the intermediate color between red and green, that is, a yellowish color is formed, These neutral colors increase the contrast of the image May cause weakening. Therefore, in the present invention, a dye is added to the biaxially oriented film itself in order to remove or weaken these intermediate colors, and the light transmittance of the biaxially oriented film over the entire wavelength region is appropriately reduced, so that the above-mentioned three primary colors are removed. By preventing the superimposed portion from being transmitted, it is possible to achieve both visibility and contrast of the hue of the image. Hereinafter, first, the biaxially oriented polyester film of the present invention will be described in detail.
本発明の二軸配向ポリエステルフィルムは、 前記の三原色の重畳部分を透過さ せないために、 波長 450〜650 nmの範囲の透過率の平均値 (Tav) が 4 0〜80%の範囲にあることが必要である。 Tavが 80%を超えるとコントラ ストを強める効果が十分に発現できず、 他方、 Tavが 40%未満では画面全域 が喑くなつて認視性が低下する。 好ましい Tavの下限は 50%、 好ましい Ta Vの上限は 70%である。 本明細書において、 以下に Tavを平均透過率と称す ることがある。 また、前記波長範囲における各波長における光線の透過率(T i) と前記波長範囲の透過率の平均値 (T a V) の比 (T i ZT a V) は、 0. 7〜 1. 3の範囲にあることが必要である。 T iZT a Vの値が 0. 7未満または 1. 3を超えると、 二軸配向ポリエステルフィルムによって透過光を着色し、 発色に 偏りができる。 T i /Tavの上限は 1. 2が好ましく、 1. 10がさらに好ま しい。他方、 T iZTa Vの下限は 0. 8が好ましく、 0. 9がさらに好ましい。 また、 本発明において吸光度を上げる際はへ一ズ値を大きくしないことが肝要 である。 本発明の二軸配向ポリエステルフィルムは、 ヘーズ値を 5%以下にする ことが必要である。 ヘーズ値が 5%より大きいと映像の色相が白濁し、 鮮映性を 欠いて認視性が低下する。 二軸配向フィルムのヘーズを 5 %以下にしつつ、 T a Vを 80 %以下にする手段としては、 例えば、 色素として粒径 500 nm以下の 顔料を用いたり染料を用いることが挙げられる。 二軸配向ポリエステルフィルム のヘーズ値は好ましくは 3%以下、 特に好ましくは 2%以下である。 なお、 色素 を添加する場合の添加量は、 二軸配向ポリエステルフィルムの厚み方向に垂直な 面の単位面積 (m2) 当り 0. 02〜0. 42gの範囲が好ましい。 The biaxially oriented polyester film of the present invention has an average transmittance (Tav) in the wavelength range of 450 to 650 nm in the range of 40 to 80% in order not to transmit the overlapping portion of the three primary colors. It is necessary. If Tav exceeds 80%, the effect of enhancing contrast cannot be sufficiently exhibited, while if Tav is less than 40%, the entire area of the screen becomes longer and visibility deteriorates. The preferred lower limit of Tav is 50%, and the preferred upper limit of TaV is 70%. In the present specification, Tav may be hereinafter referred to as an average transmittance. Further, the ratio (T i ZT a V) between the transmittance (T i) of the light beam at each wavelength in the wavelength range and the average value (T aV) of the transmittance in the wavelength range is 0.7 to 1.3. Must be in the range of When the value of TiZTaV is less than 0.7 or more than 1.3, the transmitted light is colored by the biaxially oriented polyester film, and the coloring is biased. The upper limit of T i / Tav is preferably 1.2, and more preferably 1.10. On the other hand, the lower limit of TiZTaV is preferably 0.8, and more preferably 0.9. In addition, when increasing the absorbance in the present invention, it is important not to increase the haze value. The biaxially oriented polyester film of the present invention needs to have a haze value of 5% or less. If the haze value is larger than 5%, the hue of the image becomes cloudy, and the visibility deteriorates due to lack of sharpness. Means for reducing the Haze of the biaxially oriented film to 5% or less and the T aV to 80% or less include, for example, using a pigment having a particle size of 500 nm or less or a dye as a pigment. The haze value of the biaxially oriented polyester film is preferably 3% or less, particularly preferably 2% or less. The amount of the dye added is preferably in the range of 0.02 to 0.42 g per unit area (m 2 ) of the surface perpendicular to the thickness direction of the biaxially oriented polyester film.
本発明において用いられる色素としては有機染料および顔料が挙げられる。 一 般的に有機染料は顔料に比べ耐候性が劣り、 他方顔料を用いるとその散乱光〖こよ りヘーズが上がるという二律背反の関係にある。 Dyes used in the present invention include organic dyes and pigments. Generally, organic dyes have lower weather resistance than pigments. The haze goes up.
従って、 顔料を用いる場合にはその粒径を小さくすることによりヘーズの増加 を抑える必要がある。 本発明における二軸配向ポリエステルフィルムへ配合する 顔料は、 ヘーズ値の低下を防止するため、 二軸配向ポリエステルフィルムを構成 するポリエステルへの分散性が良好であり、 分散後は粒径が小さく、 均一な粒径 分布をもち、 染料と同様な理由から各波長の吸光度を平均的に低下させるものが 好ましい。 具体的には、 ポリエステルへの分散性から、 分散後の平均粒径は 1 0 〜5 0 O nmであることが好ましい。 顔料の場合の特に好ましい添加量は二軸配 向ポリエステルフィルムの厚み方向に垂直な面の単位面積 (m2) 当り 0 2 7〜0 . 2 0 7 gが好ましい。 また、 各波長の吸光度を平均的に低下させること から、顔料としては、黒色系のカーポンプラックや酸化コバルトなどが好ましい。 また、 有色系の顔料を適宜、 色相が黒色になるよう混合したものを使用してもよ い。 有色顔料の例としては、 フタロシアニン系顔料、 キナクドリン系顔料、 ペリ レン系顔料、 ィンダンスレンブルー系顔料などが挙げられる。 Therefore, when a pigment is used, it is necessary to suppress an increase in haze by reducing the particle size. The pigment blended in the biaxially oriented polyester film of the present invention has good dispersibility in the polyester constituting the biaxially oriented polyester film to prevent a decrease in the haze value. It is preferable to use a material having an appropriate particle size distribution and reducing the absorbance at each wavelength on average for the same reason as the dye. Specifically, the average particle size after dispersion is preferably from 10 to 50 O nm from the viewpoint of dispersibility in polyester. Particularly preferable amount of the case of the pigment unit area in a plane perpendicular to the thickness direction of the biaxially Oriented polyester film (m 2) per 0 2 7~0. 2 0 7 g is preferred. Further, since the absorbance at each wavelength is reduced on average, the pigment is preferably a black car pump rack or cobalt oxide. Alternatively, a mixture of colored pigments so that the hue becomes black may be used. Examples of colored pigments include phthalocyanine pigments, quinacdrine pigments, perylene pigments, and indanthrene blue pigments.
一方、 有機染料は一般的に熱安定性おょび耐候性が顔料に比べて乏しい。 しか しながら、 本発明においては、 有機染料をポリエステルに添加しているため、 大 部分の紫外線をポリエステルが吸収することから、 ポリエステルに添加するに場 合においては耐候性の懸念なく有機染料の使用が可能である。 また本発明におい ては、 二軸配向ポリエステルフィルムへ配合する有機染料は、 最終製品までの熱 履歴を考慮し、 3 3 0 °C以下の温度では変質や劣化が生じ難いものが好ましい。 具体的には、 アントラキノン系染料、 キナクドリン系染料、 ピリノン系染料など が挙げられる。 また、 さらに染料によって選択透過性が発現すると、 透過光に偏 りができて着色するので、 少なくとも 2種の有機染料の混合物を用いて各波長の 吸光度を平均的に低下させることが好ましい。  Organic dyes, on the other hand, generally have poorer heat stability and weatherability than pigments. However, in the present invention, since the organic dye is added to the polyester, most of the ultraviolet light is absorbed by the polyester. Is possible. Further, in the present invention, the organic dye to be blended into the biaxially oriented polyester film is preferably one that hardly undergoes deterioration or deterioration at a temperature of 330 ° C. or lower in consideration of the heat history up to the final product. Specific examples include anthraquinone dyes, quinacdrine dyes, and pyrinone dyes. Further, when the selective transmittance is further developed by the dye, the transmitted light is biased and colored. Therefore, it is preferable to use a mixture of at least two types of organic dyes to reduce the absorbance at each wavelength on average.
本発明で好ましく用いられる有機染料としては、 特に、 下記式 (1 ) で表され るペリノン系染料および下記式 (2 ) 〜 (4) で表されるアントラキノン系染料 が挙げられる。
Figure imgf000007_0001
上記式 (1) 〜 (4) 中、 Ri R16は、 それぞれ独立に、 水素原子、 炭素数 1〜 6の脂肪族基、 炭素数 6〜; 14の芳香族基、 炭素数 7〜 14の芳香族アルキ ル基、 炭素数 4〜12の複素環基、 ハロゲン原子、 シァノ基、 ニトロ基、 一 CO R17、 一 COOR17、 一 NR17R18、 一 NR18C〇R19、 一 NR18S〇9R19、 一 CONR17Rls、 _S02NR17R18、 -COR19, 一 S〇2R19、 一 COR 19、 一 NR17CONR18R19、 一 C〇NR18S〇2R19または一 S02NR18C OR19を表し、 R17および R18は互いに独立に水素原子、炭素数 1〜6の脂肪族 基、 炭素数 6〜14の芳香族基または炭素数 4〜12の複素環基であるかあるい は R17および Rlsはそれらが結合している窒素原子と一緒になつて 5もしくは 6員複素環基を形成していてもよくそして R 19は炭素数 1〜 6の脂肪族基、 炭素 数 6〜 14の芳香族基または炭素数 4〜 12の複素環基を表す。
Examples of the organic dye preferably used in the present invention include a perinone dye represented by the following formula (1) and an anthraquinone dye represented by the following formulas (2) to (4).
Figure imgf000007_0001
In the above formulas (1) to (4), Ri R 16 is each independently a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, an aromatic group having 6 to 14 carbon atoms, an aromatic group having 14 carbon atoms, aromatic alkyl group, a heterocyclic group having 4 to 12 carbon atoms, a halogen atom, Shiano group, a nitro group, one CO R 17, one COOR 17, one NR 17 R 18, one NR 18 C_〇_R 19, one NR 18 S_〇 9 R 19, one CONR 17 R ls, _S0 2 NR 17 R 18, -COR 19, one S_〇 2 R 19, one COR 19, one NR 17 CONR 18 R 19, one C_〇_NR 18 S_〇 represents 2 R 19 or a S0 2 NR 18 C oR 19, R 17 and R 18 are each independently a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, 4 aromatic group or a carbon number of 6 to 14 carbon atoms there in either a 12 heterocyclic group R 17 and R ls may form a connexion 5 or 6-membered heterocyclic group together with the nitrogen atom to which they are attached and R 19 is a carbon Aliphatic group having 1 to 6 carbon atoms, aromatic group having 6 to 14 carbon atoms Other represents a heterocyclic group of 4 to 12 carbon atoms.
上記有機染料が少なくとも 2種混合された有機染料は、 可視光線全域にわたり 平均的に吸収し、 色相のずれることがない。 特に好ましい有機染料の組合せは、 前記式 ( 1 ) ~ ( 4) の 4種類の染料を、 有機染料の混合物に占めるそれぞれの 染料の割合が、 式 ( 1 ) のべリノン系染料 2 0 - 6 0モル%、 式 ( 2 ) のアント ラキノン系染料 1 0〜3 0モル%、 式 (3 ) のアントラキノン系染料 1 0〜4 0 モル%および式 (4) のアントラキノン系染料 1 0〜3 0モル%となるように混 合したものである。 このような有機染料の混合物は、 前述の三原色の光の重畳部 分をほとんど透過させることなく、 明瞭な色相のコントラストを発現する。 最も 好ましい有機染料の組合せは、 式 (1 ) のペリノン系染料 3 0〜5 0モル%、 式 ( 2 ) のアントラキノン系染料 1 0〜2 0モル%、 式 ( 3 ) のアントラキノン系 染料 2 5〜 3 5モル%および式 ( 4) のアントラキノン系染料 1 0〜2 0モル% となるように混合したものである。 The organic dye in which at least two kinds of the above organic dyes are mixed absorbs evenly over the entire visible light range and does not shift in hue. Particularly preferred combinations of organic dyes are The ratio of each of the four dyes represented by the formulas (1) to (4) in the organic dye mixture is 20 to 60 mol% of the verinone dye represented by the formula (1), and the formula (2) Of the anthraquinone dye of the formula (3), from 10 to 40 mol% of the anthraquinone dye of the formula (3) and from 10 to 30 mol% of the anthraquinone dye of the formula (4). It was done. Such a mixture of organic dyes expresses a clear hue contrast with little transmission of the above-mentioned superimposed portion of the light of the three primary colors. The most preferred combinations of organic dyes are 30 to 50 mol% of the perinone dye of the formula (1), 10 to 20 mol% of the anthraquinone dye of the formula (2), and 25 to 50 mol% of the anthraquinone dye of the formula (3). ~ 35 mol% and an anthraquinone dye of the formula (4) in an amount of from 10 to 20 mol%.
有機染料の場合の特に好ましい添加量は、 二軸配向ポリエステルフィルムの厚 み方向に垂直な面の単位面積 (m2) 当り 0. 0 2 1〜0. 2 1 4 gである。 色素の添加方法としては、 エチレングリコールなどに分散、 溶解させてポリエ ステルの重合段階で添加してもよいが、 フィルムの生産性や異物の混入防止およ び工程の簡素化といった観点から、 フィルム添加濃度よりも高濃度の色素を添加 したポリエステル樹脂のペレットもしくは色素自体を溶融固化したペレツトを作 成し、 これらを混合して添加する方法が好ましい。 色素を溶融固化する際におい ては、 適宜バインダーを添加してもよい。 混合方法としては、 特に色素を溶融固 化したペレツトにおいては、 ポリエステル榭脂のペレットと機械的物性が異なる ので小型のフィーダにより添加する方法が好ましい。 フィーダによる添加量は、 押出機の容量および添加量によって変化するが、 設備上 0. 2〜2 0 k gZh力 ί 好ましい。 ポリエステルに添加する色素の性質としては、 生産性の観点からポリ エステルの押出時にポリエステル樹脂の粘度低下の少ない色素が好ましい。 また 溶融ポリエステル樹脂の粘度低下を抑える目的で押出機のせん断変形速度 Ί 0 ( 1 秒) において滞留時間は 2 0〜4 0 0 0秒が好ましい。 この値が 2 0以下 では色素の混練が十分でなく着色の斑がみられ、 一方 4 0 0 0秒以上では粘度の 低下による切断を招きやすくなる。 In the case of the organic dye, a particularly preferred addition amount is from 0.021 to 0.214 g per unit area (m 2 ) of a plane perpendicular to the thickness direction of the biaxially oriented polyester film. As a method for adding the pigment, the pigment may be dispersed and dissolved in ethylene glycol or the like and added at the polymerization stage of the polyester.However, from the viewpoints of film productivity, prevention of contamination of foreign substances, and simplification of the process, the film A method is preferred in which pellets of a polyester resin to which a dye is added at a higher concentration than the addition concentration or a pellet obtained by melting and solidifying the dye itself are mixed and added. In melting and solidifying the dye, a binder may be appropriately added. As a mixing method, particularly in a pellet obtained by melting and solidifying a coloring matter, a method of adding with a small feeder is preferable because mechanical properties are different from pellets of polyester resin. The addition amount by the feeder varies depending on the capacity and the addition amount of the extruder, but is preferably 0.2 to 20 kgZh force on the equipment. As the properties of the dye to be added to the polyester, from the viewpoint of productivity, a dye which causes little decrease in the viscosity of the polyester resin during extrusion of the polyester is preferable. In order to suppress a decrease in the viscosity of the molten polyester resin, the residence time is preferably 20 to 400 seconds at a shear deformation rate of the extruder of 0 (1 second). When this value is less than 20, the pigment is not sufficiently kneaded and uneven coloring is observed. On the other hand, when the value is more than 400 seconds, cutting due to a decrease in viscosity is liable to occur.
本発明における二軸配向ポリエステルフィルムを構成するポリエステルは、 芳 香族二塩基酸またはそのエステル形成性誘導体と、 ジオールまたはそのエステル 形成性誘導体とから合成される線状飽和ポリエステルである。 かかるポリエステ ルの具体例として、ポリエチレンテレフタレート、ポリエチレンイソフタレート、The polyester constituting the biaxially oriented polyester film in the present invention is preferably It is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof, and a diol or an ester-forming derivative thereof. Specific examples of such a polyester include polyethylene terephthalate, polyethylene isophthalate,
—ト、 ポリプチレンテレフタレー卜、 ポリ (1, 4— —Polybutylene terephthalate, poly (1, 4—
-卜)、ポリエチレン一 2 , 6—ナフタレ ンジカルボキシレ一ト等が例示できる。 これらの共重合体あるいはプレンドであ つてもよい。 これらのなかでも、 ポリエステルの重量を基準として、 7 0重量% 以上がェチレンテレフタレートまたはェチレン一 2, 6—ナフタレンジカルポキ シレートからなるものが好ましく、 特に二軸配向ポリエステルフィルムとした際 の加工性や透明性からエチレンテレフ夕レートを主たる繰返し単位とするポリェ ステルが好ましい。  And polyethylene-1,2,6-naphthalene dicarboxylate. These copolymers or blends may be used. Among them, those comprising at least 70% by weight of ethylene based on the weight of the polyester are preferably made of ethylene terephthalate or ethylene 1,6-naphthalenedicarboxylate. Particularly, the processability of a biaxially oriented polyester film is preferred. From the viewpoint of transparency and transparency, polyester having ethylene terephthalate as a main repeating unit is preferable.
主たる繰返し単位がェチレンテレフ夕レートからなるポリエステルの共重合成 分は、 ジカルボン酸成分として例えばイソフタル酸、 フタル酸、 2, 6—ナフタ レンジカルボン酸のごとき芳香族ジカルボン酸、 アジピン酸、 ァゼライン酸、 セ バシン酸、 デカンジカルボン酸のごとき脂肪族ジカルボン酸、 シクロへキサンジ カルボン酸のごとき脂環族ジカルボン酸等が例示できる。 またジオール成分とし て例えば 1, 4一ブタンジオール、 1 , 6—へキサンジォ一ル、 ジエチレングリ コールのごとき脂肪族ジォ一ル、 1 , 4ーシクロへキサンジメタノールのごとき 脂環族ジオール、 ビスフエノール Aのごとき芳香族ジオールが、例示できる。 これ らの共重合成分は単独でも二種以上併用してもよい。これらの共重合成分のうち、 加工性や透明性などの観点からイソフタル酸が特に好ましい。  Copolysynthetic components of polyesters whose main repeating unit is ethylene terephthalate include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, azelaic acid, and Examples thereof include aliphatic dicarboxylic acids such as basic acid and decane dicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Examples of the diol component include alicyclic diols such as 1,4-butanediol, 1,6-hexanediol, aliphatic diols such as diethylene glycol, and 1,4-cyclohexanedimethanol, and bis-diols. Aromatic diols such as phenol A can be exemplified. These copolymer components may be used alone or in combination of two or more. Among these copolymer components, isophthalic acid is particularly preferred from the viewpoint of processability and transparency.
共重合成分の割合は、 その種類にもよるが、 結果としてポリマーの融点が 2 3 0〜2 5 8 °Cになる割合であることが好ましい。 融点が 2 3 0 °C未満では耐熱性 や機械的強度が劣ることがある。 このようなポリエステルとしては、 エチレンテ レフ夕レートを主たる繰返し単位としそして共重合成分をイソフタル酸とする場 合、 酸成分のモル数を基準としてィゾフタル酸の割合を 1 2 m o 1 %以下にすれ ばよい。 ここで、ポリエステルの融点測定は、 D u P o n t I n s t r um e n t s 9 1 0 D S Cを用い、昇温速度 2 0 /分で融解ピークを求める方法による。 なおサンプル量は 2 O m gとする。 The proportion of the copolymer component depends on the type thereof, but is preferably a proportion that results in a melting point of the polymer of 230 to 258 ° C. If the melting point is lower than 230 ° C, heat resistance and mechanical strength may be poor. In the case of such a polyester, when ethylene terephthalate is used as the main repeating unit and the copolymer component is isophthalic acid, the ratio of azophthalic acid is set to 12 mol 1% or less based on the number of moles of the acid component. Good. Here, the melting point of the polyester is measured by a method in which a melting peak is obtained at a heating rate of 20 / min using DuPont Instrument 910 DSC. The sample amount is 2 O mg.
本発明の二軸配向ポリエステルフィルムを構成するポリエステルの固有粘度 (オルトクロ口フエノール、 3 5 °C) は 0 . 5 2〜1 . 5 0であることが好まし く、 さらに好ましくは 0 . 5 7〜: L . 0 0、 特に好ましくは 0 . 6 0〜0 . 8 0 である。 この固有粘度が 0 . 5 2未満の場合には製膜性が不良であることがあり 好ましくない。他方、固有粘度が 1 . 5 0を超えると、成形加工性が損われたり、 押出機に過負荷をかけたり、 さらには樹脂温度の過上昇によって固有粘度が著し く低下する場合があるので好ましくない。  The intrinsic viscosity (orthochlorophenol, 35 ° C.) of the polyester constituting the biaxially oriented polyester film of the present invention is preferably 0.52 to 1.5, more preferably 0.57. ~: L.0.0, particularly preferably 0.60 to 0.80. If the intrinsic viscosity is less than 0.52, the film-forming properties may be poor, which is not preferable. On the other hand, if the intrinsic viscosity exceeds 1.50, the molding processability may be impaired, the extruder may be overloaded, or the intrinsic viscosity may decrease significantly due to an excessive rise in the resin temperature. Not preferred.
上述のポリエステルは、 それ自体公知の方法によって製造でき、 例えば、 テレ フタル酸、 エチレングリコール、 要すれば共重合成分 (例えばイソフタル酸) を エステル化反応させ、 ついで得られた反応生成物を目的とする重合度になるまで 重縮合反応させてポリエステルとする方法、 または、 テレフ夕ル酸ジメチルエス テル、 エチレングリコール、 要すれば共重合成分 (例えばイソフタル酸ジメチル エステル) をエステル交換反応させ、 ついで得られた反応生成物を目的とする重 合度になるまで重縮合反応させてポリエステルとする方法を好ましく挙げること ができる。 勿論、 要すれば、 酸成分に 2, 6—ナフ夕レンジカルボン酸またはグ リコール成分に 1, 4ーシクロへキサンジメタノールを用いることができる。 上 記の方法 (溶融重合) により得られたポリエステルは、 必要に応じて固相状態で の重合方法 (固相重合) により、 さらに重合度の高いポリマーとすることができ る。  The polyesters described above can be produced by a method known per se, for example, by subjecting terephthalic acid, ethylene glycol and, if necessary, a copolymerization component (eg, isophthalic acid) to an esterification reaction, and then subjecting the resulting reaction product to To obtain a polyester by a polycondensation reaction until the degree of polymerization reaches a desired degree of polymerization, or a transesterification reaction of dimethyl ester terephthalate, ethylene glycol and, if necessary, a copolymer component (eg, dimethyl isophthalate). A method in which the obtained reaction product is subjected to a polycondensation reaction until a desired degree of polymerization is obtained to obtain a polyester can be preferably exemplified. Of course, if necessary, 2,6-naphthylenedicarboxylic acid for the acid component or 1,4-cyclohexanedimethanol for the glycol component can be used. The polyester obtained by the above method (melt polymerization) can be converted into a polymer having a higher degree of polymerization by a polymerization method in a solid state (solid state polymerization), if necessary.
そして、 このようにして得られたポリエステルは、 それ自体公知の製膜方法、 すなわち、 ポリエステルを溶融状態にしてから線状のダイより押出して、 未延伸 フィルムとし、 これを延伸、 熱処理する方法により二軸配向ポリエステルフィル ムとすることができる。  The polyester thus obtained is subjected to a film-forming method known per se, that is, a method in which the polyester is melted and then extruded from a linear die to form an unstretched film, which is stretched and heat-treated. It can be a biaxially oriented polyester film.
本発明の二軸配向ポリエステルフィルムは、 紫外線吸収剤を含有することがで ぎる。  The biaxially oriented polyester film of the present invention can contain an ultraviolet absorber.
一般に、 光学用フィルムは主として屋内で用いられるので、 紫外線による劣ィ匕 の問題はない。 しかし、 長期間窓際などの位置で使用すると、 窓越しの紫外線に よってフィルムの劣化が進み、 色素も徐々に劣化退色して映像のコントラストを 低下させる場合がある。 そのため、 二軸配向ポリエステルフィルムに紫外線吸収 剤を含有させることは、 ポリエステルおよび色素の劣化を防止できることから、 好ましい態様である。 紫外線吸収剤としては、 例えば下記式 (5) In general, since optical films are mainly used indoors, there is no problem of inferiority due to ultraviolet rays. However, if it is used for a long period of time near a window, for example, Therefore, the deterioration of the film progresses, and the pigment gradually deteriorates and fades, sometimes lowering the contrast of the image. Therefore, it is a preferable embodiment to include an ultraviolet absorber in the biaxially oriented polyester film since deterioration of the polyester and the dye can be prevented. As the ultraviolet absorber, for example, the following formula (5)
Figure imgf000011_0001
Figure imgf000011_0001
(式中、 XQ1は上記式に表された XG1からの 2本の結合手が 1位、 2位の位置関 係にある、 2価の芳香族残基であり; nは 1、 2または 3であり; RQ1は n価の 炭化水素残基で、 これはさらにへテロ原子を含有していてもよい、 または RQ1は n= 2のとき直接結合であることができる。) ( Wherein , X Q1 is a divalent aromatic residue in which the two bonds from X G1 represented by the above formula are in the 1-position and 2-position relations; n is 1, 2 Or 3; R Q1 is an n-valent hydrocarbon residue, which may further contain a heteroatom, or R Q1 can be a direct bond when n = 2.)
および下記式 (6) And the following equation (6)
Figure imgf000011_0002
Figure imgf000011_0002
(式中、 Aは下記式 (7) で表される基であるかまたは下記式 (8)
Figure imgf000011_0003
(Wherein A is a group represented by the following formula (7) or
Figure imgf000011_0003
、 (8)  , (8)
R 03 で表される基であり;RQ2および R°3は同一もしくは異なり 1価の炭化水素残基 であり; XQ 2は 4価の芳香族残基で、 これはさらにへテロ原子を含有していても よい。) で表される環状ィミノエステルから選ばれる少なくとも 1種の化合物を、 未反応 の形態で用いるのが好ましい。 かかる環状ィミノエステルは紫外線吸収剤として 公知の化合物であり、 例えば特開昭 59—12952号公報に記載されている。 前記一般式 (5) 中、 XQ1は式 (5) に表された XQ1からの 2本の結合手が 1 位、 2位の位置関係にある 2価の芳香族残基であり; nは 1、 2または 3であり ;R Q2 and R ° 3 are the same or different and are monovalent hydrocarbon residues; X Q 2 is a tetravalent aromatic residue, which further contains a heteroatom. May be contained. ) It is preferable to use at least one compound selected from the cyclic imino esters represented by the following formulas in an unreacted form. Such a cyclic imino ester is a compound known as an ultraviolet absorber, and is described, for example, in JP-A-59-12952. In the general formula (5), X Q1 is a divalent aromatic residue in which the two bonds from X Q1 represented by the formula (5) are in the first and second positions; n Is 1, 2 or 3;
RQ1は n価の炭化水素残基で、 これはさらにへテロ原子を含有していてもよい、 または RQ1は n= 2のとき直接結合であることができる。 R Q1 is an n-valent hydrocarbon residue, which may further contain a heteroatom, or R Q1 can be a direct bond when n = 2.
X01としては、 好ましくは例えば 1, 2—フエ二レン、 1, 2—ナフチレン、X 01 is preferably, for example, 1,2-phenylene, 1,2-naphthylene,
2, 3 _ナフチレン、 下記式 (9) (9)2, 3 _ naphthylene, following formula (9) (9)
Figure imgf000012_0001
Figure imgf000012_0001
(式中、 Rは一 O—、 一CO—、 — S―、 一 S02—、 一 CH2_、 - (CH2) 2 —または一 C (CH3) 2—である。) (Wherein, R one O-, one CO-, - S-, one S0 2 -, one CH 2 _, - (CH 2 ) 2 - or a C (CH 3) 2 - and it is.)
で表される基を挙げることができる。 これらのうち、 特に 1, 2—フエ二レンが 好ましい。 And the group represented by Of these, 1,2-phenylene is particularly preferred.
XQ1について例示した上記芳香族残基は、例えば炭素数 1〜10のアルキル例 えばメチル、 ェチル、 プロピル、 へキシル、 デシル等;炭素数 6〜 12のァリー ル例えばフエニル、 ナフチル等;炭素数 5〜12のシクロアルキル例えばシク口 ペンチル、 シクロへキシル等;炭素数 8〜 20のァラルキル例えばフエ二ルェチ ル等;炭素数 1〜 10のアルコキシ例えばメトキシ、 Xトキシ、デシルォキシ等; ニトロ;ハロゲン例えば塩素、臭素等;炭素数 2〜 10のァシル例えばァセチル、 プロボニル、ゼンゾィル、デカノィル等;などの置換基で置換されていてもよい。 The aromatic residues exemplified for X Q1, for example an alkyl example when methyl having 1 to 10 carbon atoms, Echiru, propyl, hexyl, decyl and the like; Ari Le e.g. phenyl carbon number 6-12, naphthyl; number of carbon atoms 5 to 12 cycloalkyl such as pentyl pentyl, cyclohexyl and the like; aralkyl having 8 to 20 carbon atoms such as phenylethyl and the like; alkoxy having 1 to 10 carbon atoms such as methoxy, X toxic, decyloxy and the like; nitro; halogen such as It may be substituted with a substituent such as chlorine, bromine or the like; an acyl having 2 to 10 carbon atoms such as acetyl, proponyl, zenzyl, decanoyl and the like.
R01は n価 (ただし、 nは 1、 2または 3である) の炭化水素残基であるか、 または nが 2であるときに限り直接結合であることができる。 R 01 can be an n-valent (where n is 1, 2 or 3) hydrocarbon residue, or can be a direct bond only when n is 2.
1価の炭化水素残基 (n=lの場合) としては、 第 1に、 例えば炭素数 1〜1 0の未置換脂肪族基、 炭素数 6〜 12の未置換芳香族基、 炭素数 5〜 12の未置 換脂環族基が挙げられる。 炭素数 1〜: L 0の未置換脂肪族基としては、例えばメチル、ェチル、プロピル、 へキシル、 デシル等を、 炭素数 6〜12の未置換芳香族基としては、 例えばフエ ニル、 ナフチル、 ビフエエル等を;炭素数 5〜12の未置換脂環族基としては、 例えばシクロペンチル、 シクロへキシル等を挙げることができる。 As the monovalent hydrocarbon residue (when n = l), first, for example, an unsubstituted aliphatic group having 1 to 10 carbon atoms, an unsubstituted aromatic group having 6 to 12 carbon atoms, and 5 carbon atoms To 12 unsubstituted alicyclic groups. C1-C: Unsubstituted aliphatic groups having L0 include, for example, methyl, ethyl, propyl, hexyl, decyl and the like; unsubstituted aromatic groups having 6-12 carbons include, for example, phenyl, naphthyl, Examples of the unsubstituted alicyclic group having 5 to 12 carbon atoms include cyclopentyl and cyclohexyl.
また、 上記 1価の炭化水素残基としては、 第 2に、 例えば下記式 (10)
Figure imgf000013_0001
In addition, as the above monovalent hydrocarbon residue, secondly, for example, the following formula (10)
Figure imgf000013_0001
(式中、 RQ4は炭素数 2〜10のアルキレン、 フエ二レンまたはナフチレンであ る。) (Wherein, R Q4 is alkylene, phenylene, or naphthylene having 2 to 10 carbon atoms.)
で表される基、 下記式 (11)
Figure imgf000013_0002
(式中、 1^5は炭素数1へ 0のアルキル基、 フエニル基またはナフチル基であ る。)
A group represented by the following formula (11)
Figure imgf000013_0002
(In the formula, 1 ^ 5 is an alkyl group having 1 to 0 carbon atoms, a phenyl group or a naphthyl group.)
で表される基、 下記式 (12)
Figure imgf000013_0003
A group represented by the following formula (12)
Figure imgf000013_0003
(式中、 RQ4および RQ5の定義は上記に同じであり、 RQ6は水素原子または R0 5に定義された基のいずれかである。) _ (Wherein definitions of R Q4 and R Q5 is as defined above, R Q6 is any of the groups defined for hydrogen atom or R 0 5.) _
で表される基、 下記式 (13)
Figure imgf000013_0004
A group represented by the following formula (13)
Figure imgf000013_0004
(式中、 RQ4および RG6の定義は上記に同じであり、 1^7は水素原子または1^ 5に定義された基のいずれかである。) で表される置換された脂肪族残基または芳香族残基を挙げることができる。 (Wherein the definitions of R Q4 and R G6 are the same as above, and 1 ^ 7 is either a hydrogen atom or a group defined as 1 ^ 5. ) And a substituted aliphatic residue or aromatic residue represented by
また、 上記 1価の炭化水素残基としては、 第 3に、 上記未置換の芳香族残基が 例えば上記 X 01を表す芳香族残基の置換基として例示したと同じ置換基で置換 されているものを挙げることができる。 それ故、 かかる置換基で置換された場合 の例としては、 例えばトリル、 メチルナフチル、 ニトロフエニル、 ニトロナフチ ル、 クロ口フエニル、 ベンゾィルフエニイル、 ァセチルフエニルまたはァセチル ナフチル等を挙げることができる。 Moreover, as the monovalent hydrocarbon residue, in the third, is substituted by the same substituents as the aromatic residue of the unsubstituted, for example, exemplified as the substituent of the aromatic residues representing said X 01 Can be mentioned. Therefore, examples of substitution with such a substituent include, for example, tolyl, methylnaphthyl, nitrophenyl, nitronaphthyl, chlorophenyl, benzoylphenyl, acetylphenyl or acetylnaphthyl.
1価の炭化水素残基としては、 上記式 (10)、 (11)、 (12) または (13) で表される基、 すなわち置換された脂肪族残基または芳香族残基、 特にそのうち 置換された芳香族残基が好ましい。  As the monovalent hydrocarbon residue, a group represented by the above formula (10), (11), (12) or (13), that is, a substituted aliphatic residue or aromatic residue, Preferred are aromatic residues.
2価の炭化水素残基 (n = 2の場合) としては、 第 1に、 例えば 2価の、 炭素 数 2〜10の未置換の脂肪族残基、 炭素数 6〜12の未置換の芳香族残基、 炭素 数 5〜 12の未置換の脂環族残基基が挙げられる。  As divalent hydrocarbon residues (when n = 2), first, for example, divalent, unsubstituted aliphatic residues having 2 to 10 carbon atoms, unsubstituted aromatics having 6 to 12 carbon atoms Group, an unsubstituted alicyclic group having 5 to 12 carbon atoms.
2価の炭素数 2〜10の未置換の脂肪族基としては、 例えばエチレン、 トリメ チレン、 テトラメチレン、 デカメチレン等を、 2価の炭素数 6〜12の未置換の 芳香族残基としては、 例えばフエ二レン、 ナフチレン、 P, P' ービフエ二レン 等を; 2価の炭素数 5〜12の未置換の脂環族残基としては、 例えばシクロペン チレン、 シクロへキシレン等を挙げることができる。  Examples of the divalent unsubstituted aliphatic group having 2 to 10 carbon atoms include ethylene, trimethylene, tetramethylene, and decamethylene.Examples of the unsubstituted aromatic residue having 2 to 6 carbon atoms include divalent unsubstituted aromatic groups. Examples include phenylene, naphthylene, P, P'-biphenylene, and the like. Examples of the divalent unsubstituted alicyclic group having 5 to 12 carbon atoms include, for example, cyclopentylene, cyclohexylene, and the like. .
また、 上記 2価の炭化水素残基としては、 第 2に、 例えば下記式 (1 )
Figure imgf000014_0001
Also, as the divalent hydrocarbon residue, secondly, for example, the following formula (1)
Figure imgf000014_0001
(式中、 RQ8は RQ4に定義された基のいずれかである。) (Wherein R Q8 is any of the groups defined for R Q4 .)
で表される基、 または下記式 (15)
Figure imgf000014_0002
Or a group represented by the following formula (15)
Figure imgf000014_0002
(式中、 RQ 8の定義は上記に同じであり、 RQ9は RQ4に定義された基のいずれか であり、 そして R。1Qは RQ6に定義された基のいずれかである。) (Wherein, the definition of R Q 8 is the same as above, and R Q9 is any of the groups defined for R Q4 And R. 1Q is any of the groups defined in RQ6 . )
で表される置換された脂肪族残基または芳香族残基を挙げることができる。 And a substituted aliphatic residue or aromatic residue represented by
また、 上記 2価の炭化水素残基としては、 第 3に、 上記未置換の 2価の芳香族 残基が、例えば上記 X 01を表す芳香族基の置換基として例示したと同じ置換基で 置換されているものを挙げることができる。 Further, as the divalent hydrocarbon residue, a third, a divalent aromatic residue of the non-substituted, for example by the same substituents as exemplified as the substituent for the aromatic group represented by the X 01 Substituted ones can be mentioned.
nが 2の場合には、 Rfllとしては、 これらのうち直接結合または上記第 1〜第 3の群の未置換または置換された 2価の芳香族炭化水素残基が好ましく、 特に 2 本の結合手が最も離れた位置から出ている第 1または第 3の群の未置換または置 換された芳香族炭化水素残基が好ましぐ就中 p—フエ二レン、 p, p, ービフエ 二レンまたは 2, 6—ナフチレンが好ましい。 When n is 2, R fll is preferably a direct bond or an unsubstituted or substituted divalent aromatic hydrocarbon residue of the above-described first to third groups. Unsubstituted or substituted aromatic hydrocarbon residues of the first or third group in which the bond comes from the furthest position are preferred, especially p-phenylene, p, p, -biphenyl Rene or 2,6-naphthylene is preferred.
3価の炭化水素残基 (n = 3の場合) としては、 例えば 3価の炭素数 6〜: L 2 の芳香族残基を挙げることができる。  Examples of the trivalent hydrocarbon residue (when n = 3) include, for example, a trivalent aromatic residue having 6 to 6 carbon atoms: L 2.
かかる芳香族残基としては、 例えば下記式 (16)  As such an aromatic residue, for example, the following formula (16)
Figure imgf000015_0001
Figure imgf000015_0001
等を挙げることができる。 And the like.
かかる芳香族残基は、 上記 1価の芳香族残基の置換基として例示したと同じ置 換基で置換されていてもよい。  Such an aromatic residue may be substituted with the same substituent as exemplified as the substituent for the monovalent aromatic residue.
上記一般式 (5) 中、 R02および R03は同一もしくは異なり 1価の炭化水素残 基であり、 X02は 4価の芳香族炭化水素残基である。 In the above general formula (5), R 02 and R 03 are the same or different and are monovalent hydrocarbon residues, and X 02 is a tetravalent aromatic hydrocarbon residue.
R02および R03としては、 上記式 (I) の説明において、 n=lの場合の R0 1について例示したと同じ基を例として挙げることができる。 The R 02 and R 03, may be mentioned in the description of the formula (I), the same groups as exemplified for R 0 1 in the case of n = l as an example.
4価の芳香族炭化水素残基としては、 例えば下記式 (17) As the tetravalent aromatic hydrocarbon residue, for example, the following formula (17)
Figure imgf000016_0001
Figure imgf000016_0001
(ここで、 R0の定義は式 (9) に同じ。) (Here, the definition of R 0 is the same as equation (9).)
で表される基を挙げることができる。 And the group represented by
上記 4価の芳香族残基は、 上記式 (5) の説明において、 尺 を表す丄価の芳 香族残基の置換基として例示したと同じ置換基で置換されていてもよい。  The tetravalent aromatic residue may be substituted with the same substituent as that exemplified for the trivalent aromatic residue representing the length in the description of the above formula (5).
本発明において用いられる上記式 (5) および (6) で表される環状イミノエ ステルの具体例としては、 例えば下記の化合物を挙げることができる。  Specific examples of the cyclic iminoester represented by the above formulas (5) and (6) used in the present invention include the following compounds.
上記式 (5) の n=lの場合の化合物  Compound of the above formula (5) when n = l
2—メチルー 3, 1一べンゾォキサジン一 4一オン、 2—ブチル—3, 1一べ ンゾォキサジン一 4一オン、 2 _フエ二ルー 3, 1一べンゾォキサジン一 4一才 ン、 2— (1一または 2—ナフチル) 一 3, 1一べンゾォキサジン一 4一オン、 2- (4ービフエニル) 一 3, 1—べンゾォキサジン一 4一オン、 2— p—二ト 口フエニル _ 3, 1一べンゾォキサジン一 4一オン、 2— m—二トロフエ二ルー 3, 1—ベンゾォキサジン一 4一オン、 2— p—ベンゾィルフエ二ルー 3, 1一 ベンゾォキサジン一 4一オン、 2— p—メ卜キシフエ二ルー 3, 1—ベンゾォキ サジン一 4—オン、 2— o—メトキシフエ二ルー 3, 1一べンゾォキサジン一 4 —オン、 2—シクロへキシルー 3, 1—べンゾォキサジン一 4—オン、 2— p— (または m— ) フタルイミドフエ二ルー 3, 1—べンゾォキサジン— 4一オン、 N—フエ二ルー 4— (3, 1一べンゾォキサジン一 4—オン— 2—ィル) フタル イミド、 N—ベンゾィル一4一 (3, 1一べンゾォキサジン一 4—オン一 2—ィ ル) ァニリン、 N—ベンゾィル一N—メチル一4一 (3, 1—ベンゾォキサジン —4一オン一 2—ィル) ァニリン、 2— (p— (N—メチルカルポニル) フエ二 ル) 一 3, 1—べンゾォキサジン一 4一オン。 2-Methyl-3,1 benzoxazine-1 4-one, 2-butyl-3,1 benzoxazine-1 4-one, 2-phenyl-3,1 benzoxazine-1,4-one, 2- (1 1- or 2-naphthyl) 1,3,1 Benzoxazine 1-one, 2- (4-biphenyl) 1,3,1-Benzoxazine 1-41-one, 2-p-Nito-mouth phenyl 3,1,1 Nzoxazine 1-one, 2-m-Nitrophen-2,3,1-Benzoxazine 1-4-one, 2-p-Benzoyl-phen-3,1-1 Benzoxazine 1-41-on, 2-p-Methoxyx2 3, 1-Benzoxazin-1 4-one, 2-o-Methoxyphenyl 3, 1-Benzoxazine 1-4-one, 2-Cyclohexyl-3,1-benzoxazine-1 4-one, 2-p- (Or m—) phthalimide phenyl 2,1-benzoxazine—41 on, N—phenyl 4— (3,1 benzoxazine-14-on—2-yl) phthalimide, N-benzoyl 1-41 (3,1 Benzoxazine-1-4-one-2-yl) aniline, N-benzoyl-1-N-methyl-14- (3,1-benzoxazine-4-1-one-2-yl) aniline, 2— (p— (N-methylcarbonyl) phenyl) 1,3,1-benzoxazine-14-one.
上記式 (5) の n= 2の場合の化合物  Compound of the above formula (5) when n = 2
2, 2, 一ビス (3, 1—べンゾォキサジン一 4一オン)、 2, 2, 一エチレン ビス(3, 1—ベンゾォキサジン一 4 _オン)、 2, 2,一テトラメチレンビス(3, 1—ベンゾォキサジン一 4一オン)、 2, 2' —デカメチレンビス (3, 1一ベン ゾォキサジン一 4一オン)、 2, 2 ' —p—フエ二レンビス (3, 1一ベンゾォキ サジン— 4一オン)、 2, 2 ' 一 m—フエ二レンビス (3, 1_ベンゾォキサジン 一 4一オン)、 2, 2, 一 (4, 4, ージフエ二レン) ビス (3, 1一ベンゾォキ サジン一 4一オン)、 2, 2' 一 (2, 6—または 1, 5—ナフチレン) ビス (3, 1—ベンゾォキサジン一 4一オン)、 2, 2, 一 (2—メチル フエ二レン) ビス (3, 1一べンゾォキサジン一 4一オン)、 2, 2, ― (2—ニトロ一 p—フ ェニレン) ビス (3, 1一べンゾォキサジン一 4一オン)、 2, 2, 一 (2 -クロ 口一 p—フエ二レン) ビス (3, 1—ベンゾォキサジン—4 _オン)、 2, 2, 一 (1, 4ーシクロへキシレン) ビス (3, 1—ベンゾォキサジン一 4一オン)、 N -P- (3, 1一べンゾォキサジン一 4一オン一 2—ィル)フエニル、 4- (3, 1—ベンゾォキサジン— 4一オン一 2—ィル) フタルイミド、 N-P- (3, 1 一べンゾォキサジン— 4一オン— 2 _ィル) ベンゾィル、 4一 (3, 1—ベンゾ ォキサジン一 4一オン一 2—ィル) ァニリン。  2,2,1-bis (3,1-benzoxazine-1-one), 2,2,1-ethylenebis (3,1-benzoxazin-1-one), 2,2,1-tetramethylenebis (3,1 —Benzoxazine-1 4-one), 2, 2 '—Decamethylenebis (3,1-benzoxazine-1 41-one), 2, 2' —p-Phenylenebis (3,1-benzoxazine) —4-one ), 2,2'-m-phenylenebis (3,1_benzoxazine-1 4-one), 2,2,1- (4,4, diphenylene) bis (3,1-benzoxazine-1-4one) ), 2,2 '-(2,6- or 1,5-naphthylene) bis (3,1-benzobenzoxazine-one), 2,2,1- (2-methylphenylene) bis (3,1 1,2,1- (2-nitro-p-phenylene) bis (3,1-benzoxazine-1 4-one), 2,2,1- (2-k P-phenylene) bis (3,1-benzoxazine-4-one), 2,2,1- (1,4-cyclohexylene) bis (3,1-benzoxazine-1-one), N-P -(3,1 Benzoxazine-1 4-one-1-2-yl) phenyl, 4- (3,1-Benzoxazine- 4-one-1-2-yl) phthalimide, NP- (3,1 Benzoxazine) 4-one—2-yl) benzoyl, 4-one (3,1-benzoxazine-41-one-2-yl) aniline.
上記式 (5) の n= 3の場合の化合物  Compound of the above formula (5) when n = 3
1, 3, 5 _トリ (3, 1一べンゾォキサジン一 4一オン— 2—ィル) ベンゼ ン、 1, 3, 5—トリ (3, 1—べンゾォキサジン一 4一オン一 2—ィル) ナフ タレン、 2, 4, 6—トリ (3, 1一べンゾォキサジン一 4—オン一 2—^ Γル) 上記式 (6) の化合物 1,3,5-tri (3,1 benzoxazine-1 4-one-on-2-yl) Benzene, 1,3,5-tri (3,1-benzoxazine-1 4-1-on-2-yl) ) Naphthalene, 2,4,6-tri (3,1 benzoxazin-14-one-1 2- ^ Γ) Compound of the above formula (6)
2, 8—ジメチルー 4 H, 611—べンゾ(1, 2— d ; 5, 4一 d') ビス(1, 3)—ォキサジン— 4, 6—ジオン、 2, 7—ジメチルー 4 H, 9H—べンゾ(1, 2-d; 4, 5-d') ビス (1, 3) —ォキサジン一 4, 9ージオン、 2, 8— ジフエ二ルー 4H, 8H—べンゾ(1, 2-d; 5, 4一 d,) ビス (1, 3) — ォキサジン一 4, 6—ジオン、 2, 7—ジフエ二ルー 4 H, 9H—ベンゾ (1, 2-d; 4, 5-d') ビス (1, 3) —ォキサジン一 4, 6—ジオン、 6, 6 ' 一ビス (2—メチルー 4H, 3, 1—べンゾォキサジン一 4—オン)、 6, 6, — ビス (2—ェチルー 4 H, 3, 1—ベンゾォキサジン— 4一オン)、 6, 6, ービ ス (2—フエ二ルー 4 H, 3, 1一べンゾォキサジン一 4一オン)、 6, 6, ーメ チレンビス(2—メチルー 4H, 3, 1一べンゾォキサジン一 4一オン)、 6, 6' ーメチレンビス (2—フエニル— 4H, 3, 1—ベンゾォキサジン一 4一オン)、 6, 6' —エチレンビス (2—メチルー 4H, 3, 1一べンゾォキサジン一 4一 オン)、 6, 6, 一エチレンビス (2—フエ二ルー 4H, 3, 1—ベンゾォキサジ ンー 4一オン)、 6, 6 ' —ブチレンビス (2—メチル _4H, 3, 1一べンゾォ キサジン一 4—オン)、 6, 6' —ブチレンビス (2—フエ二ルー 4H, 3, 1一 ベンゾォキサジン一 4一オン)、 6, 6' 一ォキシビス (2—メチルー 4H, 3, 1一べンゾォキサジン一 4一オン)、 6, 6'—ォキシビス(2—フエニル— 4H, 3, 1 _ベンゾォキサジン一 4一オン)、 6, 6' —スルホニルビス (2—メチル 一 4H, 3, 1一べンゾォキサジン— 4一オン)、 6, 6' ースルホニルビス (2 一フエ二ルー 4 H, 3, 1一べンゾォキサジン一 4一オン)、 6, 6' 一力ルポ二 ルビス (2—メチル— 4H, 3, 1—ベンゾォキサジン一 4—オン)、 6, 6, 一 カルボニルビス (2—フエ二ルー 4H, 3, 1一べンゾォキサジン一 4一オン)、 7, 7, ーメチレンビス (2—メチル—4 H, 3, 1—ベンゾォキサジン一 4一 オン)、 7, 7 ' —メチレンビス (2—フエ二ルー 4H, 3, 1—べンゾォキサジ ンー 4—オン)、 7, 7 ' 一ビス (2—メチルー 4 H, 3, 1一べンゾォキサジン —4一オン)、 7, 7, 一エチレンビス (2—メチレ一 4H, 3, 1 _ベンゾォキ サジン一 4 _オン)、 7, 7' 一ォキシビス (2—メチルー 4H, 3, 1—ベンゾ ォキサジンー4一オン)、 , 7, ースルホニルビス (2—メチルー 4H, 3, 1 一べンゾォキサジン— 4—オン)、 7, 7 '—力ルポニルビス(2—メチル—4 H, 3, 1—ベンゾォキサジン一 4 _オン)、 6, 7,—ビス(2—メチル— 4H, 3, 1—ベンゾォキサジン一 4一オン)、 6, 7, —ビス (2—フエ二ルー 4H, 3, 1一べンゾォキサジン一 4—オン)、 6, 7,ーメチレンビス(2—メチル _4H, 3, 1一べンゾォキサジン一4—オン)、 6, 7' —メチレンビス (2—フエニル -4H, 3, 1—ベンゾォキサジン一 4—オン)。 2,8-Dimethyl-4H, 611-Venzo (1,2-d; 5,4-d ') Bis (1,3) -oxazine-4,6-dione, 2,7-Dimethyl-4H, 9H-Venzo (1,2-d; 4,5-d ') bis (1,3) -oxazine- 1,4,9-dione, 2,8-diphen-4u 4H, 8H-Venzo (1, 2-d; 5,4-d,) bis (1,3) -oxazine-1,4,6-dione, 2,7-diphenyl-4H, 9H-benzo (1,2-d; 4,5- d ') Bis (1, 3) -oxazine-1,4,6-dione, 6,6' Bis (2-methyl-4H, 3,1-benzoxazin-1-one), 6,6, —bis (2 —Ethyru 4 H, 3,1-Benzoxazine—4-one), 6,6, bis (2-Fenru 4H, 3,1 Benzoxazine—1-one), 6,6, Me Tylenebis (2-methyl-4H, 3,1 -benzoxazine-1 4-one), 6,6'-methylenebis (2-phenyl-4H, 3,1-ben) Oxazine 1 4-one), 6, 6'-Ethylenebis (2-methyl-4H, 3, 1-benzoxazine 1 4-one), 6, 6, 1-Ethylenebis (2-phenyl-4H, 3, 1) —Benzoxazine-4-one), 6, 6 '—butylenebis (2-methyl_4H, 3,1benzoxazine-1 4-one), 6, 6' —butylenebis (2-phenylene 4H, 3,1) 1-benzoxazine-1 4-one), 6,6'-oxybis (2-methyl-4H, 3,1-benzoxazine-1 4-one), 6,6'-oxybis (2-phenyl-4H, 3,1_benzoxazine) 1,4'one), 6,6'-Sulfonylbis (2-methyl-1 4H, 3,1'-benzoxazine--4'one), 6,6'-Sulfonylbis (2'-Fe2L4H, 3,1'1) Benzoxazine-1 4-one), 6,6'-Liponyl bis (2-methyl-4H, 3,1-benzoxazine-1 4- On), 6,6,1-carbonylbis (2-phenyl-4H, 3,1-benzoxazine-1 4-one), 7,7, -methylenebis (2-methyl-4H, 3,1-benzoxazine-1-4 7,7'-Methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7,7'-bis (2-methyl-4H, 3,1benzoxazine) 4,7-one-oxybis (2-methyl-4H, 3,1-benzo), 7,7,1-ethylenebis (2-methylene-4H, 3,1_benzoxazine) Oxazine-one),, 7, -sulfonylbis (2-methyl-4H, 3,1 benzoxazin-4-one), 7,7'-Ruponylbis (2-methyl-4H, 3,1-benzoxazine-1-4) _On), 6,7, -bis (2-methyl-4H, 3,1-benzoxazine-1 4-one), 6,7, -bis (2-phenyl-4H, 3,1 benzoxazine-1 4 —On), 6,7, -methylenebis (2-methyl_4H, 3,1-benzoxazin-14-one), 6,7'-methylenebis (2-phenyl-4H, 3,1-benzobenzoxazine-1-one) .
上記例示化合物のうち、 上記式 (5) の化合物、 より好ましくは n = 2の場合 の上記式 (5) の化合物、 特に好ましくは下記式 (18)  Among the above exemplified compounds, the compound of the above formula (5), more preferably the compound of the above formula (5) when n = 2, particularly preferably the following formula (18)
(18)(18)
Figure imgf000019_0001
Figure imgf000019_0001
(式中、 RQ 11は 2価の芳香族炭化水素残基である。) (In the formula, R Q 11 is a divalent aromatic hydrocarbon residue.)
で表される化合物が有利に用いられる。 The compound represented by is advantageously used.
式 (18) の化合物としては、 就中 2, 2' 一 p—フエ二レンビス (3, 1一 ベンゾォキサジン一 4一オン)、 2, 2' —(4, 4, 一ジフエ二レン) ビス(3, 1一べンゾォキサジン一 4一オン) および 2, 2' ― (2, 6—ナフチレン) ビ ス (3, 1一べンゾォキサジン一 4一オン) が好ましい。  Among the compounds of the formula (18) are, among others, 2,2′-p-phenylenebis (3,11-benzoxazine-14-one), 2,2 ′ — (4,4,1-diphenylene) bis ( Preferred are 3,1 benzoxazine and 4-one) and 2,2 '-(2,6-naphthylene) bis (3,1 benzoxazine).
これら環状ィミノエステルの紫外線吸収特性は、 例えばその代表的化合物につ いて特開昭 59- 12952号公報に記載されているので、 それを援用する。 前記環状ィミノエステルは、 ポリエステルに対して優れた相溶性を有するが、 前記特開昭 59 - 12952号公報や米国特許第 4291152号明細書に記載 されているように、ポリエステルの末端水酸基と反応する能力を有する。そこで、 環状ィミノエステルが実質的に未反応な状態で含有されるように、 環状ィミノエ ステルとポリエステルとを注意深く混合させることが求められる。 ただし、 ポリ エステルとして、 主たる割合の末端基がカルボキシル基であるポリエステルや、 末端水酸基が該環状ィミノエステルと反応性の無い末端封鎖剤で封鎖されている ポリエステルを用いる場合、 環状ィミノエステルを未反応の状態で含有する組成 物を製造するのに特別の注意を払う必要は無い。 主たる割合の末端基が水酸基で あるポリエステルを用いる場合には、 溶融混合の時間は、 以下の 2つの式 The UV-absorbing properties of these cyclic imino esters are described in, for example, JP-A-59-12952, which are representative compounds thereof, which are incorporated herein by reference. The cyclic imino ester has excellent compatibility with the polyester, but has the ability to react with the terminal hydroxyl group of the polyester as described in JP-A-59-12952 and US Pat. No. 4,291,152. Having. Therefore, it is necessary to carefully mix the cyclic imino ester and the polyester so that the cyclic imino ester is contained in a substantially unreacted state. However, as the polyester, the main proportion of the terminal group is a carboxyl group polyester or the terminal hydroxyl group is blocked with a terminal blocking agent that is not reactive with the cyclic imino ester. When polyester is used, no special precautions need to be taken to produce a composition containing the cyclic imino ester in an unreacted state. In the case of using a polyester having a major proportion of hydroxyl groups as terminal groups, the melt mixing time is calculated by the following two formulas.
1 o g t≤- 0 . 0 0 8 T + 4. 8  1 o g t≤- 0.0 .08 T +4.8
Tm<T< 3 2 0  Tm <T <3 2 0
(式中、 tは溶融混合時間(秒)、 Tは溶融混合温度 CO および Tmはポリエス テルの溶融温度 (°C) である。)  (Where t is the melt mixing time (seconds), T is the melt mixing temperature CO and Tm are the polyester melting temperatures (° C).)
を満足するように、 短時間で完了するようにするのが望ましい。 この場合、 環状 ィミノエステルとポリエステルとが少しの割合で反応する可能性があるが、 この 反応によってポリエステルの分子量は大きくなるので、 この割合によつては吸光 剤によるポリエステルの劣化による分子量低下を防ぐことが可能である。 なお、 環状ィミノエステルがポリエステルと反応した場合、 紫外線吸収波長領域が、 一 般に、 未反応の状態の紫外線吸収波長領域より低波長側にずれる傾向を示し、 そ れ故高波長側の紫外線を透過する傾向を有する。 It is desirable to complete it in a short time so that In this case, the cyclic imino ester and the polyester may react at a small ratio.However, this reaction increases the molecular weight of the polyester.According to this ratio, it is possible to prevent a decrease in the molecular weight due to the deterioration of the polyester due to the light absorbing agent. Is possible. When the cyclic iminoester reacts with the polyester, the ultraviolet absorption wavelength region generally shows a tendency to shift to a lower wavelength side than the unreacted ultraviolet absorption wavelength region, and therefore transmits the higher wavelength ultraviolet light. Have a tendency to
前記環状ィミノエステルは、 適量を添加する場合、 昇華物が殆どないので、 製 膜でダイ周辺を汚すことが少なく、 紫外線から 3 8 0 nm付近の光線を吸収する のでフィルムの着色が無く、 可視光線吸収剤やフィルムの劣化を防止する特性に 優れている。  When the cyclic imino ester is added in an appropriate amount, there is almost no sublimation, so that the periphery of the die is not stained by the film formation, and it absorbs the light near the wavelength of about 180 nm from ultraviolet rays, so that the film is not colored and visible light Excellent in preventing deterioration of absorbents and films.
前記紫外線吸収剤の添加量は、 ポリエステルに対し、 0 . 1 ~ 5重量%が好ま しく、 さらには 0 . 2〜3重量%が好ましぃ。 この量が 0 . 1 %未満では紫外線 劣化防止効果が小さく、 一方 5重量%を超えるとポリエステルの製膜特性が低下 し、 好ましくない。  The amount of the ultraviolet absorber added is preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, based on the polyester. If the amount is less than 0.1%, the effect of preventing ultraviolet light deterioration is small, while if it exceeds 5% by weight, the film-forming properties of the polyester deteriorate, which is not preferable.
上記紫外線吸収剤の添加は、 ポリエステルの重合時、 または溶融押出し時が好 ましく、 特に紫外線吸収剤をマスターペレットにして添加するのが好ましい。 また、 本発明で用いられるポリエステルの製造過程またはその後のダイより押 出すまでの過程で、 必要に応じて、 その他さらに、 酸化防止剤、 熱安定剤、 粘度 調整剤、 可塑剤、 色相改良剤、 滑剤、 核剤、 帯電防止剤、 酸化防止剤、 触媒など の添加剤を加えることができる。 上述のポリエステルにおける滑剤としては、 適 当な粗面化物質(フイラ一)を含有させることもできる。このフイラ一としては、 従来からポリエステルフィルムの滑り性付与剤として知られているものが用いら れる。 その例としては炭酸カルシウム、 酸ィ匕カルシウム、 酸化アルミニウム、 力 ォリン、 酸化珪素、 酸化亜鉛、 力一ボンブラック、 炭化珪素、 酸化錫、 架橋ァク リル樹脂粒子、 架橋ポリスチレン樹脂粒子、 メラミン樹脂粒子、 架橋シリコーン 樹脂粒子等が挙げられる。 これらの中でも、 透明性を保持しながら滑り性が得易 いことから、 平均粒径 l〜3 /mの多孔質シリカが好ましい。 多孔質シリカの添 加量は、 透明性と滑り性の観点から、 0. 0 1〜0. 0 0 5重量%が好ましぃ。 なお、 本発明の二軸配向ポリエステルフィルムの厚みは、 万一 C RTが爆縮した 場合にガラスの飛散を抑制できやすいことから 5 0 m以上であることが好まし い。 二軸配向ポリエステルフィルムの厚みの上限は、 ヘーズ値を 5 %以下に保ち やすくまたフィルムの生産性がよいことから 2 5 0 以下が好ましい。 The above-mentioned ultraviolet absorber is preferably added at the time of polymerization of polyester or at the time of melt extrusion, and it is particularly preferable to add the ultraviolet absorber in the form of master pellets. In addition, in the process of producing the polyester used in the present invention or in the subsequent process of extruding from the die, if necessary, further, an antioxidant, a heat stabilizer, a viscosity adjuster, a plasticizer, a hue improver, Additives such as lubricants, nucleating agents, antistatic agents, antioxidants, and catalysts can be added. Suitable lubricants for the above polyester Such a roughening substance (filament) can be contained. As the filler, those conventionally known as a slipperiness imparting agent for a polyester film are used. Examples include calcium carbonate, calcium oxide, aluminum oxide, aluminum oxide, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles. And cross-linked silicone resin particles. Among these, porous silica having an average particle size of l to 3 / m is preferred because it is easy to obtain slipperiness while maintaining transparency. The addition amount of the porous silica is preferably from 0.01 to 0.005% by weight from the viewpoint of transparency and slipperiness. In addition, the thickness of the biaxially oriented polyester film of the present invention is preferably 50 m or more because the scattering of glass can be easily suppressed in the event that the CRT is imploded. The upper limit of the thickness of the biaxially oriented polyester film is preferably 250 or less because the haze value is easily maintained at 5% or less and the productivity of the film is good.
また、 本発明の二軸配向ポリエステルフィルムは、 その長手方向および幅方向 の熱収縮率が 1 5 0 °Cで 3 0分間処理した際にそれぞれ 2 %以下であることが好 ましく、 より好ましい熱収縮率は 0〜: L . 5 %である。 上記熱収縮率が 2 %を超 えると光学用積層体形成時とくに反射防止層形成時の蒸着過程において、 熱変形 し、 平面性が損われやすく、 好ましくない。  Further, the biaxially oriented polyester film of the present invention preferably has a heat shrinkage in the longitudinal direction and width direction of 2% or less, respectively, when treated at 150 ° C. for 30 minutes, more preferably. The heat shrinkage is 0 to: 0.5%. If the above heat shrinkage exceeds 2%, it is not preferable because flattening is likely to occur due to thermal deformation in the vapor deposition process when forming the optical laminate, particularly when forming the antireflection layer.
本発明の二軸配向ポリエステルフィルムは映像表示面貼合せ用積層フィルムの ためのベースフィルムである。  The biaxially oriented polyester film of the present invention is a base film for a laminated film for laminating an image display surface.
次に、 上述の二軸配向ポリエステルフィルムの少なくとも片面に、 接着層を設 けた本発明の接着性フィルムについて詳述する。  Next, the adhesive film of the present invention in which an adhesive layer is provided on at least one surface of the above-mentioned biaxially oriented polyester film will be described in detail.
本発明の接着性フィルムは、 映像表示面貼合せ用積層フィルムを製造するため の中間製品に位置づけることができる。 映像表示面貼合せ用積層フィルムについ ては後述する。  The adhesive film of the present invention can be positioned as an intermediate product for producing a laminated film for laminating an image display surface. The laminated film for bonding the image display surface will be described later.
本発明の接着性フィルムを構成する接着層は、 水性ポリエステルと脂肪酸のァ ミドおよび Zまたは脂肪酸のビスアミドを主成分とする組成物からなることが好 ましい。 該接着層を形成する水性ポリエステルのガラス転移点 (T g) は、 好ま しくは 4 0〜8 5 °C、 より好ましくは 4 5〜8 0 である。 水性ポリエステルの ガラス転移点 (Tg) が 40°C未満の場合、 得られたフィルムは耐熱性が低くな つたり、耐ブロッキング性が低下し易い。他方、水性ポリエステルの Tgが 85°C を超えると接着性の向上効果が乏しくなる。 ここでいう水性ポリエステルとは、 水に可溶性または分散性のポリエステルである。 具体的には、 テレフタル酸、 ィ ソフタル酸、 フ夕ル酸、 2, 6—ナフタレンジカルボン酸、 へキサヒドロテレフ タル酸、 4, 4ージフエニルジカルボン酸、 フエニルインダンジカルボン酸、 ァ ジピン酸、 セバシン酸、 5— N aスルホイソフタル酸、 トリメリット酸、 ジメチ ロールプロピオン酸などの力ルポン酸成分とエチレングリコール、 ジエチレング リコール、 ネオペンチルダリコ一ル、 1, 4一ブタンジォ一ル、 1, 6—へキサ ンジォ一ル、 1, 4ーシク口へキサンジメ夕ノール、 グリセリン、 トリメチロー ルプロパン、 ビスフエノール Aのアルキレンォキシド付加物等のヒドロキシ化合 物成分とから製造されるポリエステルを挙げることができる。 また、 水性ポリェ ステルは、 さらに水との親和性を付与することが必要な場合、 ポリエステル中に S03N a基や COON a基を導入してもよく、 またポリエーテル成分を導入す ることもできる。 The adhesive layer constituting the adhesive film of the present invention is preferably composed of a composition mainly composed of an aqueous polyester and an amide of a fatty acid and Z or a bisamide of a fatty acid. The glass transition point (Tg) of the aqueous polyester forming the adhesive layer is preferably from 40 to 85 ° C, more preferably from 45 to 80 ° C. Water-based polyester When the glass transition point (Tg) is less than 40 ° C, the obtained film tends to have low heat resistance and low blocking resistance. On the other hand, when the Tg of the water-based polyester exceeds 85 ° C, the effect of improving the adhesiveness becomes poor. The aqueous polyester referred to here is a polyester soluble or dispersible in water. Specifically, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, 4,4-diphenyldicarboxylic acid, phenylindanedicarboxylic acid, adipic acid, sebacin Acids, 5-Na sulfoisophthalic acid, trimellitic acid, dimethylol propionic acid, etc., and sulfonic acid components and ethylene glycol, diethylene glycol, neopentyl diol, 1,4-butanediol, 1,6- Polyesters produced from hydroxy compound components such as hexanediol, 1,4-six-mouth hexanedimethanol, glycerin, trimethylolpropane, and alkylene oxide adducts of bisphenol A can be mentioned. Further, the aqueous Polje ester further if it is necessary to impart affinity for water may be introduced S0 3 N a group or COON a group in the polyester and to introduce the polyether component Rukoto Can also.
脂肪酸のアミドまたは脂肪酸のビスアミ
Figure imgf000022_0001
または C〇NHR3NHOCR2で表されるものであり、 1^(30—ぉょび1 2(:0_は脂 肪酸残基、 一 NHR3NH—はジァミン残基である。 この脂肪酸としては炭素数 6〜22の飽和または不飽和脂肪酸が好ましく、 またこのジァミンとしては炭素 数 1〜15のジァミン、 特にアルキレンジァミンが好ましい。 また、 ビスアミド としては、 炭素数が 13〜15で分子量が 200〜800の N, N' —アルキレ ンビスアミドが好ましい。 さらに具体的には、 N, N' —メチレンビスステアリ ン酸アミド、 N, N' —エチレンビスパルミチン酸アミド、 N, N, ーメチレン ビスラウリン酸アミド、 リノール酸アミド、 力プリル酸アミド、 ステアリン酸ァ ミド等を例示することができ、 これらのうち、 特に下記式で示されるビスアミド が好ましい。
Amides of fatty acids or bisamis of fatty acids
Figure imgf000022_0001
Or C〇NHR 3 NHOCR 2 and 1 ^ (30— ぉ 1 2 (: 0_ is a fatty acid residue, and 1 NHR 3 NH— is a diamine residue. Is preferably a saturated or unsaturated fatty acid having 6 to 22 carbon atoms, and the diamine is preferably a diamine having 1 to 15 carbon atoms, particularly an alkylenediamine. Preferred is N, N'-alkylenebisamide having a molecular weight of 200 to 800. More specifically, N, N'-methylenebisstearic acid amide, N, N'-ethylenebispalmitic acid amide, N, N, -methylene Bislauric acid amide, linoleic acid amide, caprylic acid amide, stearic acid amide and the like can be exemplified, and among these, the bisamide represented by the following formula is particularly preferable.
RCONH (CH2) nNHOCR RCONH (CH 2 ) n NHOCR
(ただし、 RCO—は脂肪酸残基を示し、 nは 1または 2である。) これらの脂肪酸のアミドおよび zまたは脂肪酸のビスアミドは、 塗膜を形成す る組成物中に、 3〜1 0重量%含まれていることが好ましい。 脂肪酸のアミドぉ よび Zまたは脂肪酸のビスアミドの含有量が少なすぎると十分な接着力が得られ ず、 滑り性、 耐ブロッキング性が低下する傾向があり、 逆に多すぎると、 フィル ムと塗膜との密着性が低下したり、 塗膜とガラス用接着剤との接着性が低下した り、 塗膜の脆化を招いたりすると共にヘーズが高くなりやすい。 (However, RCO— indicates a fatty acid residue, and n is 1 or 2.) These fatty acid amides and z or fatty acid bisamides are preferably contained in the composition for forming a coating film in an amount of 3 to 10% by weight. When the content of fatty acid amide and / or Z or fatty acid bisamide is too small, sufficient adhesive strength cannot be obtained, and slipperiness and blocking resistance tend to be reduced. The adhesiveness between the coating film and the adhesive for glass decreases, the coating film becomes brittle, and the haze tends to increase.
本発明における接着層は、 摩擦係数が 0 . 8以下であることが好ましく、 さら に 0 . 6 %以下であることがより好ましい。 接着層の摩擦係数が 0 . 8を超える と、 巻取り性や加工作業性が悪く、 円滑な製膜と加工ができ難い。 このような摩 擦係数の接着層を形成する手段としては、 接着層の塗膜中に平均粒径が 0 . 1 5 m以下、 特に 0 . 0 1〜0 . 1 zmの粗面化物質を含有させることが挙げられ る。 該粗面化物質の具体例としては、 炭酸カルシウム、 炭酸マグネシウム、 酸化 カルシウム、 酸化亜鉛、 酸化マグネシウム、 酸化ケィ素、 ケィ酸ソーダ、 水酸化 アルミニウム、酸化鉄、酸化ジルコニウム、硫酸バリウム、酸化チタン、酸化錫、 三酸化アンチモン、 力一ポンプラック、 二硫化モリブデン等の無機微粒子、 ァク リル系架橋重合体、 スチレン系架橋重合体、 架橋シリコーン樹脂、 フッ素樹脂、 ベンゾグアナミン樹脂、 フエノール樹脂、 ナイロン樹脂、 ポリエチレンワックス 等の有機微粒子などを挙げることができる。 これらのうち、 水不溶性の固体物質 は、 水分散液中で沈降するのを避けるため、 比重が 3を超えない超微粒子を選ぶ ことが好ましい。  The coefficient of friction of the adhesive layer in the present invention is preferably 0.8 or less, and more preferably 0.6% or less. If the friction coefficient of the adhesive layer exceeds 0.8, the winding property and the workability are poor, and it is difficult to perform a smooth film formation and processing. As a means for forming an adhesive layer having such a friction coefficient, a roughened substance having an average particle size of 0.15 m or less, particularly 0.01 to 0.1 zm, is used in the coating film of the adhesive layer. May be included. Specific examples of the surface roughening substance include calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, silicon oxide, sodium silicate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, Inorganic fine particles such as tin oxide, antimony trioxide, force pump rack, molybdenum disulfide, etc., acrylic cross-linked polymer, styrene cross-linked polymer, cross-linked silicone resin, fluoro resin, benzoguanamine resin, phenol resin, nylon resin, Organic fine particles such as polyethylene wax can be used. Among these, it is preferable to select ultrafine particles having a specific gravity of not more than 3 in order to avoid sedimentation of the water-insoluble solid substance in the aqueous dispersion.
これらの粗面化物質は、 塗膜表面を粗面化すると共に、 微粉末自体による塗膜 の補強作用があり、 さらには塗膜への耐ブロッキング性付与作用、 積層体への滑 り性付与作用を奏する。 粗面化物質の好ましい添加量は、 塗膜を形成する組成物 中に、 5〜3 0重量%である。 特に、 平均粒径が 0. 1 以上の比較的大きな 粒子を用いるときは 5〜1 0重量%範囲から、 また平均粒径が 0 . 0 1〜0 . 1 mの粒子を用いるときには 8〜 3 0重量%の範囲内から選定するのが好ましレ^ これら粗面ィ匕物質の,中の含有量が多くなり過ぎると、 得られる積層体のへ一 ズ値が 3 %を超え、 透明性が悪化しやすいので注意を要する。 また、 粗面化物質 を添加した易滑易接着層の中心線表面粗さ (R a) は 2〜1 0 nmであることが 好ましい。 R aが 2 nm未満であると、 前述の摩擦係数を達成し難く、 積層体の 巻取り時に滑り性不足のため巻き姿が悪くなつて、 以後の作業に支障をきたす。 他方、 接着層の R aが 1 O nmを超えると透明性が悪化して、 ヘーズが 5 %を超 えやすくなる。 These surface-roughening substances roughen the surface of the coating film, and also have the effect of reinforcing the coating film with the fine powder itself, as well as the effect of imparting blocking resistance to the coating film and imparting lubricity to the laminate. It works. The preferable addition amount of the surface roughening material is 5 to 30% by weight in the composition for forming a coating film. In particular, when relatively large particles having an average particle size of 0.1 or more are used, the range is 5 to 10% by weight. When particles having an average particle size of 0.01 to 0.1 m are used, 8 to 3% by weight is used. It is preferable to select from the range of 0% by weight. If the content of these roughened materials is too large, the haze value of the obtained laminate exceeds 3%, and the transparency is increased. Care must be taken, as is easy to get worse. Also, roughening substances The center line surface roughness (R a) of the slippery adhesive layer to which is added is preferably 2 to 10 nm. If Ra is less than 2 nm, it is difficult to attain the above-mentioned coefficient of friction, and the winding form becomes poor due to insufficient slippage during winding of the laminate, which hinders subsequent operations. On the other hand, if the Ra of the adhesive layer exceeds 1 O nm, the transparency deteriorates, and the haze tends to exceed 5%.
本発明における接着層は、 前述の水性ポリエステルと脂肪酸のアミドおよび/ または脂肪酸のビスアミドからなる組成物の水溶液、水分散液あるいは乳化液を、 ロールコート法、 グラビアコート法、 口一ルブラッシュ法、 スプレーコート法、 エアーナイフコート法、 含浸法、 カーテンコート法などによって好ましく形成で きる。 また、 塗膜を形成するために、 必要に応じて、 前記水性ポリエステル以外 の他の樹脂、 粗面化物質、 帯電防止剤、 界面活性剤、 紫外線吸収剤などを添加す ることもできる。 塗布液の二軸配向ポリエステルフィルムへの塗布は、 任意の段 階で行うことができ、 二軸配向ポリエステルフィルムの製膜過程で行うのが好ま しく、 特に二軸配向ポリエステルフィルムの配向結晶化が完了するまでの段階で 塗布するのが好ましい。 ここで、 結晶配向が完了するまでの段階とは、 未延伸フ ィルム、 未延仲フィルムを縦方向または横方向の何れか一方に配向せしめた一軸 配向フィルム、 さらには縦方向および横方向の二方向に低倍率延伸配向せしめた もの (最終的に縦方向また横方向に再延伸せしめて配向結晶化を完了せしめる前 の二軸延伸フィルム) などを含む。 これらのなかでも、 一方向に配向せしめた一 軸延伸フィルムに上記組成物の塗布液を塗布し、 そのまま横延伸と熱固定とを施 すのが好ましく、 このようにして得られた易滑易接着層はベースフィルムの二軸 配向ポリエステルフィルムと強固な接合力が発現する。 塗膜は必要に応じて、 フ イルムの片面のみに形成してもよいし、 両面に形成してもよく、 塗布液の塗布量 は、 塗膜の厚さが好ましくは 7 0〜1 0 0 nm、 より好ましくは 7 5〜9 5 nm の範囲となるような量であるのが好ましい。塗膜の厚さが 7 0 nm未満であると、 接着力が不足しやすく、 逆に厚過ぎて 1 0 O nmを超えると、 ブロッキングを起 こしたり、 ヘーズ値が高くなる可能性がある。  The adhesive layer in the present invention may be formed by applying an aqueous solution, an aqueous dispersion or an emulsion of the composition comprising the above-mentioned aqueous polyester and fatty acid amide and / or fatty acid bisamide to a roll coating method, a gravure coating method, a mouth-to-brush method, It can be preferably formed by a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, or the like. Further, in order to form a coating film, a resin other than the aqueous polyester, a surface roughening substance, an antistatic agent, a surfactant, an ultraviolet absorber, and the like can be added as necessary. The application of the coating solution to the biaxially oriented polyester film can be performed at any stage, and is preferably performed during the film forming process of the biaxially oriented polyester film. It is preferable to apply at the stage until completion. Here, the stage until the completion of the crystal orientation means the unstretched film, the uniaxially oriented film in which the unrolled intermediate film is oriented in either the longitudinal direction or the lateral direction, and furthermore, the two directions of the longitudinal and lateral directions. Orientation-oriented low-magnification orientation (biaxially oriented film before it is finally re-stretched longitudinally or laterally to complete oriented crystallization). Of these, it is preferable to apply the coating solution of the above composition to a uniaxially oriented film that has been oriented in one direction, and then to carry out lateral stretching and heat fixing as it is, and to obtain the slipperiness thus obtained. The adhesive layer exhibits strong bonding strength with the biaxially oriented polyester film of the base film. If necessary, the coating film may be formed on only one side of the film, or may be formed on both sides. The coating amount of the coating solution is preferably 70 to 100 It is preferred that the amount be in the range of nm, more preferably in the range of 75-95 nm. If the thickness of the coating film is less than 70 nm, the adhesive strength tends to be insufficient, and if it is too thick and exceeds 10 O nm, blocking may occur or the haze value may increase.
また、 塗布液をフィルムに塗布する際には、 塗布性を向上させるための予備処 理として塗布面にあらかじめコロナ表面処理、 火炎処理、 プラズマ処理等の物理 処理を施すか、 あるいは塗膜組成物と共にこれと化学的に不活性な界面活性剤を 併用することが好ましい。 この界面活性剤は、 ポリエステルフィルムへの水性塗 液の濡れを促進するものである。 例えば、 ポリオキシエチレンアルキルフエニル エーテル、 ポリオキシエチレン一脂肪酸エステル、 ソルビタン脂肪酸エステル、 グリセリン脂肪酸エステル、 脂肪酸金属石鹼、 アルキル硫酸塩、 アルキルスルホ ン酸塩、 アルキルスルホコハク酸塩等のァニオン型、 ノニオン型界面活性剤を挙 げることができる。 Also, when applying the coating solution to the film, take preparatory steps to improve coatability. It is preferable to apply a physical treatment such as a corona surface treatment, a flame treatment, or a plasma treatment to the coated surface in advance, or to use a chemically inert surfactant together with the coating composition. This surfactant promotes wetting of the aqueous coating liquid on the polyester film. For example, polyoxyethylene alkyl phenyl ether, polyoxyethylene monofatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal stone, alkyl sulfate, alkyl sulfonate, alkyl sulfonate, etc., nonionic, nonionic Surfactants.
ところで、 該塗液は、 原料中の不純物などの存在によって、 イオン性の低分子 化合物が混在することがある。 ここでいうイオン性の低分子化合物は、 一 S〇3 By the way, the coating liquid may contain an ionic low molecular compound depending on the presence of impurities in the raw material. The ionic low molecular compound referred to here is one S〇 3
X 1、 -coox1, - P O4 X 一 NO— X 1 (式中の X 1はアルカリ金属または アンモニゥム基を表す) などで表される分子量 1 0 0 0以下のイオン性官能基を 有する物質である。 該イオン性の低分子化合物が接着層中に 1 0 0 0 p pmを超 えて存在すると、前述の塗液を二軸配向ポリエステルフィルムに塗工するに際し、 塗液の二軸配向ポリエステルフィルムに対する濡れ性が低下し、 一定した厚みの 塗膜が得られ難くなる上に、 接着剤に対する接着性が低下しやすくなる。 該ィォ ン性低分子化合物の検出はフィルム面に塗膜を形成した後、 その塗膜面を X P S (X線光電子分光) により表面分析することによって行うことができる。 X 1, -coox 1, - substances having a PO 4 X one NO- X 1 (X 1 represents an alkali metal or Anmoniumu groups in formula) Molecular weight 1 0 0 0 The following ionic functional group represented by like It is. If the ionic low-molecular compound is present in the adhesive layer in excess of 1000 ppm, the coating liquid wets the biaxially oriented polyester film when the aforementioned coating liquid is applied to the biaxially oriented polyester film. In addition, it is difficult to obtain a coating film having a constant thickness, and the adhesiveness to the adhesive is apt to decrease. The detection of the zwitterionic low-molecular compound can be performed by forming a coating film on the film surface and analyzing the surface of the coating film by XPS (X-ray photoelectron spectroscopy).
本発明の接着性フィルムは、 接着層を裏面 (両面塗布の場合は任意の片面) と して二軸配向ポリエステルフィルムの側から可視光領域の光を、 面に対して 4 5 度の角度で入射させたとき、 接着層と二軸配向ポリエステルフィルムとの界面に おける反射率(以下、裏面反射率と称することがある。)が 0. 4 %以下であるこ とが好ましい。 裏面反射率が 0. 4 %を超えると、 表面反射への影響が無視でき なくなり、 光学用積層体としてディスプレイの防眩フィルムに用いた場合、 外来 光の反射が表面反射と裏面反射の干渉で虹模様となって目障りになり、 認視性を 損い易い。 裏面反射率を 0 . 4 %以下にするには、 塗膜の厚み方向における屈折 率 (n z ) を 1 . 5 0〜: L . 6 0にすることが好ましい。 n zが上記範囲を逸脱 すると、 可視光領域の裏面反射が 0. 4 %を超え易くなる。 また、 該屈折率がこ の範囲を超えると裏面反射の影響が顕在化し、 後述の反射防止層を設ける場合に 反射防止が困難になるという不都合が生じる場合もある。 このようにして得られ た易接着フィルムは、 表面の滑り性および接着性に優れながらも、 色相のコント ラストが明確で、 かつ、 透明性に優れている。 The adhesive film of the present invention uses the adhesive layer as the back surface (in the case of double-sided application, any single surface), and transmits light in the visible light region from the side of the biaxially oriented polyester film at an angle of 45 degrees to the surface. When incident, the reflectance at the interface between the adhesive layer and the biaxially oriented polyester film (hereinafter sometimes referred to as the back surface reflectance) is preferably 0.4% or less. When the backside reflectance exceeds 0.4%, the effect on frontside reflection cannot be ignored, and when used as an optical laminate for antiglare films for displays, the reflection of extraneous light is caused by interference between frontside reflection and backside reflection. It becomes obscured with a rainbow pattern, which easily impairs visibility. In order to make the back surface reflectivity 0.4% or less, the refractive index (nz) in the thickness direction of the coating film is preferably set to 1.50 to: L.60. If nz deviates from the above range, the backside reflection in the visible light region tends to exceed 0.4%. Also, the refractive index is If the ratio exceeds the range, the effect of back surface reflection becomes apparent, and in the case where an anti-reflection layer described later is provided, there may be a problem that it becomes difficult to prevent reflection. The easy-adhesive film thus obtained has excellent surface slipperiness and adhesiveness, but also has a clear hue contrast and is excellent in transparency.
本発明における光学用積層体は、 C R Tなどのディスプレイに貼り合わせて使 用する上で、 両面に第 1の接着層が形成された前述の本発明の接着性フィルムの 一方の面上に第 2の接着剤層を、 他方の面上にハードコート層を積層したもので ある。 本発明の積層フィルムについて、 以下に詳述する。  When the optical laminate of the present invention is used after being bonded to a display such as a CRT, a second adhesive film is formed on one surface of the adhesive film of the present invention having the first adhesive layer formed on both surfaces. And a hard coat layer laminated on the other surface. The laminated film of the present invention will be described in detail below.
本発明の積層フィルムは、 第 1の接着層の上にハ一ドコート層を積層したもの であり、これによつて本発明の積層フィルムの耐擦傷性を向上することができる。 該ノヽ一ドコート層としては、 放射線硬化系またはシラン系の樹脂を用いることが でき、 特に放射線硬化系の樹脂を用いたハードコート層が好ましく、 そのなかで も紫外線 (UV) 硬ィ匕系の樹脂を用いたハードコート層が好ましい。 ハードコー ト層の形成に用いられる UV硬化系組成物としては、ウレタン一ァクリレート系、 エポキシ一ァクリレート系、 ポリエステル—ァクリレート系などの UV硬化性組 成物が挙げられる。積層体の第 1の接着層の上にハードコート層を積層するには、 該接着層上に組成物を塗布し、 加熱、 放射線 (例えば紫外線) 照射等により該組 成物を硬化させればよい。 ハードコート層の厚さは、 特に限定されないが、 1〜 1 5 mの範囲が好ましい。  The laminated film of the present invention is obtained by laminating a hard coat layer on the first adhesive layer, whereby the abrasion resistance of the laminated film of the present invention can be improved. As the node coat layer, a radiation-curable or silane-based resin can be used. In particular, a hard coat layer using a radiation-curable resin is preferable, and among them, an ultraviolet (UV) A hard coat layer using a resin is preferable. Examples of the UV curable composition used for forming the hard coat layer include UV curable compositions such as urethane acrylate, epoxy acrylate, and polyester acrylate. In order to laminate the hard coat layer on the first adhesive layer of the laminate, the composition is applied on the adhesive layer, and the composition is cured by heating, irradiation with radiation (for example, ultraviolet rays), or the like. Good. The thickness of the hard coat layer is not particularly limited, but is preferably in the range of 1 to 15 m.
本発明における積層フィルムは、 このように形成したハードコート層の上にさ らに多重反射防止層を形成するのが好ましい。 多重反射防止層は、 屈折率の異な る複数の層を交互に積層したもので、 その構成は一般によく知られている。 例え ば、 低屈折率層 (S i〇2、 3 O nm) 一高屈折率層 (T i〇2、 3 O nm) 一低 屈折率層 (S i 02、 3 0 nm) —高屈折率層 (T i〇2、 1 0 0 nm) —低屈折 率層 (S i 02、 1 0 O nm) の層構成を有するもの、 高屈折率層 (I T〇、 2 O nm) —低屈折率層 (A 1 S i 0、 2 0 nm) —高屈折率層 ( I ΤΟ、 8 8 η m) 一低屈折率層 (A l S i〇、 8 8 nm) の層構成を有するもの、 高屈折率導 電層 (I T〇、 2 O nm) 一低屈折率層 (S i〇2、 2 O nm) - 層 (I T〇、 93 nm) 一低屈折率層 (S i〇2、 93 nm) の層構成を有する ものなどが知られている。 反射防止層の形成方法としては、 任意の方法を採用で き、 例えば、 スパッタリングによって積層すればよい。 該多重反射防止層によつ て、 本発明の積層フィルムはディスプレイの認視性を妨げる外来光の反射を抑制 できる。 反射防止層は、 これらの他にも、 単層膜で主として黄色光を中心に反射 防止するものがあるが、 ディスプレイの反射防止には、 多層反射防止膜の方が適 している。 In the laminated film of the present invention, it is preferable to further form a multiple antireflection layer on the hard coat layer thus formed. The multiple anti-reflection layer is formed by alternately laminating a plurality of layers having different refractive indexes, and the configuration is generally well known. For example, low refractive index layer (S i〇 2 , 3 O nm) high refractive index layer (T i〇 2 , 3 O nm) low refractive index layer (S i 0 2 , 30 nm) —high refractive index rate layer (T I_〇 2, 1 0 0 nm) - having a layer structure of a low refractive index layer (S i 0 2, 1 0 O nm), a high refractive index layer (IT_〇, 2 O nm) - low Refractive index layer (A 1 S i0, 20 nm) — High refractive index layer (I 8, 88 η m) and low refractive index layer (A l S i 〇, 88 nm) , High refractive index conductive layer (IT〇, 2 O nm) One low refractive index layer (S i〇 2 , 2 O nm)- Layer (IT_〇, 93 nm) such as those having a layer structure of one low refractive index layer (S I_〇 2, 93 nm) are known. As a method for forming the anti-reflection layer, any method can be adopted, and for example, the layers may be laminated by sputtering. With the multiple anti-reflection layer, the laminated film of the present invention can suppress the reflection of extraneous light that hinders the visibility of the display. In addition to these, the anti-reflection layer includes a single-layer film which mainly prevents yellow light from being mainly reflected, but a multilayer anti-reflection film is more suitable for preventing reflection of a display.
本発明における積層フィルムは、ハードコート層を形成した側とは異なる面に、 第 2の接着剤層を積層しており、 この第 2の接着剤の積層の場合も二軸配向ポリ エステルフィルムとの接着性を向上させるために、 第 1の接着層を介して積層す るのが好ましい。 実施例  In the laminated film of the present invention, the second adhesive layer is laminated on a surface different from the side on which the hard coat layer is formed. In the case of laminating the second adhesive, a biaxially oriented polyester film is also used. In order to improve the adhesiveness of these, it is preferable to laminate them via a first adhesive layer. Example
以下、 実施例を挙げて本発明をさらに詳細に説明する。 なお、 実施例中の各特 性値は以下の方法により評価した。  Hereinafter, the present invention will be described in more detail with reference to Examples. Each characteristic value in the examples was evaluated by the following methods.
(1) ヘーズ値  (1) Haze value
日本電色工業社製のヘーズ測定器 (NDH-20) を使用してヘーズ値を測定 した。 ヘーズ値は次の基準で評価した。  The haze value was measured using a haze meter (NDH-20) manufactured by Nippon Denshoku Industries Co., Ltd. The haze value was evaluated according to the following criteria.
4:ヘーズ値≤ 2. 0 % ……ヘーズ値極めて良好、  4: Haze value ≤ 2.0% …… Extremely good haze value,
3 : 2. 0 %<ヘーズ値≤ 3. 0 % ……ヘーズ値良好、 3: 2.0% <Haze value ≤ 3.0% …… Good haze value,
2 : 3. 0%くへーズ値≤5. 0% ……ヘーズ値やや良好、  2: 3.0% haze value ≤5.0% …… Haze value is slightly good
1 : 5. 0%くヘーズ値 ……ヘーズ値不良。 1: 5.0% haze value .... haze value defect.
(2) 平均透過率  (2) Average transmittance
(株) 島津製作所製 分光光度計 MP C3100を用い、 波長 450〜 650η mの可視光線の透過率を測定した。  The transmittance of visible light having a wavelength of 450 to 650 ηm was measured using a spectrophotometer MP C3100 manufactured by Shimadzu Corporation.
©>:波長450〜65011111の平均透過率 0^¥) が0. 50以上 0. 70以 下、  ©>: Average transmittance of wavelength 450 ~ 65011111 0 ^ ¥) 0.50 or more, 0.70 or less,
〇:波長450〜65011111の平均透過率 (Tav) が 0. 40以上 0. 50未 満または 0. 70超0. 80以下、 〇: Average transmittance (Tav) of wavelength 450-65011111 is 0.40 or more and 0.50 or less Full or 0.70 to 0.80 or less,
X:波長 400〜750 nmの平均吸光度 (Aav) が 0. 40未満または 0. 80超、  X: Average absorbance (Aav) at a wavelength of 400 to 750 nm is less than 0.40 or more than 0.80,
(3) 各波長における透過率  (3) transmittance at each wavelength
上記吸光度の測定法に準じ、 波長 450〜 650 nmの各波長 iにおける透過率 (T i) を測定した。 得られた結果を下記の方法で評価した。 The transmittance (T i) at each wavelength i from 450 to 650 nm was measured according to the above-mentioned method for measuring absorbance. The obtained results were evaluated by the following methods.
◎ : 0. 8≤T i/Tav≤l. 2の範囲、 ◎: 0.8≤T i / Tav≤l.2 range,
〇: 0. 7≤T i/Ta ν<0. 8または 1. 2<T i/Tav≤l. 3の範囲、 X: T iZTav く 0. 7または T i/Ta ν>1. 3の範囲、  〇: 0.7 ≤ Ti / Ta ν <0.8 or 1.2 <Ti / Tav ≤ l.3, X: TiZTav く 0.7 or Ti / Ta ν> 1.3 range,
(4) コン卜ラス卜  (4) Contrast
試験用 CRTに対し、 上方 45° より 30W蛍光灯で照らし、 正反射光が直接 入射しないほぼ水平より上方 30° で画面上の最高輝度、 最低輝度を輝度計 (ミ ノル夕製) により測定し、 コントラスト 1 (最高輝度 最低輝度) を求める。 次 に供試サンプルを CRTに粘着剤で貼付し、再度、最高輝度、最低輝度を測定し、 コントラスト 2を求めた。  The test CRT is illuminated with a 30W fluorescent lamp from above 45 °, and the maximum and minimum luminance on the screen is measured with a luminance meter (Minol Yu) at 30 ° above horizontal, where specular light is not directly incident. , Contrast 1 (highest luminance, lowest luminance). Next, the test sample was attached to a CRT with an adhesive, and the highest luminance and the lowest luminance were measured again, and the contrast 2 was obtained.
100 %の値を次の区分で評価した。
Figure imgf000028_0001
X 100%が 120%以上、 〇:(コントラスト 2 Zコントラスト 1) X 100%が 100%以上 120%未 満、
A value of 100% was evaluated in the following categories.
Figure imgf000028_0001
X 100% is 120% or more, 〇: (Contrast 2 Z Contrast 1) X 100% is 100% or more and less than 120%,
X: (コントラスト 2/コントラスト 1) X 100%が 100%未満、 X: (Contrast 2 / Contrast 1) X 100% is less than 100%,
(5) 彩度  (5) Saturation
標準光 Aに対する供試フィルムの透過スぺクトルから J I S規格 Z 8729に 準じて L * a * b *表色系における L *、 a *および b *を求めた。下記式より求めら れる a bクロマ (C*ab) で無彩色との彩度のずれを評価した。  L *, a *, and b * in the L * a * b * color system were determined from the transmission spectrum of the test film with respect to the standard light A in accordance with JIS Z 8729. The chroma deviation from the achromatic color was evaluated using the ab chroma (C * ab) obtained from the following equation.
© : C*abが 5未満 ©: C * ab is less than 5
〇: C*a bが 5以上 10未満  〇: C * ab is 5 or more and less than 10
X: C*a bが 10以下 C*a b= J (a*) 2+ (b*) 2 X: C * ab is 10 or less C * ab = J (a *) 2 + (b *) 2
(6) 裏面反射率  (6) Backside reflectance
接着性フィルムの接着層の面を裏面 (両面塗布の場合は任意の片面) とすると き、 フィルム表面から 45° の角度で点光源を照射し、 主反射から、 フィルム厚 みを dとするとき、 dZO. 707だけ離れた反射光を裏面反射とし、 これを点 光源の光量で割ったものを反射率とする。 これを次の基準で評価した。  When the surface of the adhesive layer of the adhesive film is the back side (or one side in the case of double-sided application), when a point light source is irradiated at an angle of 45 ° from the film surface, and the film thickness is d from the main reflection The reflected light separated by dZO. 707 is defined as the backside reflection, and this is divided by the amount of light from the point light source to obtain the reflectance. This was evaluated according to the following criteria.
〇:裏面反射率が 0. 4%以下 〇: Backside reflectance is 0.4% or less
X:裏面反射率が 0. 4%超 X: Backside reflectance is more than 0.4%
(7) 接着力  (7) Adhesive strength
a. 対接着剤 a. Adhesive
接着性フィルムの接着層の面に厚さ 10 mのアクリル系の粘着剤を塗設する。 60°C、 80%RHの恒温恒湿槽中に 24時間経時後、 エポキシ樹脂系の接着剤 で貼り合せ、 引き剥がし試験により、 以下の基準で評価する。  Apply an acrylic adhesive with a thickness of 10 m on the surface of the adhesive layer of the adhesive film. After 24 hours in a thermo-hygrostat at 60 ° C and 80% RH, bond with epoxy resin adhesive and evaluate by peeling test according to the following criteria.
◎:基材フィルムが破断する程度に接着力が強い ◎: Adhesive strength is strong enough to break base film
〇:剥離するが、 実用性はある 〇: Peeled, but practical
X:たやすく剥離し、 実用性無し  X: Easy peeling, no practicality
b. 対ハードコート b. Hard court
接着性フィルムの接着層の面に厚さ 5 mのハードコート層を形成して碁盤目 のクロスカット (1]11111のマス目を100個) を施し、 その上に 24mm幅のセ ロハンテープ (ニチバン社製) を貼り付け、 180度の剥離角度で急激に剥がし た後、 剥離面を観察し、 以下の基準で評価した。  A hard coat layer with a thickness of 5 m is formed on the adhesive layer of the adhesive film, cross-cut in a grid (1), 100 squares of 11111, and a 24-mm cellophane tape (Nichiban) (Manufactured by the company) and abruptly peeled off at a peeling angle of 180 °. The peeled surface was observed and evaluated according to the following criteria.
5 :剥離面積が 10 %未満……接着力極めて良好  5: Peeling area is less than 10% .... Excellent adhesive strength
4 :剥離面積が 10 %以上 20 %未満……接着力良好  4: Peeling area is 10% or more and less than 20% .... Good adhesive strength
3 :剥離面積が 20 %以上 30 %未満……接着力やや良好  3: Peeling area is 20% or more and less than 30% ... Slightly good adhesive strength
2 :剥離面積が 30 %以上 40 %未満……接着力不良 2: Peeling area is 30% or more and less than 40% ... Poor adhesive strength
1 :剥離面積が 40 %を超えるもの……接着力極めて不良  1: Peeling area exceeds 40% .... Adhesive strength is extremely poor.
(8) イオン性低分子化合物の検出  (8) Detection of ionic low molecular compounds
接着性フィルムの接着層の面を XPS(X線光電子分光)により表面分析する。 その結果により、 以下のように表示した。 The surface of the adhesive layer of the adhesive film is analyzed by XPS (X-ray photoelectron spectroscopy). According to the result, it is displayed as follows.
〇:イオン性低分子化合物の含有量が 1000 p pm以下  〇: The content of ionic low-molecular compounds is 1000 ppm or less
X:イオン性低分子化合物の含有量が 1000 p pmを超える X: The content of ionic low molecular compounds exceeds 1000 ppm
(9) フィルム/フィルム摩擦係数  (9) Film / film friction coefficient
表面と裏面を重ね合せた 2枚のフィルム試料の下側に固定したガラスを置き、 重ね合せたフィルムの下側 (ガラス板と接しているフィルム) のフィルムを定速 ロールにて引取り (10 cmZ分)、上側のフィルムの一端(下側フィルムの引取 り方向と逆端), に検出機を固定してフィルムノフィルム間の引張力 (F) を検出 する。 なお、 その時に用いる上側のフィルムの上に載せてあるスレッドは下側面 積が 50 cm2 (8 OmmX 62. 5mm) であり、 フィルムに接する面は硬度 80° のネオプレンゴムであり、 その重さ (W) は 1. 2 kgとする。 静摩擦係 数 ( iS) は以下の式で算出される。 Place the fixed glass on the lower side of the two film samples with the front and back superimposed and take off the film on the lower side of the superposed film (the film in contact with the glass plate) with a constant speed roll (10 cmZ), fix the detector to one end of the upper film (the end opposite to the direction in which the lower film is pulled out), and detect the tensile force (F) between the films. The thread placed on the upper film used at that time has a lower surface area of 50 cm 2 (8 OmmX 62.5 mm), and the surface that contacts the film is neoprene rubber with a hardness of 80 ° and its weight. (W) shall be 1.2 kg. The static friction coefficient (iS) is calculated by the following equation.
。 F (g)  . F (g)
W (g)  W (g)
(10) 易接着層の厚み方向の屈折率  (10) Refractive index in the thickness direction of the easily adhesive layer
アッベ屈折率計を用い、 ナトリウム D線を光源として測定した。 なお、 マウン ト液にはヨウ化メチレンを用い、 測定雰囲気は 25°C、 65%RHとした。 The measurement was performed using an Abbe refractometer with sodium D line as a light source. The mounting solution was methylene iodide, and the measurement atmosphere was 25 ° C and 65% RH.
(11) 認視性改良フィルムとして表面反射の評価 (11) Evaluation of surface reflection as a visibility improving film
発光していない試験用 CRTに 700 1 Xの外光を照射し、 反射輝度 1を輝度 計 (ミノルタ製) によって測定する。 次に、 供試フィルムを CRTに粘着剤で貼 付し、 再度反射輝度 2を測定した。 (反射輝度 2 Z反射輝度 1) X I 00%の値 を次の区分で評価した。  Irradiate 700 1X external light to the test CRT that does not emit light, and measure the reflected luminance 1 with a luminance meter (Minolta). Next, the test film was attached to a CRT with an adhesive, and the reflection luminance 2 was measured again. (Reflection luminance 2 Z reflection luminance 1) The value of XI 00% was evaluated in the following categories.
◎: (反射輝度 2Z反射輝度 1) X I 00%が 20%未満  ◎: (Reflection luminance 2Z Reflection luminance 1) X I 00% is less than 20%
〇··(反射輝度 2Z反射輝度 1) XI 00%が 20%以上 30%未満 ((Reflection luminance 2Z reflection luminance 1) XI 00% is 20% or more and less than 30%
Δ: (反射輝度 2Z反射輝度 1) X 100%が 30%以上 40%未満 Δ: (reflection luminance 2Z reflection luminance 1) X 100% is 30% or more and less than 40%
X: (反射輝度 2Z反射輝度 1) X 100 %が 40 %以上 X: (reflection luminance 2Z reflection luminance 1) X 100% is 40% or more
(12)認視性改良フィルムとしての耐摩耗性  (12) Wear resistance as a film with improved visibility
試料を、 スチールウール # 000を角型パッド (面積 6. 25 cm2) ί し、 往復式磨耗試験機による磨耗試験 (荷重 l kg、 50回往復) 前後のヘーズ 値の差 (Δへ一ズ) から以下のように評価した。 Specimen was coated with steel wool # 000 on square pad (area 6.25 cm 2 ) ί Then, the difference between the haze values before and after the abrasion test (load l kg, 50 reciprocations) using a reciprocating abrasion tester was evaluated as follows.
Δヘーズ = (磨耗試験後のヘーズ値) 一 (磨耗試験前のヘーズ値) ΔHaze = (Haze value after abrasion test) I (Haze value before abrasion test)
〇: Δヘーズが 10未満 〇: Δ haze is less than 10
Δ: Δヘーズが 10以上 20未満 Δ: Δ haze is 10 or more and less than 20
X: Δヘーズが 20超 X: Δ haze exceeds 20
(13) 熱収縮率  (13) Heat shrinkage
150°Cの熱風中に 30分間保持し、 フィルムの長手方向および幅方向につい て前後の寸法変化を下記式より求める。  The film is kept in hot air of 150 ° C for 30 minutes, and the dimensional change before and after in the longitudinal direction and the width direction of the film is obtained from the following formula.
熱収縮率 (%) = (L。一 L) ZLX 100  Heat shrinkage (%) = (L. One L) ZLX 100
(14) 表面粗さ  (14) Surface roughness
J I S-B 0601の中心線平均粗さ (Ra) の測定方法に準拠して、 (株)小 坂研究所の接触式表面粗さ計 (SURFCORDER SE— 30C) を用いて 測定する。 測定条件は以下の通りである。  Measure with a contact surface roughness meter (SURFCORDER SE-30C) of Kosaka Laboratory Co., Ltd. in accordance with the method of measuring the center line average roughness (Ra) of JIS-B0601. The measurement conditions are as follows.
触針先端半径: 2輝 Stylus tip radius: 2 shines
測定圧力: 3 Omg Measuring pressure: 3 Omg
カツトオフ: 0. 25mm Cut off: 0.25mm
測定長: 2. 5 mm Measuring length: 2.5 mm
データのまとめ方:同一試料について 6回繰返し測定し、 最も大きい値を 1つ除 き残り 5つのデータの平均値で表示する。 How to summarize the data: Repeat the measurement for the same sample 6 times. Excluding the largest one, display the average of the remaining five data.
(15) 反射防止層加工後の平面性  (15) Flatness after processing of anti-reflection layer
反射防止層加工後の光学用積層体の平面性 (しわ、 転写、 擦れによる傷、 フィ ルムの平面性不良) および光学用積層体の熱変形による平面性の不良の有無を 3 段階で評価した。  The flatness of the optical laminate after processing the anti-reflection layer (wrinkles, transfer, scratches due to rubbing, poor flatness of the film) and the presence of poor flatness due to thermal deformation of the optical laminate were evaluated in three steps. .
〇:良好 〇: good
△ :使用可 (一部不良個所有り)  △: Can be used (partly defective)
X:使用不可  X: Unavailable
(16) 耐光劣化性 東洋精機 (株) 製キセノンゥェザメータを使用し、 サンプルフィルムに 300 〜800 nmの波長の光線を放射照度 765WZm2で 100時間照射し、 照射 前後の三刺激値 (視感透過率を含む)、 Lab (色度座標)、 Y I (黄変度) を色 差計(日本電飾工業 (株)製 S Z S—∑ 90) を用いて測定し、 次の基準で評価 する。 〇は屋内での使用には問題が無く、 ◎は屋内だけでなく屋外での使用にも 問題がないレベルの耐光劣化性を有する。 (16) Light degradation resistance Using the Toyo Seiki Co. xenon © E The meter, the light of a wavelength of 300 to 800 nm to the sample films were irradiated at an irradiance 765WZm 2 100 hours, including tristimulus values (luminous transmission before and after irradiation ), Lab (chromaticity coordinates), and YI (yellowing degree) are measured using a colorimeter (SZS-∑90 manufactured by Nippon Denshoku Industries Co., Ltd.) and evaluated according to the following criteria. 〇 has no problem for indoor use, and ◎ has a level of light deterioration resistance that is not a problem for indoor and outdoor use.
◎:視感度透過率の変化が 3 %以内でかつ黄変度 4以内  :: Change in luminous transmittance within 3% and yellowing degree within 4
O: 視感度透過率の変化が 3%を超えるかおよぴンまたは黄変度 4超 実施例 1  O: The change in luminous transmittance exceeds 3% and the degree of yellowing or yellowing exceeds 4 Example 1
大日精化製カーボンブラック顔料を 0. 03重量%、 平均粒径1. 7 の多 孔質シリカを 0. 007重量%含有させたポリエチレンテレフタレ一ト (35°C 一オルトクロロフエノ一ルによる固有粘度 [77] =0. 65) を溶融状態でダイ より押出し、 常法により冷却ドラムで冷却して未延伸フィルムとした。 次いで、 該未延伸フィルムを一旦巻き取ることなく引き続いて、 縦方向に 9 O に加熱し た状態で延伸倍率 3. 5倍で延伸し、 横方向に 95°Cに加熱した状態で延伸倍率 3. 8倍で延伸した後、 230 °Cで緊張熱処理して、 厚み 75 mの二軸配向ポ リエステルフィルムを得た。 得られた二軸配向ポリエステルフィルムの光学特性 の評価結果を表 1に示す。  Polyethylene terephthalate containing 0.03% by weight of Dainichi Seika's carbon black pigment and 0.007% by weight of porous silica having an average particle size of 1.7 (35 ° C-ortho-chlorophenol) The intrinsic viscosity [77] = 0.65) was extruded in a molten state from a die, and cooled by a cooling drum by a conventional method to obtain an unstretched film. Subsequently, the unstretched film is continuously stretched without being wound up, and then stretched at a stretch ratio of 3.5 while heating to 9 O in the longitudinal direction, and stretched at a stretch ratio of 3.5 while heated to 95 ° C in the transverse direction. After stretching at a magnification of .times.8, the film was subjected to a tension heat treatment at 230.degree. C. to obtain a biaxially oriented polyester film having a thickness of 75 m. Table 1 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
実施例 2 Example 2
実施例 1において、 厚みを 200 mに変更し、 かつ、 色素およびその添加量 を日本化薬社製 kaya s e t B l a c k AN (染料) 0. 03重量%に変 更する以外は同様な操作を繰返した。 得られた二軸配向ポリエステルフィルムの 光学特性の評価結果を表 1に示す。  The same operation as in Example 1 was repeated except that the thickness was changed to 200 m, and the amount of the pigment and the amount of addition were changed to 0.03% by weight of kaya set B lack AN (dye) manufactured by Nippon Kayaku. Was. Table 1 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
実施例 3 Example 3
大日精化製カーポンプラック顔料を 0. 04重量%、 平均粒径 1. 7 mの多 孔質シリカを 0. 007重量%含有させたポリエチレンナフタレート (35°C— オルトクロ口フエノールによる固有粘度 [77] =0. 62) を溶融状態でダイよ り押出し、 常法により冷却ドラムで冷却して未延伸フィルムとした。 次いで、 該 未延伸フィルムを一旦巻き取ることなく引き続いて、 縦方向に 1 4 0 °Cに加熱し た状態で延伸倍率 3 . 5倍で延伸し、 横方向に 1 3 5 °Cに加熱した状態で延伸倍 率 3 . 8倍で延伸した後、 2 3 0 °Cで緊張熱処理して、 厚み 5 0 mの二軸配向 ポリエステルフィルムを得た。 得られた二軸配向ポリエステルフィルムの光学特 性の評価結果を表 1に示す。 Polyethylene naphthalate containing 0.04% by weight of Dainippon Seika's car pump rack pigment and 0.007% by weight of porous silica with an average particle size of 1.7 m (35 ° C—intrinsic viscosity by orthochlorophenol) [77] = 0.62) was extruded in a molten state from a die, and cooled with a cooling drum by a conventional method to obtain an unstretched film. Then, The unstretched film is continuously stretched without being wound, stretched at a stretch ratio of 3.5 while heating to 140 ° C in the longitudinal direction, and stretched to 135 ° C in the transverse direction. After stretching at a magnification of 3.8, the film was subjected to a tension heat treatment at 230 ° C. to obtain a biaxially oriented polyester film having a thickness of 50 m. Table 1 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
実施例 4 Example 4
実施例 3において、 厚みを 7 5 mに変更し、 かつ、 色素およびその添加量を 表 1に示すように変更する以外は同様な操作を繰返した。 得られた二軸配向ポリ エステルフィルムの光学特性の評価結果を表 1に示す。  The same operation as in Example 3 was repeated except that the thickness was changed to 75 m, and the dye and the amount of the dye were changed as shown in Table 1. Table 1 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
比較例 1〜 5 Comparative Examples 1 to 5
実施例 1において、 色素およびその添加量を表 1に示すように変更する以外は 同様な操作を繰返した。 得られたニ軸配向ポリエステルフィルムの光学特性の評 価結果を表 1に示す。  The same operation as in Example 1 was repeated except that the dye and the amount added were changed as shown in Table 1. Table 1 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
比較例 6 Comparative Example 6
実施例 3において、 厚みと色素の添加量を表 1に示すように変更する以外は同 様な操作を繰返した。 得られたニ軸配向ポリエステルフィルムの光学特性の評価 結果を表 1に示す。 In Example 3, the same operation was repeated except that the thickness and the amount of the dye added were changed as shown in Table 1. Table 1 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
厚み 色素 平均透過率 各波長の ヘーズ コン卜ラス卜 彩度Thickness Dye Average transmittance Haze contrast Saturation of each wavelength
(重量%) g/m2 透過率 (Wt%) g / m 2 permeability
実施例 1 75 A(0.03) 0.032 〇 〇 2 〇 〇 実施例 2 200 B(0.03) 0.084 ◎ ◎ 4 ◎ ◎ 実施例 3 50 A (0.04) 0.028 〇 〇 3 〇 〇 実施例 4 75 C(0.07) 0.074 ◎ 〇 4 ◎ ◎ 比較例 1 75 なし X ◎ ' X ◎ 比較例 2 75 D(0.35) 0.368 〇 X 4 〇 X 比較例 3 75 A(0.20) 0.210 X ◎ 1 ◎ 〇 比較例 4 75 B(0.02) 0.021 〇 ◎ 4 X ◎ 比較例 5 75 C(0.25) 0.263 〇 X 4 〇 X 比較例 6 200 A (0.10) 0.280 X ◎ 1 ◎ 〇 Example 1 75 A (0.03) 0.032 〇 〇 2 〇 例 Example 2 200 B (0.03) 0.084 ◎ ◎ 4 ◎ ◎ Example 3 50 A (0.04) 0.028 〇 〇 3 〇 〇 Example 4 75 C (0.07) 0.074 ◎ 〇 4 ◎ ◎ Comparative Example 1 75 None X ◎ 'X ◎ Comparative Example 2 75 D (0.35) 0.368 〇 X 4 〇 X Comparative Example 3 75 A (0.20) 0.210 X ◎ 1 ◎ 比較 Comparative Example 4 75 B ( 0.02) 0.021 ◎ ◎ 4 X ◎ Comparative Example 5 75 C (0.25) 0.263 〇 X 4 〇 X Comparative Example 6 200 A (0.10) 0.280 X ◎ 1 ◎ 〇
なお、 表 1における色素の記号 (A, B, Cおよび D) は以下の染料および顔 料を示す。 The symbols (A, B, C and D) of the dyes in Table 1 indicate the following dyes and pigments.
A:大日精化製力一ボンブラック (顔料)  A: Dainichi Seika Power Bonbon Black (pigment)
B: 日本化薬製 kay a s e t B l ac k AN (染料) B: Nippon Kayaku kay a se t B l ac k AN (dye)
C:日本化薬製 kaya s e t Gr e en AB (染料) /k ay a s e t V i o 1 e t AR (染料) の重量比 1 : 1混合物 C: Nippon Kayaku's kaya set Gleen AB (dye) / kay aset Vio1et AR (dye) weight ratio 1: 1 mixture
D:日本化藥製 kaya s e t B 1 a c kG (染料) D: Nippon Kayaku kaya set B 1 a c kG (dye)
実施例 5 Example 5
大日精化製カーボンブラック顔料を 0. 03重量%、 平均粒径 1. マ mの多 ?し質シリカを 0. 007重量%含有した溶融ポリエチレンテレフタレート ([77] =0. 65) をダイより押出し、 常法により冷却ドラムで冷却して未延伸フィル ムとし、 次いで縦方向に 90°Cの温度で延伸倍率 3. 5倍で延伸した後、 その両 面に以下の塗膜用組成物の濃度 8%の水性液を口一ルコーターで均一に塗布し、 その後、引き続いて 95 °Cで乾燥しながら横方向に 120°Cで 3.8倍に延伸し、 230°Cで熱固定して、 厚さ 75 111の易接着フィルムを得た。 なお、 塗膜の厚 さは 0. 15 mであった。 得られた易接着フィルムの評価結果を表 2に示す。 塗膜用組成物  0.03% by weight of carbon black pigment manufactured by Dainichi Seika, average particle size 1. A molten polyethylene terephthalate ([77] = 0.65) containing 0.007% by weight of silica was extruded from a die, cooled by a cooling drum in a conventional manner to form an unstretched film, and then 90 ° C in the longitudinal direction. After drawing at a draw ratio of 3.5 times at a temperature of 5%, an aqueous liquid having a concentration of 8% of the following coating composition was uniformly applied to both surfaces with a mouth coater, and then continuously at 95 ° C. While drying, the film was stretched 3.8 times in the transverse direction at 120 ° C and heat-set at 230 ° C to obtain an easily adhesive film having a thickness of 75111. The thickness of the coating film was 0.15 m. Table 2 shows the evaluation results of the obtained easily adhesive films. Composition for coating film
酸成分がテレフタル酸 (90モル%)、 イソフタル酸(6モル%)および 5—ス ルホイソフタル酸力リゥム(4モル%)、ダリコール成分がエチレングリコール(9 5モル%)およびネオペンチルダリコ一ル(5モル%)から合成される Tg 68 の共重合ポリエステル  The acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and 5-sulfoisophthalic acid (4 mol%), and the daricol component is ethylene glycol (95 mol%) and neopentyl diol. (5 mol%) Tg 68 copolymerized polyester
80重量%  80% by weight
N, N' —エチレンビス力プリル酸アミド 5重量%  N, N'—Ethylene bis-forced prillamide 5% by weight
ァクリル系樹脂微粒子 (平均粒径 0. 03/zm) 10重量% Acryl resin fine particles (average particle size 0.03 / zm) 10% by weight
ポリオキシエチレンノニルフエニルエーテル 5重量% 5% by weight of polyoxyethylene nonylphenyl ether
実施例 6〜 8 Examples 6 to 8
塗膜用組成物の組成を表 2に示すように変更した以外は、 実施例 6と同様にし て厚さ 75 mの光学用易接着性フィルムを得た。 なお、 塗膜の厚さは 0. 15 mであった。 得られた易接着フィルムの評価結果を表 2に示す。 A 75 m thick easily adhesive optical film was obtained in the same manner as in Example 6, except that the composition of the coating composition was changed as shown in Table 2. The thickness of the coating is 0.15 m. Table 2 shows the evaluation results of the obtained easily adhesive films.
表 2 易接着性塗膜用組成 ^ > (重量%) 裏面 塗膜厚み 塗面の 接着力 水性 脂肪酸アミド 粗面化 界面 反射率 係数 方向屈折率 表面粗さ ハ-ドコ-ト ホ°リエステル 脂肪酸ビスアミド 物質 活性剤 ( ) (nm) Table 2 Composition for easily adhesive coatings ^> (wt%) Back coating thickness Adhesive strength of coated surface Water-based fatty acid amide Roughened interface Reflectivity Coefficient Directional refractive index Surface roughness Hard coat Polyester Fatty acid bisamide Substance Activator () (nm)
実施例 5 Ρ(80) J (5) Κ(10) Υ(5) 〇 0.70 1.559 10 〇 4 実施例 6 Ρ(80) H(5) Κ(10) Υ(5) 〇 0.72 1.552 10 〇 4 実施例 7 Q(80) H(5) αο) Υ(5) 〇 0.75 1.550 9 ◎ 5 実施例 8 Q(80) 1 (5) καο) Υ(5) 〇 0.72 1.549 9 ◎ 5 Example 5 Ρ (80) J (5) Κ (10) Υ (5) 〇 0.70 1.559 10 〇 4 Example 6 Ρ (80) H (5) Κ (10) Υ (5) 〇 0.72 1.552 10 〇 4 Example 7 Q (80) H (5) αο) Υ (5) 〇 0.75 1.550 9 ◎ 5 Example 8 Q (80) 1 (5) καο) Υ (5) 〇 0.72 1.549 9 ◎ 5
表 2における塗膜用組成物の記号 (P、 Q、 H、 I、 J、 Gおよび Y) は、 そ れぞれ以下の重合体または化合物であることを示す。 The symbols (P, Q, H, I, J, G and Y) of the coating film compositions in Table 2 indicate that they are the following polymers or compounds, respectively.
水性ポリエステル Water-based polyester
Ρ:酸成分がテレフタル酸(90モル%)、 イソフタル酸(6モル%) および 5— スルホイソフ夕ル酸カリウム (4モル%)、グリコール成分がェチレングリコール (95モル%) およびネオペンチルダリコール (5モル%) の共重合ポリエステ ル (T g = 68 nC) Ρ: The acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%), and the glycol components are ethylene glycol (95 mol%) and neopentyldalicol. (5 mol%) copolymerized polyester (T g = 68 nC )
Q:酸成分がテレフタル酸 (85モル%) およびイソフタル酸 (15モル%)、 グ リコール成分がエチレングリコール (57モル%)、 1, 4一ブタンジオール (4 0モル%)、ジエチレンダリコール(2モル%)およびポリエチレンダリコール(分 子量 600) (1モル%) の共重合ポリエステル (Tg = 47°C)  Q: The acid components are terephthalic acid (85 mol%) and isophthalic acid (15 mol%), the glycol components are ethylene glycol (57 mol%), 1,4-butanediol (40 mol%), and diethylenedalicol ( 2 mol%) and polyethylene dalicol (molecular weight 600) (1 mol%) copolymerized polyester (Tg = 47 ° C)
脂肪酸のアミド、 脂肪酸のビスアミド Amide of fatty acid, bisamide of fatty acid
H: N, N' —メチレンビススァテリン酸アミド  H: N, N'—methylenebisphosphate amide
I : N, N' —エチレンビスパルミチン酸アミド  I: N, N'—Ethylenebispalmitic acid amide
J : N, N' —エチレンビス力プリル酸アミド J: N, N '—Ethylenebis-caprolamide
粗面化物質 Roughening material
K:ァクリル系樹脂微粒子 (平均粒径 0. O S urn)  K: Acryl-based resin fine particles (average particle size: 0.0 Surn)
界面活性剤 Surfactant
Y:ポリオキシエチレンノニルフエニルエーテル  Y: Polyoxyethylene nonylphenyl ether
実施例 9 Example 9
実施例 5の易接着フィルムの片面の塗膜上に、 以下の組成からなる UV硬化系 組成物を口一ルコ一夕一を用いて、 硬化後の膜厚が 5 mとなるように均一に塗 布した。  A UV-curable composition having the following composition was uniformly applied on one surface of the easy-adhesive film of Example 5 using a mouth-to-mouth solution so that the film thickness after curing was 5 m. Coated.
UV硬化組成物  UV curable composition
ペン夕エリスリ! ルァクリレート 45重量%  Eri Eri Suri! 45% by weight acrylate
N—メチロールアクリルアミド 40重量%  N-methylol acrylamide 40% by weight
N一ビニルピ口リドン 10重量%  N-vinyl lipidone 10% by weight
'ェニルケトン 5重量% その後、 8 0W/ c mの強度を有する高圧水銀灯で 3 0秒間紫外線を照射して 硬化させ、 ハードコート層を形成した。 5% by weight of enyl ketone Thereafter, ultraviolet light was irradiated for 30 seconds using a high-pressure mercury lamp having an intensity of 80 W / cm to cure the film, thereby forming a hard coat layer.
そして、 該ハードコート層の上に、 低屈折率層 (S i〇2、 3 0 nm)、 高屈折 率層 (T i〇2、 3 0 nm)、 低屈折率層 (S i〇2、 3 0 nm)、 高屈折率層 (T i〇2、 1 0 0 nm) および低屈折率層 (S i〇2、 1 0 0 nm) がこの順で積層 されてなる反射防止層をスパッタリングによって形成した。 得られた光学用積層 体の評価結果を表 3に示す。 Then, on the hard coat layer, a low refractive index layer (S i〇 2 , 30 nm), a high refractive index layer (T i〇 2 , 30 nm), and a low refractive index layer (S i〇 2 , 3 0 nm), by sputtering a high refractive index layer (T I_〇 2, 1 0 0 nm) and a low refractive index layer (S I_〇 2, 1 0 0 nm) anti-reflection layer they are laminated in this order Formed. Table 3 shows the evaluation results of the obtained optical laminate.
実施例 1 0〜 1 2 Examples 10 to 12
実施例 9において、 二軸配向フィルムおよびその延伸温度と延伸倍率を実施例 2〜4のものに変更する以外は同様な操作を繰返した。 得られた光学用積層体の 評価結果を表 3に示す。  In Example 9, the same operation was repeated except that the biaxially oriented film and the stretching temperature and the stretching ratio were changed to those of Examples 2 to 4. Table 3 shows the evaluation results of the obtained optical laminate.
比較例 7〜 1 2 Comparative Examples 7 to 12
実施例 9において、 二軸配向フィルムおよびその延伸温度と延伸倍率を比較例 1〜6のものに変更し、 かつ、 易滑易接着層を形成するのに用いる塗膜用組成物 を以下に示すように変更する以外は同様な操作を繰返した。 得られた光学用積層 体の評価結果を表 3に示す。  In Example 9, the biaxially oriented film and the stretching temperature and stretching ratio were changed to those of Comparative Examples 1 to 6, and the coating composition used to form the slippery adhesive layer is shown below. The same operation was repeated except for the above change. Table 3 shows the evaluation results of the obtained optical laminate.
塗膜用組成物 Composition for coating film
酸成分がテレフタル酸 ( 9 0モル%)、 イソフタル酸(6モル%)および 5—ス ルホイソフタル酸力リゥム(4モル%)、ダリコール成分がエチレンダリコール(9 5モル%)およびネオペンチルダリコール(5モル%)から合成される T g 6 8 °C の共重合ポリエステル  The acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and 5-sulfoisophthalic acid (4 mol%), and the dalicol component is ethylene dalicol (95 mol%) and neopentyldaricol. (5 mol%) copolymerized polyester with T g 68 ° C
8 0重量%  80% by weight
N, N ' —エチレンビス力プリル酸アミド 5重量%  N, N'—Ethylene bis-forced prillamide 5% by weight
ァクリル系樹脂微粒子 (平均粒径 0. 0 3 xm) Acryl-based resin fine particles (average particle size: 0.03 xm)
ポリォキシェチレンノニルフェニルェ一テル 表 3 ベース 厚み 色素 防眩フィルムとしての評価 Polyoxetylene nonylphenyl ether Table 3 Evaluation of base thickness dye as antiglare film
フィルム Om) (重量%) g/m2 ヘーズ コン卜ラス卜 彩度 表面反 IT 耐磨耗性 実施例 9 実施例 1 75 A (0.03) 0.032 2 〇 〇 ◎ 良好 Film Om) (wt%) g / m 2 Haze Contrast Saturation Surface anti-IT Abrasion resistance Example 9 Example 1 75 A (0.03) 0.032 2 〇 ◎ ◎ Good
実施例 10 実施例 2 200 B(0.03) 0.084 4 ◎ ◎ ◎ 良好 Example 10 Example 2 200 B (0.03) 0.084 4 ◎ ◎ ◎ Good
実施例 11 実施例 3 50 A (0.04) 0.028 3 〇 〇 ◎ 良好 Example 11 Example 3 50 A (0.04) 0.028 3 〇 〇 ◎ Good
実施例 12 実施例 4 75 C(0.07) 0.074 4 ◎ ◎ ◎ 良好 Example 12 Example 4 75 C (0.07) 0.074 4 ◎ ◎ ◎ Good
比較例 7 比較例 1 75 なし 4 X ◎ ◎ 良好 Comparative Example 7 Comparative Example 1 75 None 4 X ◎ ◎ Good
比較例 8 比較例 2 75 D(0.35) 0.368 4 〇 X ◎ 良好 Comparative Example 8 Comparative Example 2 75 D (0.35) 0.368 4 〇 X ◎ Good
比較例 9 比較例 3 75 A (0.20) 0.210 1 ◎ 〇 ◎ 良好 Comparative Example 9 Comparative Example 3 75 A (0.20) 0.210 1 ◎ 〇 ◎ Good
比較例 10 比較例 4 75 B(0.02) 0.021 4 X ◎ ◎ 良好 C 比較例 11 比較例 5 75 C(0.25) 0.263 4 〇 X ◎ 良好 Comparative Example 10 Comparative Example 4 75 B (0.02) 0.021 4 X ◎ ◎ Good C Comparative Example 11 Comparative Example 5 75 C (0.25) 0.263 4 〇 X ◎ Good
比較例 12 比較例 6 200 A (0.10) 0.280 1 ◎ 〇 ◎ 良好 Comparative Example 12 Comparative Example 6 200 A (0.10) 0.280 1 ◎ 〇 ◎ Good
以下、 表 1〜3を考察する。 表 1から明らかなように本発明の二軸配向ポリエ ステルフィルム(実施例 1〜4)は透明性、映像のコントラスト性に優れている。 そしてこれらの本発明の二軸配向ポリエステルフィルムに接着性 mを塗設した 接着性フィルム (実施例 5〜8) は表 2から明らかなようにガラス用接着剤およ び Λ—ドコートに対して良好な接着性を有しながら光学特性を損わない。しかも、 これらの本発明の接着性フィルムにハードコート層および反射防止層を設けた積 層フィルム (実施例 9〜12) は、 映像のコントラストに加えて、 耐摩耗性や反 射防止能にも優れるものであった。 これに対して、 本発明の要件のいずれかを満 たしていない比較例 1〜 6の二軸配向ポリエステルフィルムおよび比較例 7〜 1 2の積層フィルムは、 乏しい光学特性しか示さなかった。 Hereinafter, Tables 1 to 3 will be considered. As is clear from Table 1, the biaxially oriented polyester films of the present invention (Examples 1 to 4) are excellent in transparency and image contrast. The adhesive films (Examples 5 to 8) obtained by coating the biaxially oriented polyester film of the present invention with the adhesive m (Examples 5 to 8) showed that the adhesive film for glass and the cord coat were clear as shown in Table 2. It has good adhesiveness and does not impair optical properties. Moreover, the laminated films in which the hard coat layer and the antireflection layer are provided on the adhesive film of the present invention (Examples 9 to 12) not only have an image contrast, but also have abrasion resistance and antireflection ability. It was excellent. On the other hand, the biaxially oriented polyester films of Comparative Examples 1 to 6 and the laminated films of Comparative Examples 7 to 12, which did not satisfy any of the requirements of the present invention, showed only poor optical characteristics.
実施例 13 Example 13
以下の一般式 (1') (2,) (3,) (4') で示される染料をそれぞれ 40. 6m o 1 %、 16. 7mo l %、 26. 2mo l%および 16. 6mo 1 %の比率で 混合した染料混合物と平均粒径 1. 7 の多孔質シリカとを、 固有粘度 0. 6 5 (35。C、 o—クロ口フエノール) のポリエチレンテレフ夕レートに、 それぞ れ 0. 08重量%と 0. 007重量%となるように配合させてから、 該ポリェチ レンテレフ夕レートを溶融状態でダイより押出し、 常法により冷却ドラムで冷却 して未延伸フィルムとした。 次いで、 該未延伸フィルムを縦方向に 90°Cの温度 で延伸倍率 3. 5倍で延伸した後、 その両面に以下の塗膜用組成物の濃度 8%の 水性液を口一ルコ一夕一で均一に塗布し、 その後、 引き続いて 95 °Cで乾燥した 後、 横方向に 12 O で延伸倍率 3. 8倍で延伸し、 23 Ot:で熱固定して、 厚 さ 75 At mの易接着フィルムを得た。なお、塗膜の厚さは 0. 15
Figure imgf000041_0001
た。 得られた易接着フィルムの評価結果を表 4に示す。
Figure imgf000042_0001
塗膜用組成物
The dyes represented by the following general formulas (1 ′), (2,), (3,) and (4 ′) were converted to 40.6 mol 1%, 16.7 mol%, 26.2 mol% and 16.6 mol 1%, respectively. The dye mixture and the porous silica having an average particle size of 1.7 were mixed into polyethylene terephthalate having an intrinsic viscosity of 0.65 (35.C, o-chlorophenol), respectively. After blending so as to be 08% by weight and 0.007% by weight, the polyethylene terephthalate was extruded in a molten state from a die, and cooled by a cooling drum by a conventional method to obtain an unstretched film. Next, the unstretched film was stretched in the longitudinal direction at a temperature of 90 ° C. at a stretch ratio of 3.5, and an aqueous liquid having a concentration of 8% of the following coating composition was applied to both surfaces thereof. And then dried at 95 ° C, stretched transversely with 12 O at a stretch ratio of 3.8 times, heat-fixed with 23 Ot: and a thickness of 75 Atm. An easily adhesive film was obtained. The thickness of the coating film is 0.15
Figure imgf000041_0001
Was. Table 4 shows the evaluation results of the obtained easily adhesive films.
Figure imgf000042_0001
Composition for coating film
酸成分がテレフタル酸 (90モル%)、 イソフタル酸(6モル%)および 5—ス ルホイソフタル酸カリウム( 4モル%)、グリコール成分がェチレンダリコール(9 5モル%)およびネオペンチルダリコール(5モル%)から合成される Tg 68°C の共重合ポリエステル  The acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%), and the glycol component is ethylendalicol (95 mol%) and neopentyldaricol ( (5 mol%) copolymerized polyester with Tg of 68 ° C
80重量%  80% by weight
N, N' —エチレンビス力プリル酸アミド 5重量%  N, N '-ethylene bis-forced prillamide 5% by weight
ァクリル系樹脂微粒子 (平均粒径 0. 03 ΐΐύ 10重量% Acryl-based resin fine particles (Average particle size: 0.03-10% by weight
ポリォキシェチレンノニルフェニルエーテル Polyoxetylene nonyl phenyl ether
実施例 14〜16、 比較例 13 Examples 14 to 16, Comparative Example 13
実施例 13において、 厚み、 染料の種類および染料の添加量を、 それぞれ表 4 に示すように変更する以外は同様な操作を繰返した。 得られた二軸配向ポリエス テルフィルムの光学特性の評価結果を表 4に示す。  The same operation as in Example 13 was repeated except that the thickness, the type of dye and the amount of dye added were changed as shown in Table 4, respectively. Table 4 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
比較例 14、 1 5 実施例 1 3において、 染料の種類と染料の添加量を表 4に示すように変更し、 かつ、 滑剤として平均粒径 4. 0 mの多孔質シリカを 0. 0 0 7重量%添加す る以外は同様な操作を繰返した。 得られた二軸配向ポリエステルフィルムの光学 特性の評価結果を表 4に示す。 Comparative Examples 14, 15 In Example 13, the type of dye and the amount of dye added were changed as shown in Table 4, and 0.07% by weight of porous silica having an average particle size of 4.0 m was added as a lubricant. Other than the above, the same operation was repeated. Table 4 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
表 4 厚み 色素 滑剤 熱固定温度 熱収縮率 (%) 表面粗さ 透過率へ -ス" コントラスト 彩度 AR加工後のTable 4 Thickness Dye Lubricant Heat setting temperature Heat shrinkage (%) Surface roughness To transmittance -S "Contrast Saturation After AR processing
(βΐΏ) (重量%) g/mz (°C) 長手方向 幅方向 (nm) (%) (%) (一) (一) 表面性 (一) 実施例 13 75 EC0.08) 0.084 S 230 1.60 0.80 5.1 〇 1.3 ◎ ◎ 〇 実施例 14 200 FC0.03) 0.084 S 230 1.54 0.60 5.2 〇 2.1 ◎ 〇 〇 実施例 15 50 GC0.04) 0.028 S 230 1.39 0.76 5.4 〇 0.9 〇 〇 〇 実施例 16 75 G(0.07) 0.074 S 230 1.61 0.60 5.0 〇 1.2 ◎ 〇 〇 比較例 13 75 なし S 230 1.63 0.50 5.4 X 1.3 X ◎ 〇 比較例 14 75 EC0.08) 0.084' T 230 1.60 0.79 22.2 〇 8.2 ◎ ◎ 〇 比較例 15 75 G(0.07) 0.074 T 230 1.58 0.98 18.9 〇 7.6 ◎ ◎ 〇 (βΐΏ) (% by weight) g / m z (° C) Longitudinal width (nm) (%) (%) (1) (1) Surface properties (1) Example 13 75 EC0.08) 0.084 S 230 1.60 0.80 5.1 〇 1.3 ◎ ◎ 〇 Example 14 200 FC0.03) 0.084 S 230 1.54 0.60 5.2 〇 2.1 ◎ 〇 〇 Example 15 50 GC0.04) 0.028 S 230 1.39 0.76 5.4 〇 0.9 〇 〇 例 Example 16 75 G (0.07) 0.074 S 230 1.61 0.60 5.0 〇 1.2 ◎ 〇 比較 Comparative example 13 75 None S 230 1.63 0.50 5.4 X 1.3 X ◎ 比較 Comparative example 14 75 EC0.08) 0.084 'T 230 1.60 0.79 22.2 〇 8.2 ◎ ◎ 〇 〇 Comparative Example 15 75 G (0.07) 0.074 T 230 1.58 0.98 18.9 〇 7.6 ◎ ◎ 〇
ここで、 表 4中の記号 E, Fおよび Gで表された染料は、 実施例 4の一般式で 表された (1') (2') (3') (4') の染料を、 以下の割合で混合させたものであ る。 Here, the dyes represented by the symbols E, F and G in Table 4 are the dyes of (1 ′) (2 ′) (3 ′) (4 ′) represented by the general formula of Example 4, It was mixed in the following ratio.
E: (1,) : (2,) : (3,) : (4')  E: (1,): (2,): (3,): (4 ')
=40. 6 : 16. 7 : 26. 2 : 16. 6 (mo 1 )  = 40.6: 16.7: 26.2: 16.6 (mo 1)
F: (1'): (2'): (3,) : (4,)  F: (1 '): (2'): (3,): (4,)
= 35. 3 : 28. 9 : 14. 2 : 21. 6 (mo 1 %)  = 35.3: 28.9: 14.2: 21.6 (mo 1%)
G: (1,) : (2,) : (3'): (4,) G: (1,): (2,): (3 '): (4,)
= 30. 5 : 25. 0 : 19. 7 : 24. 9 (mo 1 )  = 30.5: 25. 0: 19.7: 24.9 (mo 1)
さらにまた、 表 1中の記号 Sおよび Tは以下の滑剤を示す。  Furthermore, the symbols S and T in Table 1 indicate the following lubricants.
:平均粒径1. 7 /zmの多孔質シリカ (0. 0038wt%)  : Porous silica with an average particle size of 1.7 / zm (0.0038wt%)
T:平均粒径 0. 9 xmの天然力オリン粒子 ( 0. 08 Owt ) T: Natural force Olin particles with an average particle size of 0.9 xm (0.08 Owt)
実施例 17〜 20 Examples 17 to 20
塗膜用組成物の組成を表 5に示すように変更した以外は、 実施例 13と同様に して厚さ 75 mの光学用易接着性フィルムを得た。 なお、 塗膜の厚さは 0. 1 5 mであった。 得られた易接着フィルムの評価結果を表 5に示す。 An optically-adhesive film with a thickness of 75 m was obtained in the same manner as in Example 13 except that the composition of the coating composition was changed as shown in Table 5. The thickness of the coating film was 0.15 m. Table 5 shows the evaluation results of the obtained easily adhesive films.
表 5 実施例 17 実施例 18 実施例 19 実施例 20 Table 5 Example 17 Example 18 Example 19 Example 20
水性ホ°リエステル (重量%) P(80) Ρ(80) Q(80) Q(80)  Aqueous polyester (wt%) P (80) Ρ (80) Q (80) Q (80)
脂肪酸アミド or脂肪酸ビスアミド(重量%) J (5) Η(5) Η(5) 1(5)  Fatty acid amide or fatty acid bisamide (% by weight) J (5) Η (5) Η (5) 1 (5)
易接着性塗膜用組成物 Composition for easily adhesive coating
粗面化物質 (重量%) K(10) Κ(10) Κ(10) Κ(10)  Roughening substance (wt%) K (10) Κ (10) Κ (10) Κ (10)
界面活性剤 (重量%) Y(5) Υ(5) Υ(5) Υ(5)  Surfactant (% by weight) Y (5) Υ (5) Υ (5) Υ (5)
裏面反射率 (一) 〇 〇 〇 〇  Backside reflectance (1) 〇 〇 〇 〇
(一) 0.70 0.72 0.75 0.75  (One) 0.70 0.72 0.75 0.75
厚み方向屈折率 屈折率 1.559 1.552 1.550 1.549  Thickness direction refractive index Refractive index 1.559 1.552 1.550 1.549
表面粗さ (nm) 10 10 9 9  Surface roughness (nm) 10 10 9 9
耐接着剤 (一) 〇 〇 ◎ ◎  Adhesive resistance (1) 〇 ◎ ◎ ◎
藤、 -ドコ-ト (一) 4 4 5 5 0 Wisteria, -document (one) 4 4 5 5 0
ここで、 表 5中の記号 P、 Q、 H、 I、 J、 Kおよび Yは、 塗膜用組成物にお けるそれぞれ以下の重合体または化合物を示す。 Here, the symbols P, Q, H, I, J, K and Y in Table 5 represent the following polymers or compounds in the coating composition, respectively.
水性ポリエステル Water-based polyester
P:酸成分がテレフタル酸 ( 9 0モル%)、 イソフ夕ル酸(6モル%) および 5— スルホイソフタル酸カリウム(4モル%)、グリコール成分がエチレングリコール ( 9 5モル%) およびネオペンチルダリコール (5モル%) の共重合ポリエステ ル (T g = 6 8 °C)  P: The acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%), and the glycol components are ethylene glycol (95 mol%) and neopen Copolymerized polyester of tildaricol (5 mol%) (T g = 68 ° C)
Q:酸成分がテレフタル酸 ( 8 5モル%) およびイソフタル酸 ( 1 5モル%)、 グ リコール成分がエチレングリコール(5 7モル%)、 1, 4一ブタンジオール(4 0モル%)、ジエチレンダリコール( 2モル%)およびポリエチレンダリコ一ル(分 子量 6 0 0 ) ( 1モル%) の共重合ポリエステル (T g = 4 7 °C)  Q: Acid components are terephthalic acid (85 mol%) and isophthalic acid (15 mol%), glycol components are ethylene glycol (57 mol%), 1,4-butanediol (40 mol%), diethylene Copolyester of Daricol (2 mol%) and Polyethylene Daricol (molecular weight: 600) (1 mol%) (T g = 47 ° C)
脂肪酸のアミド、 脂肪酸のビスアミド Amide of fatty acid, bisamide of fatty acid
H: N, N ' —メチレンビススァテリン酸アミド  H: N, N'-methylenebisphosphate amide
I : N, N ' —エチレンビスパルミチン酸アミド  I: N, N'—Ethylenebispalmitic acid amide
J : N, N ' 一エチレンビスカプリル酸アミド  J: N, N 'monoethylenebiscaprylic amide
粗面化物質 Roughening material
K:ァクリル系樹脂微粒子 (平均粒径 0 . 0 3 m)  K: Acryl resin fine particles (average particle diameter: 0.03 m)
界面活性剤 Surfactant
Y:ポリオキシエチレンノエルフエニルエーテル  Y: polyoxyethylene noenyl ether
実施例 2 1 Example 2 1
実施例 1 3の易接着フィルムの片面の塗膜上に、 以下の組成からなる UV硬化 系組成物を口一ルコ一夕一を用いて、 硬化後の膜厚が 5 mとなるように均一に 塗布した。  Example 1 A UV-curable composition having the following composition was uniformly applied on one surface of the easy-adhesive film of Example 3 using a mouth-to-mouth solution so that the film thickness after curing was 5 m. Was applied.
UV硬化組成物 UV curable composition
ペン夕エリスリトールァクリレート 4 5重量%  Pen evening erythritol acrylate 45 5% by weight
N—メチ口一ルアクリルアミド 4 0重量%  N-methyl acrylamide 40% by weight
N—ビニルピロリドン 1 0重量%  N-vinylpyrrolidone 10% by weight
1ーヒドロキシシクロへキシルフェニルケトン 5重量% その後、 8 O WZ c mの強度を有する高圧水銀灯で 3 0秒間紫外線を照射して 硬ィ匕させ、 ハードコート層を形成した。 1-hydroxycyclohexyl phenyl ketone 5% by weight Thereafter, ultraviolet irradiation was performed for 30 seconds with a high-pressure mercury lamp having an intensity of 8 OWZ cm to perform hardening, thereby forming a hard coat layer.
そして、 該ノヽードコート層の上に、 低屈折率層 (S i〇2、 3 0 nm)、 高屈折 率層 (T i〇2、 3 0 nm)、 低屈折率層 (S i 02、 3 0 nm)、 高屈折率層 (T i〇2、 1 0 0 nm) および低屈折率層 (S i〇2、 1 0 0 nm) がこの順で積層 されてなる反射防止層をスパッタリングによって形成した。 得られた光学用積層 体の評価結果を表 6に示す。 Then, on the node coat layer, a low refractive index layer (Si 2 , 30 nm), a high refractive index layer (Ti 2 , 30 nm), a low refractive index layer (Sio 2 , 3 0 nm), by sputtering a high refractive index layer (T I_〇 2, 1 0 0 nm) and a low refractive index layer (S I_〇 2, 1 0 0 nm) anti-reflection layer are laminated in this order Formed. Table 6 shows the evaluation results of the obtained optical laminate.
実施例 2 2〜 2 4 Example 22 to 24
実施例 2 1において、 易接着フィルムおよびその製造工程における延伸温度と 延伸倍率を実施例 1 4〜 1 6のものに変更する以外は同様な操作を繰返した。 得 られた光学用積層体の評価結果を表 6に示す。  The same operation as in Example 21 was repeated except that the stretching temperature and the stretching ratio in the easily adhesive film and the production process thereof were changed to those of Examples 14 to 16. Table 6 shows the evaluation results of the obtained optical laminate.
比較例 1 6〜 1 8 Comparative Example 16 to 18
実施例 2 1において、 易接着フィルムおよびその製造工程における延伸温度と 延伸倍率を比較例 1 3〜1 5のものに変更し、 かつ、 対接着剤易接着性塗膜を形 成するのに用いる塗膜用組成物を以下に示すように変更する以外は同様な操作を 繰返した。 得られた光学用積層体の評価結果を表 6に示す。  In Example 21, the stretching temperature and the stretching ratio in the easy-adhesion film and the manufacturing process thereof were changed to those of Comparative Examples 13 to 15 and used to form an easily-adhesive coating film with respect to the adhesive. The same operation was repeated except that the coating composition was changed as shown below. Table 6 shows the evaluation results of the obtained optical laminate.
塗膜用組成物 Composition for coating film
酸成分がテレフタル酸 ( 9 0モル%)、 イソフタル酸(6モル%)および 5—ス ルホイソフタル酸カリウム(4モル%)、グリコール成分がェチレングリコ一ル(9 5モル%)およびネオペンチルグリコ一ル(5モル%)から合成される T g 6 8 °C の共重合ポリエステル  The acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%), and the glycol component is ethylene glycol (95 mol%) and neopentyl glycol. (5 mol%) copolymerized polyester with T g 68 ° C
8 0重量%  80% by weight
N, N' —エチレンビス力プリル酸アミド 5重量%  N, N'—Ethylene bis-forced prillamide 5% by weight
ァクリル系樹脂微粒子 (平均粒径 0. 0 3 m) 1 0重量% Acryl resin fine particles (average particle diameter: 0.03 m) 10% by weight
ポリオキシエチレンノニルフエ二ルェ一テル 5重量% 表 6 へ― _·入マ J字み 色素 防眩フィルムとしての評価 フィルム (重量%) ヘーズ コントラスト 彩度 表面反射 耐磨耗性 実施例 21 実施例 13 75 Ε(0.08) 0.084 1.3 ◎ ◎ 〇 良好 実施例 22 実施例 14 200 F(0.03) 0.084 2.1 ◎ 〇 〇 良好 実施例 23 実施例 15 50 G(0.04) 0.028 0.9 〇 〇 〇 良好 実施例 24 実施例 16 75 G(0.07) 0.074 1.2 ◎ 〇 〇 良好 比較例 16 比較例 13 75 なし 1.3 X ◎ 〇 良好 比較例 17 比較例 14 75 ECO.08) 0.084 8.2 ◎ ◎ X 良好 比較例 18 比較例 15 75 G(0.07) 0.074 7.6 ◎ 〇 X 良好 5% by weight of polyoxyethylene nonylphenyl ether Go to Table 6-_ · Insertion J-shape Dye Evaluation as anti-glare film Film (% by weight) Haze Contrast Saturation Surface reflection Abrasion resistance Example 21 Example 13 75 Ε (0.08) 0.084 1.3 ◎ ◎ 良好 Good Example 22 Example 14 200 F (0.03) 0.084 2.1 ◎ 〇 〇 Good Example 23 Example 15 50 G (0.04) 0.028 0.9 〇 〇 Good Example 24 Example 16 75 G (0.07) 0.074 1.2 ◎ 〇 〇 Good Comparative Example 16 Comparative Example 13 75 None 1.3 X ◎ 良好 Good Comparative Example 17 Comparative Example 14 75 ECO.08) 0.084 8.2 ◎ ◎ X Good Comparative Example 18 Comparative Example 15 75 G (0.07) 0.074 7.6 ◎ 〇 X Good
以下、 表 4〜6を考察する。 表 4から明らかなように本発明の接着性フィルム (実施例 13~16) は透明性、 映像のコントラスト性に優れている。 そしてこ れらの本発明の接着性フィルム (実施例 17〜20) は表 5から明らかなように ガラス用接着剤および八一ドコートに対して良好な接着性を有しながら光学特性 を損わない。 しかも、 これらの本発明の接着性フィルムにハードコート層および 反射防止層を設けた積層フィルム (実施例 21〜22) は、 B央像のコントラスト に加えて、 耐摩耗性や反射防止能にも優れるものであった。 これに対して、 本発 明の要件のいずれかを満たしていない比較例 13〜15の易接着性フィルムおよ び比較例 16〜18の積層フィルムは、 乏しい光学特性しか示さなかった。 実施例 25 Hereinafter, Tables 4 to 6 are considered. As is clear from Table 4, the adhesive films of the present invention (Examples 13 to 16) are excellent in transparency and image contrast. As is clear from Table 5, these adhesive films of the present invention (Examples 17 to 20) have good adhesiveness to glass adhesives and eighty-one coats while deteriorating optical characteristics. Absent. Moreover, the laminated films (Examples 21 to 22) in which the hard coat layer and the anti-reflection layer are provided on the adhesive film of the present invention have not only the contrast of the B image but also the abrasion resistance and the anti-reflection ability. It was excellent. In contrast, the easily adhesive films of Comparative Examples 13 to 15 and the laminated films of Comparative Examples 16 to 18 which did not satisfy any of the requirements of the present invention showed only poor optical characteristics. Example 25
実施例 2において、 色素に加えて、 紫外線吸収剤として 2, 2 '― p—フエ二 レンビス (3, 1—ベンゾォキサジノン一 4一オン) を 0. 5重量%添加する以 外は同様な操作を繰返した。 得られたニ軸配向ポリエステルフィルムの光学特性 の評価結果を表 7に示す。  Example 2 is the same as Example 2 except that 0.5% by weight of 2,2′-p-phenylenebis (3,1-benzoxazidinone-141) is added as an ultraviolet absorber in addition to the dye. Operation was repeated. Table 7 shows the evaluation results of the optical properties of the obtained biaxially oriented polyester film.
実施例 26 Example 26
実施例 25において、 紫外線吸収剤を 2, 2 ' -P, p '—ジフエ二レンビス (3, 1一べンゾォキサジノン一 4一オン)に変更し、その添加量を 1. 0重量% に変更する以外は同様な操作を繰返した。 得られた二軸配向ポリエステルフィル ムの光学特性の評価結果を表 7に示す。  In Example 25, the UV absorber was changed to 2,2′-P, p′-diphenylenebis (3.1-benzozozidinone-one), and the added amount was changed to 1.0% by weight. Other than the above, the same operation was repeated. Table 7 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
実施例 27 Example 27
実施例 26において、 2, 2 ' -P, p '—ジフエ二レンビス (3, 1—ベン ゾォキサジノン一 4一オン) の添加量を 0. 5重量%に変更する以外は同様な操 作を繰返した。 得られた二軸配向ポリエステルフィルムの光学特性の評価結果を 表 7に示す。  In Example 26, the same operation was repeated except that the addition amount of 2,2′-P, p′-diphenylenebis (3,1-benzoxazidinone-one) was changed to 0.5% by weight. Was. Table 7 shows the evaluation results of the optical characteristics of the obtained biaxially oriented polyester film.
実施例 28 Example 28
実施例 25において、 紫外線吸収剤を 2— p—二トロフエ二ルー 3, 1—ベン ゾォキサジノン一 4—オンに変更し、 その添加量を 0. 5重量%に変更する以外 は同様な操作を繰返した。 得られた二軸配向ポリエステルフィルムの光学特性の 評価結果を表 7に示す。 In Example 25, the same operation was repeated except that the ultraviolet absorbent was changed to 2-p-nitrophenyl-3,1-benzoxazinone-1-one and the added amount was changed to 0.5% by weight. Was. Of the optical properties of the obtained biaxially oriented polyester film Table 7 shows the evaluation results.
表 7  Table 7
Figure imgf000051_0001
ここで、 表 7中の記号 U, Vおよび Wで表された紫外線吸収剤は、 以下のもの である。
Figure imgf000051_0001
Here, the ultraviolet absorbers represented by the symbols U, V and W in Table 7 are as follows.
U: 2, 2 ' _p—フエ二レンビス (3, 1ーブンゾォキサジノンー 4一オン) V: 2— p—二トロフエ二ルー 3, 1一べンゾォキサジノン一 4—オン  U: 2, 2 '_p-phenylene bis (3,1-bunzoxazidinone-4-one) V: 2-p-ditrofu-2-ru 3, 1-benzozoxazinone-4-one
W: 2, 2 '一 p, p '—ジフエ二レンビス (3, 1—ベンゾォキサジノン一 4 一オン) W: 2,2'-p, p'-diphenylenebis (3,1-benzoxazidinone 4-one)
実施例 29 Example 29
日本化薬社製 Kaya s e t B 1 a c k AN (染料) を 0. 03重量%、 平均粒径 1· 7 /zmの多孔質シリカを 0. 007重量%含有した溶融ポリェチレ ンテレフタレート ([?7] =0. 65) をダイより押出し、 常法により冷却ドラム で冷却して未延伸フィルムとし、 次いで縦方向に 90 の温度で延伸倍率 3. 5 倍で延伸した後、 その両面に以下の塗膜用組成物の濃度 8 %の水性液をロールコ 一夕一で均一に塗布し、 その後、 引き続いて 95°Cで乾燥しながら横方向に 12 0°Cで 3. 8倍に延伸し、 230°Cで熱固定して、 厚さ 75 /mの易接着フィル ムを得た。 なお、 塗膜の厚さは 0. 15 mであった。 得られた易接着フィルム の評価結果を表 8に示す。  Molten polyethylene terephthalate containing 0.03% by weight of Kaya set B 1 ack AN (dye) manufactured by Nippon Kayaku Co. and 0.007% by weight of porous silica having an average particle diameter of 1.7 / zm ([? 7] = 0.65) from a die, cooled with a cooling drum by a conventional method to form an unstretched film, and then stretched in a longitudinal direction at a temperature of 90 at a stretch ratio of 3.5 times. Aqueous liquid with a concentration of 8% of the composition for application is uniformly applied all over a roll, then stretched 3.8 times at 120 ° C in the horizontal direction while drying at 95 ° C, then 230 ° By heat fixing with C, an easily adhesive film having a thickness of 75 / m was obtained. Incidentally, the thickness of the coating film was 0.15 m. Table 8 shows the evaluation results of the obtained easily adhesive film.
塗膜用組成物 Composition for coating film
酸成分がテレフタル酸 (90モル%)、イソフタル酸(6モル%)および 5—ス ルホイソフタル酸カリゥム(4モル%)、ダリコール成分がエチレンダリコール( 9 5モル%)およびネオペンチルグリコール( 5モル%)から合成される T g 6 8 °C の共重合ポリエステル The acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%), and the daricol component is ethylene dalicol (9 mol%). 5 mol%) and neopentyl glycol (5 mol%), T g 68 ° C copolymerized polyester
8 0重量%  80% by weight
N, N' —エチレンビス力プリル酸アミド  N, N'—Ethylene bis-caprolamide
ァクリル系樹脂微粒子 (平均粒径 0. 0 3 m) 1 0重量% Acryl resin fine particles (average particle diameter: 0.03 m) 10% by weight
ポリオキシエチレンノニルフエニルエーテル 5重量% 5% by weight of polyoxyethylene nonylphenyl ether
実施例 3 0 Example 30
実施例 2 9において、 色素に加えて、 紫外線吸収剤として 2, 2 '— p—フエ 二レンビス (3, 1—ブンゾォキサジノン一 4—オン) を 0 . 5重量%添加する 以外は同様な操作を繰返した。得られた易接着フィルムの評価結果を表 8に示す。 実施例 3 1〜3 3  Example 29 is the same as Example 29 except that 0.5% by weight of 2,2′-p-phenylenebis (3,1-bunzoxazinone-1-one) was added as an ultraviolet absorber in addition to the dye. Operation was repeated. Table 8 shows the evaluation results of the obtained easily adhesive film. Example 31 to 33
実施例 3 0において、 紫外線吸収剤およびその添加量を、 表 8に示すように変 更する以外は同様な操作を繰返した。 得られた易接着フィルムの評価結果を表 8 に示す。  In Example 30, the same operation was repeated except that the ultraviolet absorber and the amount of addition thereof were changed as shown in Table 8. Table 8 shows the evaluation results of the obtained easily adhesive films.
表 8  Table 8
Figure imgf000052_0001
表 8における塗膜用組成物の記号 (P、 Q、 H、 I、 J、 Kおよび Y) は、 そ れぞれ以下の重合体または化合物である。
Figure imgf000052_0001
The symbols (P, Q, H, I, J, K and Y) of the coating composition in Table 8 are the following polymers or compounds, respectively.
水性ポリエステル Water-based polyester
Ρ:酸成分がテレフタル酸 ( 9 0モル%)、 イソフタル酸(6モル%)および 5— スルホイソフタル酸カリウム(4モル%)、グリコール成分がエチレングリコール (95モル%) およびネオペンチルダリコール (5モル%) の共重合ポリエステ ル (Tg=68。C) Ρ: Acid component is terephthalic acid (90 mol%), isophthalic acid (6 mol%) and potassium 5-sulfoisophthalate (4 mol%), glycol component is ethylene glycol (95 mol%) and neopentyldaricol (5 mol%) copolymerized polyester (Tg = 68.C)
Q:酸成分がテレフタル酸 (85モル%) およびイソフタル酸 (15モル%)、 グ Uコール成分がエチレングリコール (57モル%)、 1, 4—ブタンジオール (4 0モル%)、ジエチレングリコール(2モル%)およびポリエチレングリコール(分 子量 600) (1モル%) の共重合ポリエステル (Tg = 47 )  Q: The acid component is terephthalic acid (85 mol%) and isophthalic acid (15 mol%), the glycol component is ethylene glycol (57 mol%), 1,4-butanediol (40 mol%), diethylene glycol (2 mol%). Mol%) and polyethylene glycol (molecular weight 600) (1 mol%) copolymerized polyester (Tg = 47)
脂肪酸のアミド、 脂肪酸のビスアミド Amide of fatty acid, bisamide of fatty acid
H: N, N' —メチレンビススァテリン酸アミド H: N, N'—methylenebisphosphate amide
I : N, N, 一エチレンビスパルミチン酸アミド  I: N, N, monoethylenebispalmitic acid amide
J : N, N' —エチレンビス力プリル酸アミド J: N, N'—Ethylene bis-forced prillamide
粗面化物質 Roughening material
K:ァクリル系樹脂微粒子 (平均粒径 0. 03 m)  K: Acryl resin fine particles (average particle size: 0.03 m)
界面活性剤 Surfactant
Y:ポリオキシエチレンノエルフエニルエーテル  Y: polyoxyethylene noenyl ether
実施例 34 Example 34
実施例 29の易接着フィルムの片面の塗膜上に、 以下の組成からなる UV硬化 系組成物をロールコ一ターを用いて、 硬化後の膜厚が 5 mとなるように均一に 塗布した。  A UV curable composition having the following composition was uniformly applied on one surface of the easily adhesive film of Example 29 using a roll coater so that the film thickness after curing was 5 m.
UV硬化組成物 UV curable composition
ペン夕エリスリトールァクリレート 45重量%  Penyu erythritol acrylate 45% by weight
N—メチ口一ルアクリルアミド 40重量%  N-methyl acrylamide 40% by weight
N—ビニルピロリドン 10重量%  N-vinylpyrrolidone 10% by weight
1ーヒドロキシシクロへキシルフェニルケトン 5重量%  1-hydroxycyclohexyl phenyl ketone 5% by weight
その後、 8 OW/ cmの強度を有する高圧水銀灯で 30秒間紫外線を照射して 硬化させ、 ハードコート層を形成した。  Thereafter, ultraviolet rays were irradiated for 30 seconds with a high-pressure mercury lamp having an intensity of 8 OW / cm to cure, thereby forming a hard coat layer.
そして、 該ハードコ一ト層の上に、 低屈折率層 (S i 02、 30nm)、 高屈折 率層 (T i〇2、 30nm)、 低屈折率層 (S i〇2、 30nm)、 高屈折率層 (T i〇2、 100 nm) および低屈折率層 (S i〇2、 100 nm) がこの順で積層 されてなる反射防止層をスパッタリングによって形成した。 得られた光学用積層 体の評価結果を表 9に示す。 Then, on of the hard coat one coat layer, a low refractive index layer (S i 0 2, 30 nm), a high refractive index layer (T I_〇 2, 30 nm), a low refractive index layer (S I_〇 2, 30 nm), High refractive index layer (Ti 2 , 100 nm) and low refractive index layer (Si 2 , 100 nm) are stacked in this order The resulting anti-reflection layer was formed by sputtering. Table 9 shows the evaluation results of the obtained optical laminate.
実施例 3 5〜 3 8 Example 35 to 38
実施例 3 4において、 易接着フィルムを実施例 3 0〜3 3のものに変更する以 外は同様な操作を繰返した。 得られた光学用積層体の評価結果を表 9に示す。 In Example 34, the same operation was repeated, except that the easily adhesive film was changed to those of Examples 30 to 33. Table 9 shows the evaluation results of the obtained optical laminate.
表 9 ベース 厚み 紫外線吸収剤 防眩フィルムとしての評価 フィルム ( u m) ヘーズ コントラスト 彩度 表面反射 耐磨耗性 耐光劣化性 実施例 3 4 実施例 2 200 4 ◎ ◎ ◎ 良好 〇 実施例 3 5 実施例 2 5 200 U (0. 5) 4 ◎ ◎ ◎ 良好 ◎ 実施例 3 6 実施例 2 6 200 W(1. 0) 4 ◎ ◎ ◎ 良好 ◎ 実施例 3 7 実施例 2 7 200 W(0. 5) 4 ◎ ◎ ◎ 良好 ◎ 実施例 3 7 実施例 2 8 200 V (0. 5) 4 ◎ ◎ ◎ 良好 ◎ Table 9 Base Thickness UV absorber Evaluation as anti-glare film Film (um) Haze Contrast Saturation Surface reflection Abrasion resistance Light degradation Example 3 4 Example 2 200 4 ◎ ◎ ◎ Good 〇 Example 3 5 Example 2 5 200 U (0.5) 4 ◎ ◎ ◎ Good ◎ Example 3 6 Example 2 6 200 W (1.0) 4 ◎ ◎ ◎ Good ◎ Example 3 7 Example 2 7 200 W (0.5 ) 4 ◎ ◎ ◎ Good ◎ Example 3 7 Example 2 8 200 V (0.5) 4 ◎ ◎ ◎ Good ◎
以下、 表 7〜9を考察する。 表 7から明らかなように紫外線吸収剤が添加され た本発明の二軸配向ポリエステルフィルム (実施例 2 5〜2 8 ) は、 優れた耐光 劣化性を有し、 それらを用いた本発明の接着性フィルム (実施例 3 0〜3 3 ) お よび積層フィルム (実施例 3 5〜3 8 ) も同様に優れた耐光劣ィヒ性を有するもの であった。 Hereinafter, Tables 7 to 9 are considered. As is clear from Table 7, the biaxially oriented polyester film of the present invention to which an ultraviolet absorber was added (Examples 25 to 28) had excellent light degradation resistance, and the adhesive of the present invention using them was used. The transparent films (Examples 30 to 33) and the laminated films (Examples 35 to 38) also had excellent light resistance.
以上のとおり、 本発明によれば、 透明性を損うことなく映像のコントラストが 高い二軸配向ポリエステルフィルムおよびその積層フィルムが得られる。 さらに また、 本発明によれば、 積層フィルムの接着力の向上や裏面反射率の縮小をすれ ば、 表面硬度ゃ耐摩耗性等が良好で、 しかも十分な透明性、 防眩性および防爆性 などを備えた積層フィルムを堤供することもでき、 特にパソコンディスプレイの 表面保護板として有用である。 また、 本発明の二軸配向ポリエステルフィルムお よびその積層フィルムは、 前述のパソコンディスプレイの表面保護板に加えて、 窓ガラス、 ショーケース、 眼鏡、 計器類、 写真、 絵画、 イラスト、 看板等の表面 保護シートとしても好適に使用でき、 工業的価値の高いものである。  As described above, according to the present invention, it is possible to obtain a biaxially oriented polyester film having high image contrast without impairing transparency and a laminated film thereof. Furthermore, according to the present invention, if the adhesive strength of the laminated film is improved and the back surface reflectance is reduced, the surface hardness / abrasion resistance and the like are good, and sufficient transparency, anti-glare properties and explosion-proof properties are obtained. It can be used as a protective film for personal computer displays. Further, the biaxially oriented polyester film of the present invention and the laminated film thereof may be used in addition to the above-mentioned surface protective plate of a personal computer display, as well as the surface of window glass, showcases, glasses, instruments, photographs, paintings, illustrations, signs, etc. It can be suitably used as a protective sheet and has high industrial value.

Claims

請求の範囲 The scope of the claims
1. (1) 色素を含有し、 1. (1) Contains a dye,
(2) へ一ズ値が 5%以下であり、  (2) The haze value is 5% or less,
(3) 波長 450〜650 nmにおける光線の透過率の平均値 (Ta v) が 40 〜80 %であり、  (3) The average value (Ta v) of the light transmittance at a wavelength of 450 to 650 nm is 40 to 80%,
(4) 波長 450〜650 nmにおける各波長 iの光線の透過率 (T i ) を Ta Vで割った値が 0. 7〜; 1. 3であり、 そして  (4) The value obtained by dividing the transmittance (T i) of light of each wavelength i at a wavelength of 450 to 650 nm by Ta V is 0.7 to 1.3; and
(5) 映像表示面貼合せ用積層フィルムのためのベースフィルムである、 ことを特徴とする二軸配向ポリエステルフィルム。  (5) A biaxially oriented polyester film, which is a base film for a laminated film for laminating an image display surface.
2. 色素が有機染料および平均粒径 10〜500 nmの顔料よりなる群から選ば れる少なくとも 1種である請求項 1に記載の二軸配向ホポリエステルフィルム。 3. 色素が少なくとも 2種の有機染料の組合せである請求項 1に記載の二軸配向 ポリエステルフィルム。 2. The biaxially oriented polyester film according to claim 1, wherein the pigment is at least one selected from the group consisting of organic dyes and pigments having an average particle size of 10 to 500 nm. 3. The biaxially oriented polyester film according to claim 1, wherein the pigment is a combination of at least two kinds of organic dyes.
4. 有機染料が下記式 (1) 〜 (4): 4. The organic dye has the following formula (1) to (4):
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000057_0001
Figure imgf000058_0001
ここで、 Ri R16は、それぞれ独立に、水素原子、炭素数 1〜6の脂肪族基、 炭素数 6〜 14の芳香族基、 炭素数 7〜 14の芳香族アルキル基、 炭素数 4〜 12の複素環基、 ハロゲン原子、 シァノ基、 ニトロ基、 一 C〇R17、 -COO R17、 —NR17R18、 — NR18COR19、 一 NR18S02R19、 一 CONR1 7R18、 一 S02NR17R18、 -COR19, 一 S〇2R19、 -COR19, —N R17CONR18R19、 一 C〇NR18S02R19または一 SOsNR COR1 9を表し、 R17および R18は互いに独立に水素原子、炭素数 1〜6の脂肪族基、 炭素数 6〜14の芳香族基または炭素数 4〜12の複素環基であるかあるい は R17および R18はそれらが結合している窒素原子と一緒になつて 5もしく は 6員複素環基を形成していてもよくそして R 19は炭素数 1〜 6の脂肪族基、 炭素数 6〜 14の芳香族基または炭素数 4〜 12の複素環基を表す、 のいずれかで表される請求項 2または 3に記載の二軸配向ポリエステルフィルム c Here, Ri R 16 is each independently a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, an aromatic group having 6 to 14 carbon atoms, an aromatic alkyl group having 7 to 14 carbon atoms, and 4 to 4 carbon atoms. 12 heterocyclic group, a halogen atom, Shiano group, a nitro group, one C_〇_R 17, -COO R 17, -NR 17 R 18, - NR 18 COR 19, one NR 18 S0 2 R 19, one CONR 1 7 R 18, one S0 2 NR 17 R 18, -COR 19, one S_〇 2 R 19, -COR 19, a -NR 17 CONR 18 R 19, one C_〇_NR 18 S0 2 R 19 or a SOsNR COR 1 9 R 17 and R 18 are each independently a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, an aromatic group having 6 to 14 carbon atoms or a heterocyclic group having 4 to 12 carbon atoms or R 17 and R 18 may be taken together with the nitrogen atom to which they are attached to form a 5- or 6-membered heterocyclic group, and R 19 is an aliphatic group having 1 to 6 carbon atoms, An aromatic group having 6 to 14 or a heterocyclic group having 4 to 12 carbon atoms The biaxially oriented polyester film c according to claim 2 or 3, which is represented by
5. 色素が前記式 (1) 〜 (4) の各式で表される 4種の有機染料の組合せから なり、 そして式 (1)、 (2)、 (3) および (4) で表される有機染料がそれぞれ 20〜60モル%、 10〜30モル%、 10〜40モル%および 10〜30モル% である請求項 2または 3に記載の二軸配向ポリエステルフィルム。 5. The dye consists of a combination of four organic dyes represented by the above formulas (1) to (4), and is represented by the formulas (1), (2), (3) and (4). 4. The biaxially oriented polyester film according to claim 2, wherein the organic dyes are 20 to 60 mol%, 10 to 30 mol%, 10 to 40 mol% and 10 to 30 mol%, respectively.
6. 色素の含有量がフィルム面の単位面積 (m2) 当り 02〜0. 42 で ある請求項 1に記載の二軸配向ポリエステルフィルム。 6. unit area of content film surface of the dye (m 2) per 02 to 0.42 biaxially oriented polyester film of claim 1.
7. 紫外線吸収剤をさらに含有する請求項 1に記載の二軸配向ポリエステルフィ ルム。 7. The biaxially oriented polyester film according to claim 1, further comprising an ultraviolet absorber.
8. 紫外線吸収剤が、 下記式 (5) 8. The UV absorber has the following formula (5)
位、 2位の位 り; RD1は n い、 または R Position, 2nd position; R D1 is n or R
Figure imgf000059_0001
Figure imgf000059_0001
で表される基であるかまたは Or a group represented by
下記式 (8)
Figure imgf000059_0002
The following equation (8)
Figure imgf000059_0002
で表される基であり; RQ2および RQ3は同一もしくは異なり 1価の炭化水素残基 であり; X 02は 4価の芳香族残基で、 これはさらにへテロ原子を含有していても よい。) R Q2 and R Q3 are the same or different and are monovalent hydrocarbon residues; X 02 is a tetravalent aromatic residue, which further contains a heteroatom. Also Good. )
で表される環状ィミノエステルから選ばれる少なくとも 1種の化合物である請求 項 7に記載の二軸配向ポリエステルフィルム。 The biaxially oriented polyester film according to claim 7, which is at least one compound selected from the cyclic imino esters represented by
9. 紫外線吸収剤の含有量が、 ポリエステルの重量を基準として、 0. 1〜5重 量%である請求項 7に記載の二軸配向ポリエステルフィルム。 9. The biaxially oriented polyester film according to claim 7, wherein the content of the ultraviolet absorbent is 0.1 to 5% by weight based on the weight of the polyester.
10. へ一ズ値が 3%以下である請求項 1に記載の二軸配向ポリエステルフィル ム。 10. The biaxially oriented polyester film according to claim 1, which has a haze value of 3% or less.
11. Tavが 50〜70%である請求項 1に記載の二軸配向ポリエステルフィ ルム。 11. The biaxially oriented polyester film according to claim 1, wherein Tav is 50 to 70%.
12. T i/Tavの値が 0. 8〜1. 2である請求項 1に記載の二軸配向ポリ エステルフィルム。 12. The biaxially oriented polyester film according to claim 1, wherein the value of Ti / Tav is 0.8 to 1.2.
13. 150°Cにおける熱収縮率が 2%以下である請求項 1に記載の二軸配向ポ リエステルフィルム。 13. The biaxially oriented polyester film according to claim 1, having a heat shrinkage at 150 ° C of 2% or less.
14. 請求項 1に記載の二軸配向ポリエステルフィルムおよび上記フィルムの少 なくとも片面上に設けられた第 1接着層からなる接着性フィルム。 14. An adhesive film comprising the biaxially oriented polyester film according to claim 1 and a first adhesive layer provided on at least one side of the film.
15. 入射光が二軸配向ポリエステルフィルムと第 1接着層との界面で反射する 反射率が、 入射光に対して 0. 4 %以下である請求項 14に記載の接着性フィル ム。 15. The adhesive film according to claim 14, wherein a reflectance at which an incident light is reflected at an interface between the biaxially oriented polyester film and the first adhesive layer is 0.4% or less with respect to the incident light.
16. 第 1接着層の厚み方向の屈折率 (nz) が 1. 50〜1. 60の範囲にあ る請求項 15に記載の接着性フィルム。 16. The adhesive film according to claim 15, wherein the refractive index (nz) of the first adhesive layer in the thickness direction is in the range of 1.50 to 1.60.
1 7. 第 1接着層の厚みが 7 0〜1 0 0 nmの範囲にある請求項 1 5に記載の接 着性フィルム。 17. The adhesive film according to claim 15, wherein the thickness of the first adhesive layer is in the range of 70 to 100 nm.
1 8. 請求項 1に記載の二軸配向ポリエステルフィルム、 このフィルムの両面上 に設けられた第 1接着層、 一方の第 1接着層の二軸配向ポリエステルフィルムと 接触している面とは異なる面上に設けられたハードコ一ト層および他方の第 1接 着層の二軸配向ポリエステルフィルムと接触している面とは異なる面上に設けら れた第 2接着層からなる映像表示面貼合せ用積層フィルム。 1 8. The biaxially oriented polyester film according to claim 1, a first adhesive layer provided on both sides of the film, and the first adhesive layer is different from a surface of the first adhesive layer which is in contact with the biaxially oriented polyester film. The image display surface is composed of a hard coat layer provided on the surface and a second adhesive layer provided on a surface different from the surface of the other first adhesive layer in contact with the biaxially oriented polyester film. Laminated film for lamination.
1 9. ハードコ一ト層の第 1接着層と接触している面とは異なる面上に多層反射 防止層をさらに有する請求項 1 8に記載の積層フィルム。 19. The laminated film according to claim 18, further comprising a multilayer antireflection layer on a surface of the hard coat layer different from the surface in contact with the first adhesive layer.
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JP7503545B2 (en) 2018-10-26 2024-06-20 トリンゼオ ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング Polymeric composition containing particles and colorants, method for preparing same and use thereof - Patents.com
JP7503544B2 (en) 2018-10-26 2024-06-20 トリンゼオ ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング Polymer composition suitable for injection molding containing particles and colorants, method for preparing same and use thereof - Patents.com
CN115298251A (en) * 2020-03-25 2022-11-04 东洋纺株式会社 Flame-retardant biaxially oriented polyester film
CN115298251B (en) * 2020-03-25 2024-01-02 东洋纺株式会社 Flame retardant biaxially oriented polyester film
US11940593B2 (en) 2020-07-09 2024-03-26 Corning Incorporated Display articles with diffractive, antiglare surfaces and methods of making the same
US11971519B2 (en) 2020-07-09 2024-04-30 Corning Incorporated Display articles with antiglare surfaces and thin, durable antireflection coatings
US11977206B2 (en) 2020-07-09 2024-05-07 Corning Incorporated Display articles with diffractive, antiglare surfaces and thin, durable antireflection coatings
US12147009B2 (en) 2021-07-07 2024-11-19 Corning Incorporated Textured region to reduce specular reflectance including a low refractive index substrate with higher elevated surfaces and lower elevated surfaces and a high refractive index material disposed on the lower elevated surfaces

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