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WO2011148504A1 - Film diffuseur de lumière, procédé de fabrication de ce dernier ainsi que plaque de polarisation, plaque de polarisation en forme de rouleau et dispositif d'affichage à cristaux liquides qui utilisent ce dernier - Google Patents

Film diffuseur de lumière, procédé de fabrication de ce dernier ainsi que plaque de polarisation, plaque de polarisation en forme de rouleau et dispositif d'affichage à cristaux liquides qui utilisent ce dernier Download PDF

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Publication number
WO2011148504A1
WO2011148504A1 PCT/JP2010/059108 JP2010059108W WO2011148504A1 WO 2011148504 A1 WO2011148504 A1 WO 2011148504A1 JP 2010059108 W JP2010059108 W JP 2010059108W WO 2011148504 A1 WO2011148504 A1 WO 2011148504A1
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WO
WIPO (PCT)
Prior art keywords
light
film
resin
diffusion film
polarizing plate
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Ceased
Application number
PCT/JP2010/059108
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English (en)
Japanese (ja)
Inventor
啓史 別宮
耕二 田代
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Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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Priority to PCT/JP2010/059108 priority Critical patent/WO2011148504A1/fr
Publication of WO2011148504A1 publication Critical patent/WO2011148504A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0221—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133504—Diffusing, scattering, diffracting elements

Definitions

  • the present invention relates to a light diffusing film, a production method thereof, a polarizing plate using the same, a roll-shaped polarizing plate, and a liquid crystal display device. More specifically, the present invention relates to a light diffusion film and a display member, and more particularly, to a light diffusion film and a display device that uniformly diffuses light from a light emitting diode (LED) light source or the like.
  • LED light emitting diode
  • a display member or device having a light source on the back side of the display object diffuses light from the light source using a light diffusion film or the like, and makes the light from the light source uniform, or on the back side from the light diffusion film such as the light source It is performed not to make the member in the visible.
  • the transparent plate or printing member cannot hide the light source or substrate existing on the back side of the light diffusion film, the light diffusibility is emphasized, the light from the light source is made uniform, and the back member and light source are It is required to make it invisible.
  • a transparent plate or a printed member on which desired information is printed on the viewer side is provided. It can arrange
  • Patent Document 1 discloses a light diffusion film having a light diffusion layer produced by applying a curable resin in which light diffusion particles are dispersed on a resin base material.
  • the light diffusibility of the light diffusion layer is increased by forming wavy irregularities around the light diffusion particles.
  • diffusing particles beams
  • the diffusion function is improved by forming irregularities on the surface.
  • the unevenness pitch depends on the size of the diffusing particles, the pitch of the irregularities is increased, so that a significant improvement in the diffusion function cannot be expected.
  • corrugation by embossing is also known.
  • Patent Document 2 discloses a method of manufacturing a light diffusion film in which a dope containing fine particles is cast on a support, dried after being peeled, and a film having a haze of 30% or more is produced.
  • the light diffusion film since it contains fine particles, internal diffusion is the center and light loss occurs.
  • diffusing particles are put in the cellulose ester, and when particles are present in the film when imparting a diffusing function to the polarizing plate protective film, when the alkali treatment is performed in the saponification step, And since gas barrier property improves when bonding with a polarizer, moisture permeability becomes low, ie, it becomes difficult to dry, and productivity will fall. Furthermore, there is a problem that particles fall off during the process and contaminate the process.
  • the present invention has been made in view of the above-described problems and situations, and a solution to the problem is a light diffusing film that is excellent in productivity at an appropriate moisture permeability and has little luminance unevenness and sticking unevenness, and a method for manufacturing the same. Is to provide. Moreover, it is providing the polarizing plate, roll-shaped polarizing plate, and liquid crystal display device which used the said light-diffusion film.
  • a light diffusing film for diffusing light from a light source having a concavo-convex structure on at least one surface of the light diffusing film, and Fourier based on an image obtained by measuring the concavo-convex structure with a 3D measurement laser microscope
  • the average pitch of the irregularities in the converted image is in the range of 50 nm to 3 ⁇ m
  • the average difference (depth) between the highest point of the convex part and the lowest point of the concave part is in the range of 5 nm to 5 ⁇ m.
  • a polarizing plate comprising the light diffusing film according to any one of the first to third items.
  • a roll-shaped polarizing plate comprising the light diffusion film according to any one of items 1 to 3 above.
  • a liquid crystal display device comprising the light diffusing film according to any one of items 1 to 3.
  • a light diffusing film having an appropriate moisture permeability and excellent productivity, and having less unevenness of brightness and unevenness of sticking, and a method for producing the same.
  • a polarizing plate, a roll-shaped polarizing plate, and a liquid crystal display device using the light diffusion film can be provided.
  • the surface of the light diffusion film of the present invention has many fine irregularities, the light diffusion effect is high, and it is difficult to stick to an adjacent member when shrinking, thereby preventing uneven brightness and uneven sticking. .
  • the conceptual diagram which shows an example of the Fourier-transform image based on the image obtained by measuring an uneven
  • the light diffusing film of the present invention is a light diffusing film that diffuses light from a light source, and has a concavo-convex structure on at least one surface of the light diffusing film, and the concavo-convex structure is measured with a 3D measurement laser microscope.
  • the average pitch of the irregularities is in the range of 50 nm to 3 ⁇ m
  • the average value of the difference (depth) between the highest point of the convex part and the lowest point of the concave part is 5 nm to 5 ⁇ m It is in the range of.
  • the surface roughness Ra of the surface having the concavo-convex structure is preferably in the range of 50 to 1000 nm from the viewpoint of manifesting the effects of the present invention.
  • the surface haze value is preferably 10% or more.
  • the moisture permeability at a temperature of 40 ° C. and a relative humidity of 90% RH is preferably 300 to 1500 g / m 2 ⁇ 24 h.
  • the poor solvent is preferably a mixed solvent of water and alcohols or a mixed solvent of water and ketones.
  • the light diffusion film of the present invention can be suitably used for polarizing plates and liquid crystal display devices.
  • it can be suitably used for a liquid crystal display device using a light emitting diode (LED) as a backlight light source.
  • LED light emitting diode
  • the light diffusing film of the present invention is a light diffusing film that diffuses light from a light source, and has a concavo-convex structure on at least one surface of the light diffusing film, and the concavo-convex structure is measured with a 3D measurement laser microscope.
  • the average pitch of the irregularities is in the range of 50 nm to 3 ⁇ m
  • the average value of the difference (depth) between the highest point of the convex part and the lowest point of the concave part is 5 nm to 5 ⁇ m It is in the range of.
  • the average pitch of the irregularities is preferably in the range of 100 nm to 1 ⁇ m.
  • the average value of the difference (depth) between the highest point of the convex portion and the lowest point of the concave portion is preferably in the range of 10 nm to 1 ⁇ m.
  • the pitch of the unevenness according to the present invention and the difference (depth) between the highest point of the convex portion and the lowest point of the concave portion are values measured by the following method (see FIG. 1).
  • the measurement conditions with a laser microscope are a magnification of 350 times.
  • the said image is acquired from the direction which sees the surface of a light-diffusion film perpendicularly
  • this image is subjected to waveform separation by Fourier transform to obtain an FFT image (fast Fourier transform image).
  • FFT image fast Fourier transform image
  • the pitch of the unevenness and the difference (depth) between the highest point of the convex portion and the lowest point of the concave portion were measured based on the profile.
  • concave portion the portion below the horizontal line including the midpoint of the highest and lowest points of each concavo-convex shape in the FFT image
  • convex portion the portion above the horizontal plane
  • the highest point of the convex portion means the highest point (the point at which the height is the maximum value) of the convex portion in each concave and convex shape.
  • the lowest point of the concave portion refers to the lowest point (the point at which the height is a minimum value) of the concave portion in each uneven shape.
  • Uneven pitch refers to the interval between the highest points (peaks) between adjacent convex portions.
  • the “average pitch of unevenness” is the average of values obtained by dividing 130 ⁇ m by the number of highest points (peaks) of convex portions existing in the measurement area of 130 ⁇ m for each of the five FFT images. Value.
  • the difference (depth) between the highest point of the convex portion and the lowest point of the concave portion refers to the difference between the lowest point between the adjacent convex portion and the highest point of the concave portion.
  • the average value of the difference (depth) is an average value of values obtained by measuring each unevenness existing in the measurement area of 130 ⁇ m for each of the FFT images of the five images.
  • manufacturing conditions are optimized in the following manufacturing method. Can be done.
  • the surface roughness Ra of the surface having the concavo-convex shape structure is preferably in the range of 50 to 1000 nm.
  • the surface haze value is preferably 10% or more.
  • the moisture permeability at a temperature of 40 ° C. and a relative humidity of 90% RH is preferably 300 to 1500 g / m 2 ⁇ 24 h. Furthermore, it is preferable that it is 1000 g / m ⁇ 2 > * 24h or less.
  • This method is common with the method of controlling within the predetermined range, and can be performed by optimizing the manufacturing conditions in the following manufacturing method.
  • the method for producing a light diffusing film of the present invention is a method for producing a light diffusing film having a concavo-convex structure on the surface, and a mixed solvent containing a poor solvent in a resin film substrate containing at least one of acrylic resin or cellulose ester It is preferable that it is a manufacturing method of the aspect which has the process of apply
  • the present invention is characterized in that a mixed solvent containing a poor solvent is applied as a means for forming and imparting a concavo-convex structure on the surface.
  • the pH of the poor solvent is preferably lower than the pH of the treatment solution used in the alkaline saponification treatment such as cellulose ester film, and is preferably in the range of pH 5.5 to 7.5 at 25 ° C., for example.
  • the surface roughness Ra of the film to which the mixed solvent coating is applied and the surface roughness Ra of the film to which the mixed solvent coating is not applied differ by 3 nm or more.
  • a method for the adjustment a method based on selection of solvent chemical species of the mixed solvent to be applied, amount, mixed composition, temperature of solvent, optimization of conditions such as drying temperature, and the like are preferable.
  • a mixed solvent of ethanol and pure water heated to 40 to 60 ° C. in a ratio of 50:50 to 80:20 Vol% is applied to the film surface. It is preferable to spray-coat and then dry while transporting in a drying zone of 110 to 150 ° C.
  • the manufacturing method of the light-diffusion film of this invention has the process of applying the mixed solvent containing a poor solvent to the resin film base material containing at least one of an acrylic resin or a cellulose ester, and the process of drying, It is characterized by the above-mentioned. .
  • the poor solvent means that when a solvent whose solubility is to be measured is added to a solid content equivalent to 3 g of the following thermoplastic resin so that the total amount becomes 20 g and stirred at a temperature of 25 ° C., dust is recognized. If the sample is thickened or separated, it is considered to be a poor solvent for the sample.
  • thermoplastic resin is, for example, a polyester resin or a polyester urethane resin
  • examples of the poor solvent include xylene, ethyl cellosolve, propylene glycol monomethyl ether, isobutanol, isopropanol, ethanol, methanol, hexane, and purified water. be able to.
  • thermoplastic resin is an acrylic resin
  • examples of the poor solvent include ethyl cellosolve, propylene glycol monomethyl ether, isobutanol, isopropanol, ethanol, methanol, hexane, and purified water.
  • the poor solvent for the thermoplastic resin is preferably used by mixing two or more of the above solvents.
  • a mixed solvent of water and alcohols methanol, ethanol, isopropanol, etc.
  • it may be a mixed solvent of water and ketones (acetone, propanone, butanone, etc.).
  • thermoplastic resin As the resin film substrate according to the present invention, various conventionally known resins can be used, but it is preferable to use a thermoplastic resin. However, it is preferable that an acrylic resin or a cellulose ester is always included.
  • thermoplastic resin refers to a resin that becomes soft when heated to the glass transition temperature or melting point and can be molded into the desired shape.
  • thermoplastic resins include cellulose esters, polyethylene (PE), high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene. (PS), polyvinyl acetate (PVAc), Teflon (registered trademark) (polytetrafluoroethylene, PTFE), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin (PMMA), etc., soluble in solvents It is preferable to dissolve the material appropriately and treat it by the method of the present invention.
  • PA polyamide
  • nylon polyacetal
  • PC polycarbonate
  • m-PPE modified polyphenylene ether
  • PBT polybutylene terephthalate
  • PET Polyethylene terephthalate
  • GF-PET glass fiber reinforced polyethylene terephthalate
  • COP cyclic polyolefin
  • polyphenylene sulfide PPS
  • polytetrafluoroethylene PTFE
  • polysulfone polyethersulfone
  • amorphous polyarylate liquid crystal polymer
  • polyetherether A ketone thermoplastic polyimide (PI)
  • PAI polyamideimide
  • the thickness of the support is appropriately selected according to the application.
  • the upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting method, the upper limit is about 250 ⁇ m from the viewpoint of applicability, foaming, solvent drying, and the like.
  • the resin substrate preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%. In order to achieve excellent transparency expressed by such total light transmittance, it is necessary not to introduce additives and copolymerization components that absorb visible light, or to remove foreign substances in the polymer by high-precision filtration. It is effective to reduce the diffusion and absorption of light inside the film.
  • the cellulose ester resin that can be used in the present invention is selected from cellulose (di, tri) acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose phthalate. It is preferable that there is at least one.
  • particularly preferred cellulose esters include cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate.
  • substitution degree of the mixed fatty acid ester when an acyl group having 2 to 4 carbon atoms is used as a substituent, the substitution degree of the acetyl group is X, and the substitution degree of the propionyl group or butyryl group is Y.
  • a cellulose resin containing a cellulose ester that simultaneously satisfies the following formulas (I) and (II) is preferable.
  • the cellulose ester used in the present invention preferably has a weight average molecular weight Mw / number average molecular weight Mn ratio of 1.5 to 5.5, particularly preferably 2.0 to 5.0, The cellulose ester is preferably 2.5 to 5.0, more preferably 3.0 to 5.0.
  • the raw material cellulose of the cellulose ester used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferable.
  • a cotton linter is preferably used from the viewpoint of peelability during film formation.
  • the cellulose ester made from these can be mixed suitably or can be used independently.
  • the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (conifer): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.
  • cellulose ester resin 1 g is added to 20 ml of pure water (electric conductivity 0.1 ⁇ S / cm or less, pH 6.8), and the pH is 6 when stirred in a nitrogen atmosphere at 25 ° C. for 1 hr. It is preferable that the electric conductivity is 1 to 100 ⁇ S / cm.
  • the acrylic resin that can be used in the present invention includes a methacrylic resin.
  • the resin is not particularly limited, but a resin comprising 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith is preferable.
  • Examples of other copolymerizable monomers include alkyl methacrylates having 2 to 18 alkyl carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, alkyl acrylates such as acrylic acid and methacrylic acid.
  • Examples thereof include unsaturated nitrile, maleic anhydride, maleimide, N-substituted maleimide, and glutaric anhydride, and these can be used alone or in combination of two or more.
  • methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate and the like are preferable, and methyl acrylate and n-butyl acrylate are particularly preferable.
  • acrylic resins can also be used.
  • Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned. .
  • cyclic olefin resin examples include norbornene resins, monocyclic olefin resins, cyclic conjugated diene resins, vinyl alicyclic hydrocarbon resins, and hydrides thereof.
  • norbornene-based resins can be suitably used because of their good transparency and moldability.
  • Examples of the norbornene-based resin include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and another monomer, a hydride thereof, and a norbornene structure.
  • a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly suitable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, lightness, and the like. Can be used.
  • Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 2,5 ] deca-3,7-diene. (Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0. 1 2,5 . 1 7,10 ] dodec-3-ene (common name: tetracyclododecene) and derivatives of these compounds (for example, those having a substituent in the ring).
  • examples of the substituent include an alkyl group, an alkylene group, and a polar group.
  • these substituents may be the same or different and a plurality may be bonded to the ring.
  • Monomers having a norbornene structure can be used singly or in combination of two or more.
  • Examples of the polar group include heteroatoms or atomic groups having heteroatoms.
  • Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom.
  • Specific examples of the polar group include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxyl group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.
  • monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof, cyclic conjugated dienes such as cyclohexadiene, cycloheptadiene, and the like. And derivatives thereof.
  • a ring-opening polymer of a monomer having a norbornene structure and a ring-opening copolymer of a monomer having a norbornene structure and another monomer copolymerizable with the monomer have a known ring-opening polymerization catalyst. It can be obtained by (co) polymerization in the presence.
  • Examples of other monomers that can be addition-copolymerized with a monomer having a norbornene structure include, for example, ⁇ -olefins having 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene, and derivatives thereof; cyclobutene, cyclopentene, Examples thereof include cycloolefins such as cyclohexene and derivatives thereof; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. These monomers can be used alone or in combination of two or more. Among these, ⁇ -olefin is preferable, and ethylene is more preferable.
  • An addition polymer of a monomer having a norbornene structure and an addition copolymer of another monomer copolymerizable with a monomer having a norbornene structure can be used in the presence of a known addition polymerization catalyst. It can be obtained by polymerization.
  • a known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to the polymer solution, and the carbon-carbon unsaturated bond is preferably hydrogenated by 90% or more.
  • X bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.1 2,5 ] decane-7 are used as repeating units.
  • 9-diyl-ethylene structure the content of these repeating units is 90% by mass or more based on the entire repeating units of the norbornene resin, and the X content ratio and the Y content ratio are The ratio of X: Y is preferably 100: 0 to 40:60.
  • the molecular weight of the cyclic olefin resin used in the present invention is appropriately selected according to the purpose of use.
  • Polyisoprene or polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography using cyclohexane (toluene if the polymer resin does not dissolve) as a solvent usually 20,000 to 150,000. . It is preferably 25,000 to 100,000, more preferably 30,000 to 80,000.
  • Mw weight average molecular weight measured by gel permeation chromatography using cyclohexane (toluene if the polymer resin does not dissolve) as a solvent, usually 20,000 to 150,000. . It is preferably 25,000 to 100,000, more preferably 30,000 to 80,000.
  • the glass transition temperature of the cyclic olefin resin may be appropriately selected according to the purpose of use. From the viewpoint of durability and stretchability, it is preferably in the range of 130 to 160 ° C, more preferably 135 to 150 ° C.
  • the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the cyclic olefin resin is 1.2 to 3.5, preferably 1.5 to 3.0, from the viewpoint of relaxation time, productivity and the like. More preferably, it is 1.8 to 2.7.
  • the cyclic olefin resin used in the present invention preferably has an absolute value of photoelastic coefficient of 10 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less, more preferably 7 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less, and more preferably 4 ⁇ 10 12 It is particularly preferably ⁇ 12 Pa ⁇ 1 or less.
  • the cyclic olefin resin does not substantially contain particles.
  • substantially free of particles means that even if particles are added to a film made of a cyclic olefin resin, the amount of increase in haze from the non-added state is allowed to be in the range of 0.05% or less. Means you can.
  • the alicyclic polyolefin resin lacks affinity with many organic particles and inorganic particles. Therefore, when a cyclic olefin resin film to which particles exceeding the above range are added is stretched, voids are easily generated, and as a result, There is a risk that a significant decrease in haze occurs.
  • ⁇ Polycarbonate resin> various known polycarbonate resins can also be used.
  • a polymer material generically called polycarbonate is a generic term for a polymer material in which a polycondensation reaction is used in its synthesis method and the main chain is linked by a carbonic acid bond.
  • Phosgene, diphenyl carbonate and the like obtained by polycondensation.
  • an aromatic polycarbonate represented by a repeating unit having 2,2-bis (4-hydroxyphenyl) propane, which is called bisphenol-A, as a bisphenol component is preferably selected.
  • bisphenol-A 2,2-bis (4-hydroxyphenyl) propane
  • Various bisphenol derivatives should be appropriately selected.
  • an aromatic polycarbonate copolymer can be constituted.
  • bisphenol-A bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -2-phenyl Ethane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) sulfide, bis ( 4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) -3,3,5-to It can be exemplified methyl cyclohexane.
  • aromatic polyester carbonate partially containing terephthalic acid and / or isophthalic acid components.
  • a structural unit as a part of the structural component of the aromatic polycarbonate composed of bisphenol-A, the properties of the aromatic polycarbonate, such as heat resistance and solubility, can be improved.
  • the present invention is also effective for coalescence.
  • the viscosity average molecular weight of the aromatic polycarbonate used here is preferably 10,000 to 200,000.
  • a viscosity average molecular weight of 20,000 to 120,000 is particularly preferred. If a resin having a viscosity average molecular weight lower than 10,000 is used, the mechanical strength of the resulting film may be insufficient, and if it has a high molecular weight of 400000 or more, the viscosity of the dope becomes too high, causing problems in handling.
  • the viscosity average molecular weight can be measured by commercially available high performance liquid chromatography.
  • the glass transition temperature of the aromatic polycarbonate according to the present invention is preferably 200 ° C. or higher in order to obtain a highly heat-resistant film, and more preferably 230 ° C. or higher. These can be obtained by appropriately selecting the copolymerization component.
  • the glass transition temperature can be measured with a DSC apparatus (differential scanning calorimetry apparatus). For example, the Seiko Instruments Inc. product: RDC220 calculates the temperature at 10 ° C./min. It is the temperature that begins to do.
  • the solvent used in the dope composition containing the aromatic polycarbonate is a mixed solvent containing 4 to 14 parts by mass of methylene chloride and a linear or branched aliphatic alcohol having 1 to 6 carbon atoms. It is preferable.
  • the mixing amount of the linear or branched aliphatic alcohol having 1 to 6 carbon atoms is preferably 4 to 12 parts by mass.
  • the type of alcohol added is limited by the solvent used. It is a necessary condition that the alcohol and the solvent are compatible. These may be added alone or in combination of two or more.
  • the alcohol in the present invention is preferably a linear or branched aliphatic alcohol having 1 to 6, preferably 1 to 4, more preferably 2 to 4 carbon atoms. Specific examples include methanol, ethanol, isopropanol, and tert-butanol. Of these, ethanol, isopropanol, and tertiary-butanol can achieve almost the same effect, but methanol is slightly less effective. Although the reason is not clear, it is presumed that the boiling point of the solvent, that is, the ease of flying during drying is related. Higher alcohols higher than that are not preferred because they have a high boiling point and are likely to remain after film formation.
  • the amount of alcohol to be added must be carefully selected. These alcohols are completely poor in solubility in aromatic polycarbonate and are completely poor solvents. Therefore, it cannot be added too much, and should be the minimum amount that provides satisfactory peelability. As described above, it is 4 to 14 parts by mass, preferably 4 to 12 parts by mass with respect to methylene chloride. When the addition amount is in the range of 4 to 14 parts by mass with respect to the amount of methylene chloride, the solubility of the solvent in the polymer and the dope stability are improved, and the effect of improving the peelability is increased.
  • the present invention is composed of the above methylene chloride and aliphatic alcohol in the dope composition, but other solvents can also be used.
  • the remaining solvent is not particularly limited as long as it dissolves the aromatic polycarbonate at a high concentration and is compatible with alcohol, and is a low-boiling solvent.
  • halogen solvents such as chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, 1,3-dioxolane, 1, Examples include cyclic ether solvents such as 4-dioxane and tetrahydrofuran, and ketone solvents such as cyclohexanone.
  • the effects here include mixing the solvent without sacrificing solubility and stability, for example, improving the surface properties of the film formed by the solution casting method (leveling effect), evaporation rate and system These include viscosity adjustment and crystallization suppression effects. What is necessary is just to determine the kind and addition amount of the solvent to mix by the degree of these effects, and you may use 1 type (s) or 2 or more types as a solvent to mix.
  • solvents preferably used include halogen solvents such as chloroform and 1,2-dichloroethane, hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate and butyl acetate.
  • halogen solvents such as chloroform and 1,2-dichloroethane
  • hydrocarbon solvents such as toluene and xylene
  • ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone
  • ethyl acetate and butyl acetate examples include ester solvents, ether solvents such as ethylene glycol dimethyl ether and methoxyethyl acetate.
  • the dope composition according to the present invention may be prepared by any method as long as a transparent solution with low haze is obtained as a result.
  • a predetermined amount of alcohol may be added to the aromatic polycarbonate solution dissolved in a certain solvent in advance, or the aromatic polycarbonate may be dissolved in a mixed solvent containing alcohol.
  • alcohol is a poor solvent, the method of adding the latter after the former may cause clouding of the dope due to the precipitation of the polymer. Therefore, the method of dissolving in the latter mixed solvent is preferable.
  • the polyester resin that can be used in the present invention is obtained by polymerizing a dicarboxylic acid and a diol, and 70% or more of dicarboxylic acid structural units (constituent units derived from dicarboxylic acid) are derived from aromatic dicarboxylic acid, and 70% or more of the diol constituent units (constituent units derived from the diol) are derived from the aliphatic diol.
  • the proportion of the structural unit derived from the aromatic dicarboxylic acid is 70% or more, preferably 80% or more, and more preferably 90% or more.
  • the proportion of the structural unit derived from the aliphatic diol is 70% or more, preferably 80% or more, and more preferably 90% or more. Two or more polyester resins may be used in combination.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid such as 2,7-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. 3,4'-biphenyldicarboxylic acid and the like, and ester-forming derivatives thereof.
  • polyester resin aliphatic dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid, and monocarboxylic acids such as benzoic acid, propionic acid, and butyric acid can be used without departing from the object of the present invention.
  • Examples of the aliphatic diol include ethylene glycol, 1,3-propylene diol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, and ester-forming derivatives thereof.
  • polyester resin monoalcohols such as butyl alcohol, hexyl alcohol, and octyl alcohol, and polyhydric alcohols such as trimethylolpropane, glycerin, and pentaerythritol can be used as long as the object of the present invention is not impaired.
  • a known esterification method or transesterification method can be applied to the production of the polyester resin.
  • polycondensation catalysts used in the production of polyester resins include known antimony compounds such as antimony trioxide and antimony pentoxide, germanium compounds such as germanium oxide, titanium compounds such as titanium acetate, and aluminum compounds such as aluminum chloride. Yes, but not limited to.
  • Preferred polyester resins include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polyethylene-1,4-cyclohexanedimethylene-terephthalate copolymer resin, polyethylene-2,6-naphthalene dicarboxylate resin, polyethylene-2, 6-naphthalene dicarboxylate-terephthalate copolymer resin, polyethylene-terephthalate-4,4'-biphenyldicarboxylate resin, poly-1,3-propylene-terephthalate resin, polybutylene terephthalate resin, polybutylene-2,6-naphthalene There are dicarboxylate resins and the like.
  • polyester resins include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polyethylene-1,4-cyclohexanedimethylene-terephthalate copolymer resin, polybutylene terephthalate resin, and polyethylene-2,6-naphthalene dicarboxylate. Resin.
  • thermoplastic resin substrate according to the present invention can contain various compounds as additives depending on the purpose.
  • a plasticizer, an antioxidant, an acid scavenger, a light stabilizer, an ultraviolet absorber, an optical anisotropy control agent, a matting agent, an antistatic agent, a release agent, and the like can be contained.
  • the retardation increasing agent is preferably an aromatic compound having at least two aromatic rings.
  • the aromatic compound is preferably used in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin. And it is preferable to use in 0.05-15 mass parts, and it is still more preferable to use in 0.1-10 mass parts. Two or more aromatic compounds may be used in combination.
  • the aromatic ring of the aromatic compound includes an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring).
  • the aromatic heterocycle is generally an unsaturated heterocycle.
  • the aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring.
  • Aromatic heterocycles generally have the most double bonds.
  • a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable.
  • aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring. Details of these are described in JP-A No. 2004-109410, JP-A No. 2003-344655, JP-A No. 2000-275434, JP-A No. 2000-1111914, JP-A No. 12-275434, and the like.
  • thermoplastic resin substrate according to the present invention and various functional layers provided on the substrate can contain various compounds as additives depending on the purpose.
  • a plasticizer, an antioxidant, an acid scavenger, a light stabilizer, an ultraviolet absorber, an optical anisotropy control agent, a matting agent, an antistatic agent, a release agent, and the like can be contained.
  • the retardation increasing agent is preferably an aromatic compound having at least two aromatic rings.
  • the aromatic compound is preferably used in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin. And it is preferable to use in 0.05-15 mass parts, and it is still more preferable to use in 0.1-10 mass parts. Two or more aromatic compounds may be used in combination.
  • the aromatic ring of the aromatic compound includes an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring).
  • the aromatic heterocycle is generally an unsaturated heterocycle.
  • the aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring.
  • Aromatic heterocycles generally have the most double bonds.
  • a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable.
  • aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring. Details of these are described in JP-A No. 2004-109410, JP-A No. 2003-344655, JP-A No. 2000-275434, JP-A No. 2000-1111914, JP-A No. 12-275434, and the like.
  • fine particles may be added as a matting agent in order to prevent the manufactured film from being scratched or being deteriorated in transportability.
  • examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples thereof include magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
  • the average primary particle size of the fine particles is preferably 5 to 400 nm, more preferably 10 to 300 nm. These may be mainly contained as secondary aggregates having a particle size of 0.05 to 0.3 ⁇ m, and may be contained as primary particles without being aggregated if the particles have an average particle size of 100 to 400 nm. preferable.
  • the content of these fine particles in the light diffusing film is preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass. In the case of a light diffusing film having a multilayer structure by the co-casting method, it is preferable to contain fine particles of this addition amount on the surface.
  • Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can.
  • Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
  • Examples of the polymer include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.
  • Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the haze of the light diffusion film low.
  • the dynamic friction coefficient of at least one surface is preferably 0.2 to 1.0.
  • Production method of light diffusion film As a method for producing the resin film substrate according to the present invention as a film, production methods such as a normal inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, and a hot press method can be used.
  • the solution casting method and the melt casting method by a casting method are preferable from the viewpoints of suppression of coloring, suppression of defects of foreign matters, suppression of optical defects such as die lines, and the like.
  • an organic solvent useful for forming the dope can be used without limitation as long as it dissolves a thermoplastic resin such as a cellulose ester resin. .
  • methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, ethyl lactate, lactic acid , Diacetone alcohol, etc., preferably methylene chloride, methyl acetate, ethyl acetate,
  • the dope may contain 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
  • a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
  • thermoplastic resin should be a dope composition in which at least 10 to 45% by mass of the thermoplastic resin is dissolved in a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. preferable.
  • linear or branched aliphatic alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, and good drying properties.
  • thermoplastic resin and other additives are dissolved in an organic solvent mainly composed of a good solvent for the thermoplastic resin while stirring to form a dope.
  • thermoplastic resin For the dissolution of the thermoplastic resin, a method carried out at normal pressure, a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544, JP-A-9-95557 Alternatively, various dissolution methods such as a method using a cooling dissolution method as described in JP-A-9-95538 and a method using a high pressure as described in JP-A-11-21379 can be used. The method of pressurizing at a boiling point or higher is preferred.
  • Recycled material is a finely pulverized film, which is generated when the film is formed, cut off on both sides of the film, or the original film that has been speculated out due to scratches, etc. Reused.
  • An endless metal belt such as a stainless steel belt or a rotating metal drum, which supports the dope is fed to a pressure die through a liquid feed pump (for example, a pressurized metering gear pump) and supported infinitely. This is a step of casting a dope from a pressure die slit to a casting position on the body.
  • a liquid feed pump for example, a pressurized metering gear pump
  • ⁇ Pressure dies that can adjust the slit shape of the die base and make the film thickness uniform are preferred.
  • the pressure die include a coat hanger die and a T die, and any of them is preferably used.
  • the surface of the metal support is a mirror surface.
  • two or more pressure dies may be provided on the metal support, and the dope amount may be divided and stacked. Or it is also preferable to obtain the film of a laminated structure by the co-casting method which casts several dope simultaneously.
  • Solvent evaporation step In this step, the web (the dope is cast on the casting support and the formed dope film is called a web) is heated on the casting support to evaporate the solvent.
  • the web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C. In order to maintain the atmosphere at 40 to 100 ° C., it is preferable to apply hot air at this temperature to the upper surface of the web or heat by means such as infrared rays.
  • Peeling process It is the process of peeling the web which the solvent evaporated on the metal support body in a peeling position. The peeled web is sent to the next process.
  • the temperature at the peeling position on the metal support is preferably 10 to 40 ° C, more preferably 11 to 30 ° C.
  • the amount of residual solvent at the time of peeling of the web on the metal support at the time of peeling is preferably 50 to 120% by weight depending on the strength of drying conditions, the length of the metal support, and the like.
  • the amount of solvent is determined.
  • the amount of residual solvent in the web is defined by the following formula.
  • Residual solvent amount (%) (mass before web heat treatment ⁇ mass after web heat treatment) / (mass after web heat treatment) ⁇ 100 Note that the heat treatment for measuring the residual solvent amount represents performing heat treatment at 115 ° C. for 1 hour.
  • the peeling tension at the time of peeling the metal support and the film is usually 196 to 245 N / m. However, if wrinkles easily occur at the time of peeling, it is preferable to peel with a tension of 190 N / m or less. It is preferable to peel at a minimum tension of ⁇ 166.6 N / m, and then peel at a minimum tension of ⁇ 137.2 N / m, and particularly preferable to peel at a minimum tension of ⁇ 100 N / m.
  • the temperature at the peeling position on the metal support is preferably ⁇ 50 to 40 ° C., more preferably 10 to 40 ° C., and most preferably 15 to 30 ° C.
  • a drying device 35 that transports the web alternately through rolls arranged in the drying device and / or a tenter stretching device 34 that clips and transports both ends of the web with clips. And dry the web.
  • the drying means is generally to blow hot air on both sides of the web, but there is also a means to heat by applying microwaves instead of wind. Too rapid drying tends to impair the flatness of the finished film. Drying at a high temperature is preferably performed from about 8% by mass or less of the residual solvent. Throughout the drying is generally carried out at 40-250 ° C. It is particularly preferable to dry at 40 to 160 ° C.
  • tenter stretching apparatus When using a tenter stretching apparatus, it is preferable to use an apparatus that can independently control the film gripping length (distance from the start of gripping to the end of gripping) left and right by the left and right gripping means of the tenter. In the tenter process, it is also preferable to intentionally create compartments having different temperatures in order to improve planarity.
  • the stretching operation may be performed in multiple stages, and it is also preferable to perform biaxial stretching in the casting direction and the width direction.
  • biaxial stretching When biaxial stretching is performed, simultaneous biaxial stretching may be performed or may be performed stepwise.
  • stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible. That is, for example, the following stretching steps are possible.
  • Simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension.
  • the preferred draw ratio for simultaneous biaxial stretching can be in the range of x1.01 to x1.5 in both the width direction and the longitudinal direction.
  • the amount of residual solvent in the web is preferably 20 to 100% by mass at the start of the tenter, and drying is preferably performed while the tenter is applied until the amount of residual solvent in the web is 10% by mass or less. More preferably, it is 5% by mass or less.
  • the drying temperature is preferably 30 to 160 ° C., more preferably 50 to 150 ° C., and most preferably 70 to 140 ° C.
  • the temperature distribution in the width direction of the atmosphere is small from the viewpoint of improving the uniformity of the film.
  • the temperature distribution in the width direction in the tenter process is preferably within ⁇ 5 ° C, and within ⁇ 2 ° C. Is more preferable, and within ⁇ 1 ° C. is most preferable.
  • Winding process This is a process in which the amount of residual solvent in the web becomes 2% by mass or less, and is taken up by the winder 37 as a film, and the dimensional stability is achieved by setting the residual solvent amount to 0.4% by mass or less. Can be obtained. It is particularly preferable to wind up at 0.00 to 0.10% by mass.
  • a generally used one may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, etc., and these may be used properly.
  • the film according to the present invention is preferably a long film, specifically a film having a thickness of about 100 m to 5000 m, and usually in a form provided in a roll shape.
  • the film width is preferably 1.3 to 4 m, more preferably 1.4 to 2 m.
  • the film thickness of the film according to the present invention is not particularly limited, but is preferably 20 to 200 ⁇ m, more preferably 25 to 150 ⁇ m, and particularly preferably 30 to 120 ⁇ m.
  • thermoplastic resin film used for melt extrusion is usually preferably kneaded in advance and pelletized.
  • Pelletization may be performed by a known method. For example, a dry thermoplastic resin and an additive depending on the purpose are supplied to an extruder with a feeder, and kneaded using a single-screw or twin-screw extruder. Extruded into a shape, water-cooled or air-cooled and cut.
  • cellulose ester easily absorbs moisture, it is preferable to dry it at 70 to 140 ° C. for 3 hours or more with a dehumidifying hot air dryer or a vacuum dryer so that the moisture content is 200 ppm or less, and further 100 ppm or less.
  • Additives may be fed into the extruder and fed into the extruder, or may be fed through individual feeders. In order to mix a small amount of additives such as an antioxidant uniformly, it is preferable to mix them in advance.
  • the antioxidant may be mixed with each other, and if necessary, the antioxidant may be dissolved in a solvent, impregnated with a thermoplastic resin and mixed, or mixed by spraying. May be.
  • a vacuum nauter mixer or the like is preferable because drying and mixing can be performed simultaneously. Further, if the contact with air, such as the exit from the feeder unit or die, it is preferable that the atmosphere such as dehumidified air and dehumidified N 2 gas.
  • the extruder is preferably processed at as low a temperature as possible so as to be able to be pelletized so that the shear force is suppressed and the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.).
  • a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
  • Film formation is performed using the pellets obtained as described above. It is also possible to feed the raw material powder directly to the extruder with a feeder and form a film as it is without pelletization.
  • the pellets produced are extruded using a single-screw or twin-screw extruder, the melting temperature Tm during extrusion is set to about 200 to 300 ° C., filtered through a leaf disk type filter or the like to remove foreign matter, and then the T-die The film is coextruded into a film, solidified on a cooling roll, and cast while pressing with an elastic touch roll.
  • Tm is the temperature of the die exit portion of the extruder.
  • defects are also referred to as die lines, but in order to reduce surface defects such as die lines, it is preferable to have a structure in which the resin retention portion is minimized in the piping from the extruder to the die. . It is preferable to use a die that has as few scratches as possible inside the lip.
  • the inner surface that comes into contact with the molten resin is preferably subjected to surface treatment that makes it difficult for the molten resin to adhere to the surface by reducing the surface roughness or using a material with low surface energy.
  • a hard chrome plated or ceramic sprayed material is polished so that the surface roughness is 0.2 S or less.
  • the cooling roll there is no particular limitation on the cooling roll, but it is a roll having a structure in which a heat medium or a coolant that can be controlled in temperature flows with a highly rigid metal roll, and the size is not limited. It is sufficient that the film is large enough to cool the film, and the diameter of the cooling roll is usually about 100 mm to 1 m.
  • the surface material of the cooling roll includes carbon steel, stainless steel, aluminum, titanium and the like. Further, in order to increase the hardness of the surface or improve the releasability from the resin, it is preferable to perform a surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, or ceramic spraying.
  • the surface roughness of the cooling roll surface is preferably 0.1 ⁇ m or less in terms of Ra, and more preferably 0.05 ⁇ m or less.
  • the smoother the roll surface the smoother the surface of the resulting film.
  • the surface processed is further polished to have the above-described surface roughness.
  • the film obtained as described above can be further stretched 1.01 to 3.0 times in at least one direction after passing through the step of contacting the cooling roll.
  • the film is stretched 1.1 to 2.0 times in both the longitudinal (film transport direction) and lateral (width direction) directions.
  • the stretching method a known roll stretching machine or tenter can be preferably used.
  • the light diffusion film also serves as a polarizing plate protective film
  • the slow axis of the light diffusion film becomes the width direction by stretching in the width direction.
  • the draw ratio is 1.1 to 3.0 times, preferably 1.2 to 1.5 times
  • the drawing temperature is usually Tg to Tg + 50 ° C. of the resin constituting the film, preferably Tg to Tg + 50 ° C. In the temperature range.
  • the stretching is preferably performed under a uniform temperature distribution controlled in the longitudinal direction or the width direction.
  • the temperature is preferably within ⁇ 2 ° C, more preferably within ⁇ 1 ° C, and particularly preferably within ⁇ 0.5 ° C.
  • the film-like resin film produced by the above method When the film-like resin film produced by the above method is used as a light diffusion film, the film may be contracted in the longitudinal direction or the width direction for the purpose of reducing retardation adjustment and dimensional change rate of the light diffusion film. .
  • Uniformity in the slow axis direction is also important, and the angle is preferably ⁇ 5 to + 5 ° with respect to the film width direction, more preferably in the range of ⁇ 1 to + 1 °, particularly ⁇ 0.
  • a range of 5 to + 0.5 ° is preferable, and a range of ⁇ 0.1 to + 0.1 ° is particularly preferable.
  • the light diffusing film of the present invention is preferably a long film.
  • the light diffusing film has a thickness of about 100 m to 5000 m and is usually provided in a roll shape.
  • the film width is preferably 1.3 to 4 m, more preferably 1.4 to 2 m.
  • the film thickness of the film-like resin film according to the present invention is not particularly limited, and is preferably changed according to the purpose.
  • the thickness is preferably 20 to 200 ⁇ m, more preferably 25 to 150 ⁇ m, and particularly preferably 30 to 120 ⁇ m.
  • FIG. 2 is a schematic flow sheet showing the overall configuration of an example of the light diffusion film manufacturing apparatus according to the present invention.
  • the light diffusing film is produced by mixing a film material such as a thermoplastic resin and then extruding it from the casting die 4 onto the first cooling roll 5 using the extruder 1. 5, and further circumscribed in order with a total of three cooling rolls, that is, the second cooling roll 7 and the third cooling roll 8, and cooled and solidified to form a film 10.
  • the film 10 peeled off by the peeling roll 9 is then stretched in the width direction by holding both ends of the film by the stretching device 12 and then wound by the winding device 16.
  • a touch roll 6 is provided that clamps the molten film on the surface of the first cooling roll 5 in order to correct the flatness.
  • the touch roll 6 has an elastic surface and forms a nip with the first cooling roll 5.
  • a device for automatically cleaning the belt and the roll it is preferable to add a device for automatically cleaning the belt and the roll to the manufacturing apparatus.
  • the cleaning device there is no particular limitation on the cleaning device, but for example, a method of niping a brush roll, a water absorbing roll, an adhesive roll, a wiping roll, etc., an air blowing method for spraying clean air, a laser incinerator, or a combination thereof. is there.
  • a polarizing plate When using the light-diffusion film which concerns on this invention as a protective film for polarizing plates, a polarizing plate can be produced by a general method. It is preferable that an adhesive layer is provided on the back surface side of the light diffusion film according to the present invention, and is bonded to at least one surface of a polarizer produced by immersion and stretching in an iodine solution.
  • the light diffusing film of the present invention may be used, or another polarizing plate protective film may be used.
  • a commercially available cellulose ester film for example, Konica Minoltack KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UE, KC4FR-4, KC4FR-3, KC4FR-3, KC4FR-4 -1, KC8UY-HA, KC8UX-RHA, manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.
  • a polarizer which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass.
  • a typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol.
  • iodine is dyed on a system film and one in which dichroic dye is dyed.
  • the polarizer is formed by forming a polyvinyl alcohol aqueous solution into a film and dyeing the film by uniaxial stretching or dyeing or uniaxially stretching, and then performing a durability treatment with a boron compound.
  • a pressure-sensitive adhesive having a storage elastic modulus at 25 ° C. in the range of 1.0 ⁇ 10 4 to 1.0 ⁇ 10 9 Pa in at least a part of the pressure-sensitive adhesive layer is used. It is preferable to use a curable pressure-sensitive adhesive that forms a high molecular weight body or a crosslinked structure by various chemical reactions after the pressure-sensitive adhesive is applied and bonded.
  • urethane adhesives examples include, for example, urethane adhesives, epoxy adhesives, aqueous polymer-isocyanate adhesives, curable adhesives such as thermosetting acrylic adhesives, moisture-curing urethane adhesives, polyether methacrylate types
  • curable adhesives such as thermosetting acrylic adhesives, moisture-curing urethane adhesives, polyether methacrylate types
  • anaerobic pressure-sensitive adhesives such as ester-based methacrylate type and oxidized polyether methacrylate, cyanoacrylate-based instantaneous pressure-sensitive adhesives, and acrylate-peroxide-based two-component instantaneous pressure-sensitive adhesives.
  • the above-mentioned pressure-sensitive adhesive may be a one-component type or a type in which two or more components are mixed before use.
  • the pressure-sensitive adhesive may be a solvent system using an organic solvent as a medium, or may be an aqueous system such as an emulsion type, a colloidal dispersion type, or an aqueous solution type that is a medium containing water as a main component. It may be a solventless type.
  • concentration of the pressure-sensitive adhesive liquid may be appropriately determined depending on the film thickness after adhesion, the coating method, the coating conditions, and the like, and is usually 0.1 to 50% by mass.
  • a protective film is bonded to the surface of the polarizer protective film on one side, a separate film is bonded to the surface of the pressure-sensitive adhesive layer on the other side, and the roll is wound It is also suitably used for the roll-shaped polarizing plate produced by
  • liquid crystal display device By incorporating the polarizing plate bonded with the light diffusion film according to the present invention into a liquid crystal display device, it is possible to produce various liquid crystal display devices with excellent visibility, especially large liquid crystal display devices, digital signage, etc. It is preferably used for a liquid crystal display device for outdoor use.
  • the polarizing plate according to the present invention is bonded to a liquid crystal cell via the adhesive layer or the like.
  • the polarizing plate according to the present invention is a reflective type, transmissive type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type (including FFS type), etc. It is preferably used in LCDs of various driving methods. In particular, in a large-screen display device with a VA screen of 30 or more, particularly 30 to 54, there is no white spot at the periphery of the screen and the effect is maintained for a long time.
  • a backlight light source of a liquid crystal display device a flat fluorescent lamp, a light emitting diode (LED) backlight having red (R), green (G), and blue (B) light emitting diodes (LED), organic electroluminescence
  • a white backlight using an element substrate can be used.
  • the light diffusion film of the present invention is suitable for a light emitting diode (LED) backlight.
  • Dianal BR85 manufactured by Mitsubishi Rayon Co., Ltd.
  • Mw 200000
  • the produced dope liquid was uniformly cast on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and peeling was performed from the stainless steel band support with a peeling tension of 162 N / m.
  • the web in which the mixture of the peeled acrylic resin and cellulose ester resin is compatible is evaporated at 35 ° C., slit to 1.6 m width, and then stretched 1.1 times in the width direction with a tenter, 135 ° C. It dried at the drying temperature of. At this time, the residual solvent amount when starting stretching with a tenter was 10%.
  • the core was wound around a core having an inner diameter of 15.24 cm at a tension of 110 N / m, and a mixture of an acrylic resin and a cellulose ester resin was compatible with each other to obtain a light diffusing film 1 which is a surface fine uneven resin film.
  • the draw ratio in the MD direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.
  • the residual solvent amount of the light diffusion film 1 shown in Table 1 was 0.1%, the film thickness was 60 ⁇ m, and the winding length was 5000 m.
  • Example 2 Production of light diffusion film 2
  • ⁇ Composition of main dope solution> Methylene chloride 340 parts by weight Ethanol 64 parts by weight Cellulose ester (cellulose acetate propionate acyl group total substitution degree 2.46, acetyl group substitution degree 1.58, propionyl group substitution degree 0.88, Mw 200000) 100 parts by weight Mono Pet SB (Daiichi Kogyo Seiyaku Co., Ltd.) 10 parts by mass
  • the above was put into a closed container and dissolved while stirring to prepare a dope solution.
  • the dope solution was uniformly cast on a stainless steel belt support at a temperature of 33 ° C. and a width of 1500 mm. The temperature of the stainless steel belt was controlled at 50 ° C.
  • the solvent was evaporated until the residual solvent amount in the cast (cast) film became 75%, and then peeled off from the stainless steel belt support with a peeling tension of 70 N / m.
  • a cellulose ester film coated with a poor solvent mixed solvent was stretched 37% in the width direction using a tenter while applying heat at 155 ° C.
  • the residual solvent at the start of stretching was 15%.
  • drying was terminated while the drying zone was conveyed by a number of rolls.
  • the drying temperature was 120 ° C. and the transport tension was 90 N / m.
  • Example 3 Production of light diffusion film 3
  • Additive AC1 ((meth) acrylic copolymer 10 parts by mass Methylene chloride 430 parts by mass Ethanol 40 Part by mass or more was put into a sealed container, heated, and completely dissolved while stirring.
  • the belt was uniformly cast on a stainless steel band support at a temperature of 35 ° C. and a width of 2.0 m.
  • the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support 101 was peeled off.
  • the web of the peeled cellulose ester film was evaporated at 35 ° C., slit to 1.80 m width, and then stretched 1.4 times in the TD direction (direction perpendicular to the film transport direction) with a tenter, It was dried at a drying temperature of 135 ° C. At this time, the residual solvent amount when starting stretching with a tenter was 20%.
  • the maximum stress during TD stretching was 10 MPa.
  • Example 4 Light diffusion film 4
  • the light diffusion film 4 was produced in the same manner as the light diffusion film 3 except that the substitution degree of the cellulose ester was changed to 2.4 and the acetone / water mixed solvent was applied to the tenter before being stretched.
  • the residual solvent amount of the light diffusion film was 0.2%, the film thickness was 40 ⁇ m, and the winding number was 7000 m.
  • Example 5 Light diffusion film 5
  • Dianal BR85 manufactured by Mitsubishi Rayon Co., Ltd.
  • a light diffusion film 5 was produced by applying a mixed solvent of ethanol and pure water heated to 60 ° C. in a ratio of 80:20 Vol% to the film surface.
  • Example 6 The film produced in Example 3 was attached to a light-emitting diode (LED) backlight television described later for evaluation.
  • LED light-emitting diode
  • the above-prepared fine particle dispersion was added to the dope, and a film was formed in the same manner as in Example 3 without applying a mixed solvent to obtain a comparative light diffusion film.
  • the wound film thickness was 60 ⁇ m and the number of turns was 3000 m.
  • Comparative Example 2 100 parts by mass of an ultraviolet curable acrylic resin (refractive index 1.52) and a true spherical acrylic resin (“Fine Powder MX300” manufactured by Soken Chemical Co., Ltd., refractive index 1.49) 3 having an average particle diameter of 3 ⁇ m as a filler 3
  • a dope was prepared by mixing 3 parts of an amorphous filler having a mean particle diameter of 3 ⁇ m (“Silicia 540” manufactured by Fuji Silysia Chemical Ltd., refractive index 1.50).
  • the dope was stirred with a screw stirrer and then applied onto a release-treated PET film, heated at 100 ° C., and then irradiated with ultraviolet rays to obtain a comparative light diffusion film having a thickness of 10 ⁇ m.
  • Comparative Example 3 A comparative light-diffusion film was produced by pressing a web produced using the same material as the dope liquid of Example 3 onto a roll with unevenness immediately after peeling from a stainless steel belt.
  • the film thickness was 60 ⁇ m and the winding length was 4000 m. However, a large amount of peeling residue was generated on the uneven roll, resulting in a uniform film and a decrease in productivity.
  • the conditions for measurement with a laser microscope were a magnification of 350 times.
  • the image was acquired from the direction which looks at the surface of a light-diffusion film perpendicularly
  • this image was subjected to waveform separation by Fourier transform to obtain an FFT image (fast Fourier transform image).
  • FFT image fast Fourier transform image
  • the pitch of the unevenness and the difference between the highest point of the convex portion and the lowest point of the concave portion were measured based on the profile of the FFT images of five images.
  • Measurement conditions Objective lens: 50 ⁇ intermediate lens zoom: 1 ⁇ camera resolution: 320 ⁇ 240 30 Hz Scan length: 5 ⁇ m (5 sec) Minimum modulation tolerance (min mod): 7% (Moisture permeability) The moisture permeability was measured according to the method described in JIS Z 0208 at a temperature of 40 ° C. and a relative humidity of 90% RH.
  • the surface haze of the light diffusion film of the present invention was measured by the following procedure. (1) The total haze (H) is measured as described above. (2) A polyethylene terephthalate film with an adhesive having an acrylic adhesive applied on one surface is attached to the surface of the light diffusion film of the present invention, and the total haze value H0 (%) is measured for the whole attached film. (3) Separately, the total haze value Ht of only the polyethylene terephthalate film with pressure-sensitive adhesive to which the acrylic pressure-sensitive adhesive was applied was measured, and the value obtained by subtracting Ht from the previously measured H0 was defined as the internal haze value Hi.
  • a 120- ⁇ m-thick long roll polyvinyl alcohol film was immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched in the transport direction 5 times at 50 ° C. to produce a polarizer.
  • the light diffusing film was bonded to one surface of the polarizer using a polyvinyl alcohol-based adhesive.
  • Konica Minolta Tack KC8UCR-5 (made by Konica Minolta Opto Co., Ltd.), a retardation film that has been subjected to alkali saponification treatment with a 1N KOH solution under saponification conditions at 45 ° C. for 30 seconds, is bonded to the other surface of the polarizer. And dried to produce various polarizing plates.
  • the light diffusing film of the present invention had no problem in drying property or contamination in the saponification process or the drying process.
  • the polarizing plates on both sides of the 32-inch TV AQ-32AD5 manufactured by Sharp Corporation were peeled off in advance, and the light polarizing films of the present invention were placed on the glass surface side of the liquid crystal cell. And it bonded so that an absorption axis might face in the same direction as the polarizing plate previously bonded, and each liquid crystal display device was produced.
  • the backlight was continuously turned on for 12 hours, and the entire black display state was visually observed in a dark room to evaluate luminance unevenness and unevenness due to sticking.
  • the light-emitting diode (LED) backlight TV used was a 46-inch TV LC-46LX-1 manufactured by Sharp Corporation.
  • the light diffusing sheet produced in the example is placed on the backlight unit for the liquid crystal display device, and a luminance meter (product name: CS-1000, manufactured by Konica Minolta Co., Ltd.) is installed at a distance of 50 cm. It was measured.
  • a luminance meter product name: CS-1000, manufactured by Konica Minolta Co., Ltd.
  • the evaluation was evaluated as “ ⁇ ” when the luminance was in the range from ⁇ 10% to less than + 10%, and “ ⁇ ” when the luminance decrease was 10% or more.
  • the light diffusion film according to the present invention is superior in scattering characteristics (surface haze), unevenness preventing property, and luminance as compared with the comparative example.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Liquid Crystal (AREA)

Abstract

La présente invention se rapporte à un film diffuseur de lumière qui est amélioré pour présenter une perméabilité à l'humidité adéquate et une productivité remarquable, et des variations réduites en termes de luminosité et d'adhésion. La présente invention se rapporte également à un procédé de fabrication du film diffuseur de lumière. En outre, la présente invention se rapporte à une plaque de polarisation, à une plaque de polarisation en forme de rouleau et à un dispositif d'affichage à cristaux liquides qui utilisent le film diffuseur de lumière. Le film diffuseur de lumière diffuse des rayons de lumière provenant d'une source de lumière et présente une structure faite de bosses et de creux sur au moins une des surfaces du film diffuseur de lumière. Le film diffuseur de lumière est caractérisé en ce que, dans une image de transformée de Fourier qui est basée sur une image acquise en mesurant la structure des bosses et des creux sous un microscope à laser de mesure en 3D, le pas moyen des bosses et des creux se situe dans la plage allant de 50 nm à 3 µm et la valeur moyenne des différences (des profondeurs) entre le point le plus haut d'une bosse et le point le plus bas d'un creux se situe dans la plage allant de 5 nm à 5 µm.
PCT/JP2010/059108 2010-05-28 2010-05-28 Film diffuseur de lumière, procédé de fabrication de ce dernier ainsi que plaque de polarisation, plaque de polarisation en forme de rouleau et dispositif d'affichage à cristaux liquides qui utilisent ce dernier Ceased WO2011148504A1 (fr)

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PCT/JP2010/059108 WO2011148504A1 (fr) 2010-05-28 2010-05-28 Film diffuseur de lumière, procédé de fabrication de ce dernier ainsi que plaque de polarisation, plaque de polarisation en forme de rouleau et dispositif d'affichage à cristaux liquides qui utilisent ce dernier

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PCT/JP2010/059108 WO2011148504A1 (fr) 2010-05-28 2010-05-28 Film diffuseur de lumière, procédé de fabrication de ce dernier ainsi que plaque de polarisation, plaque de polarisation en forme de rouleau et dispositif d'affichage à cristaux liquides qui utilisent ce dernier

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020164254A1 (fr) * 2019-02-14 2020-08-20 深圳市华星光电技术有限公司 Procédé de préparation de film de diffusion optique et module de rétroéclairage

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06265705A (ja) * 1993-03-16 1994-09-22 Ono Gijutsu Kenkyusho:Kk 光拡散反射部材
WO2008102487A1 (fr) * 2007-02-21 2008-08-28 Oji Paper Co., Ltd. Feuille ayant un motif non régulier formé sur celle-ci et son procédé de fabrication
JP2009282279A (ja) * 2008-05-22 2009-12-03 Oji Paper Co Ltd 反射シートおよびバックライトユニット

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06265705A (ja) * 1993-03-16 1994-09-22 Ono Gijutsu Kenkyusho:Kk 光拡散反射部材
WO2008102487A1 (fr) * 2007-02-21 2008-08-28 Oji Paper Co., Ltd. Feuille ayant un motif non régulier formé sur celle-ci et son procédé de fabrication
JP2009282279A (ja) * 2008-05-22 2009-12-03 Oji Paper Co Ltd 反射シートおよびバックライトユニット

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020164254A1 (fr) * 2019-02-14 2020-08-20 深圳市华星光电技术有限公司 Procédé de préparation de film de diffusion optique et module de rétroéclairage

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