[go: up one dir, main page]

WO2013080514A1 - Film optique, procédé de fabrication, plaque de polarisation et dispositif d'affichage à cristaux liquides - Google Patents

Film optique, procédé de fabrication, plaque de polarisation et dispositif d'affichage à cristaux liquides Download PDF

Info

Publication number
WO2013080514A1
WO2013080514A1 PCT/JP2012/007578 JP2012007578W WO2013080514A1 WO 2013080514 A1 WO2013080514 A1 WO 2013080514A1 JP 2012007578 W JP2012007578 W JP 2012007578W WO 2013080514 A1 WO2013080514 A1 WO 2013080514A1
Authority
WO
WIPO (PCT)
Prior art keywords
optical film
film
meth
film according
acrylic resin
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2012/007578
Other languages
English (en)
Japanese (ja)
Inventor
齋藤　浩一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2013546988A priority Critical patent/JP6123677B2/ja
Publication of WO2013080514A1 publication Critical patent/WO2013080514A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid

Definitions

  • the present invention relates to an optical film, a manufacturing method thereof, a polarizing plate, and a liquid crystal display device.
  • Liquid crystal display devices are widely used as liquid crystal displays for televisions and personal computers.
  • the liquid crystal display device includes a liquid crystal cell, a pair of polarizing plates sandwiching the liquid crystal cell, and a backlight.
  • the polarizing plate usually has a polarizer and a pair of protective films that sandwich the polarizer.
  • the polarizing plate and the liquid crystal cell are bonded together with an adhesive. At that time, if a bonding error occurs, the polarizing plate may be peeled off from the liquid crystal cell and reattached. However, when the polarizing plate is peeled off from the liquid crystal cell, there is a problem that the polarizing plate is easily torn. Therefore, the protective film constituting the polarizing plate is required to be able to be easily peeled off without tearing the polarizing plate from the liquid crystal cell when a bonding error occurs (good reworkability). .
  • cellulose ester films with adjusted water absorption modulus for example, Patent Document 1
  • cellulose ester films with adjusted tan ⁇ for example, Patent Document 2
  • acyl group substitution degree are adjusted.
  • a film containing cellulose ester for example, Patent Document 3
  • a pressure-sensitive adhesive composition containing a (meth) acrylic resin and a crosslinking agent for example, Patent Document 4
  • Patent Document 4 has been proposed as a pressure-sensitive adhesive for bonding a polarizing plate and a liquid crystal cell and improving reworkability. Yes.
  • the protective film not only a film mainly composed of cellulose ester but also a film mainly composed of (meth) acrylic resin is used depending on the required optical properties.
  • a molding material containing a (meth) acrylic resin as a main component for example, a resin composition containing a (meth) acrylic resin and an alkyl phosphate metal salt is known (for example, Patent Document 5).
  • the film mainly composed of (meth) acrylic resin is harder and more brittle than the film mainly composed of cellulose ester as described in Patent Documents 1 to 4. Therefore, the polarizing plate including a film containing a (meth) acrylic resin as a main component has a problem that when it is peeled off from the liquid crystal cell once bonded, it is easily torn and has low reworkability.
  • the protective film is required to be thinner.
  • a protective film having a thin film thickness has a problem that reworkability is further lowered because of its low mechanical strength.
  • the (meth) acrylic resin film is usually produced by a melt film forming method. Therefore, in order to increase the flexibility of the (meth) acrylic resin film, it is effective to increase the melting temperature and increase the fluidity of the molten resin. However, when the melting temperature is increased, there is a problem that the molten resin is easily deteriorated, and the resulting film is colored, is brittle and has low flexibility, or does not satisfy desired optical characteristics.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide an optical film containing a (meth) acrylic resin as a main component, having no coloring, a thin film thickness, and excellent reworkability. To do.
  • An optical film comprising a composition containing a (meth) acrylic resin and an acid trapping agent, having a breaking stress of 70 MPa or more, a tear strength of 10 mN or more, and a film thickness of 10 to 45 ⁇ m. .
  • a polarizing plate protective film comprising the optical film according to any one of [1] to [8].
  • the polarizing plate protective film according to [9] which is defined by the following formula and has a thickness direction retardation Rth measured at a wavelength of 590 nm of ⁇ 5 nm to 5 nm.
  • a polarizing plate comprising a polarizer and the polarizing plate protective film according to [9] or [10] disposed on at least one surface of the polarizer.
  • a liquid crystal display device comprising a liquid crystal cell and the polarizing plate according to [11] disposed on at least one surface of the liquid crystal cell.
  • an optical film that contains (meth) acrylic resin as a main component, is not colored, has a thin film thickness, and has excellent reworkability.
  • optical film of this invention contains the composition containing a (meth) acrylic resin and an acid trap agent.
  • the composition preferably further contains a cellulose ester.
  • the (meth) acrylic resin is preferably a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and another copolymerizable monomer.
  • the content ratio of the structural unit derived from methyl methacrylate in the copolymer is preferably 50% by mass or more, and more preferably 70% by mass or more.
  • copolymer monomers in the copolymer include alkyl methacrylates having 2 to 18 carbon atoms in the alkyl portion; alkyl acrylates having 1 to 18 carbon atoms in the alkyl portion; hydroxyl groups that can form a lactone ring structure described later.
  • Alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl moiety Alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl moiety; ⁇ , ⁇ -unsaturated acids such as acrylic acid and methacrylic acid; unsaturated group-containing divalent carboxylic acids such as maleic acid, fumaric acid and itaconic acid
  • Aromatic vinyl compounds such as styrene and ⁇ -methylstyrene
  • ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • N-vinylpyrrolidone (VP) and the like are included . These may 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 are used to improve the thermal decomposition resistance and fluidity of the copolymer.
  • Alkyl (meth) acrylates having a hydroxyl group such as methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are preferred.
  • acryloylmorpholine and the like are preferable.
  • the (meth) acrylic resin preferably contains a lactone ring structure from the viewpoint of enhancing the heat resistance of the resulting optical film or adjusting the photoelastic coefficient.
  • the lactone ring structure contained in the (meth) acrylic resin is preferably represented by the following general formula (1).
  • R 1 to R 3 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
  • the organic residue may contain an oxygen atom.
  • Examples of organic residues include linear or branched alkyl groups, linear or branched alkylene groups, aryl groups, —OAc groups (Ac is an acetyl group), —CN groups, and the like.
  • the lactone ring structure represented by the formula (1) is a structure derived from an alkyl (meth) acrylate having a hydroxyl group, as will be described later.
  • the (meth) acrylic resin containing a lactone ring structure further includes a structural unit derived from an alkyl (meth) acrylate having 1 to 18 carbon atoms in the alkyl portion, and if necessary, a monomer containing a hydroxyl group, an unsaturated carboxylic acid
  • a structural unit derived from an acid, a monomer represented by the general formula (2), or the like may be further included.
  • R 4 in the general formula (2) represents a hydrogen atom or a methyl group.
  • X is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, —OAc group (Ac: acetyl group), —CN group, acyl group, or —C—OR group (R is a hydrogen atom or 1 to 20 organic residues).
  • the content ratio of the lactone ring structure represented by the formula (1) in the (meth) acrylic resin containing a lactone ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, More preferably, it is 15 to 70% by mass.
  • the content of the lactone ring structure is more than 90% by mass, the molding processability is low, and the flexibility of the obtained film tends to be low.
  • the content of the lactone ring structure is less than 5% by mass, it is difficult to obtain a film having a necessary retardation, and heat resistance, solvent resistance, and surface hardness may not be sufficient.
  • the content of the structural unit derived from the alkyl (meth) acrylate is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, Preferably, the content is 30 to 85% by mass.
  • the content ratio of the structural unit derived from the hydroxyl group-containing monomer, the unsaturated carboxylic acid, or the monomer represented by the general formula (2) is preferably independently from 0 to 30. % By mass, more preferably 0 to 20% by mass, and still more preferably 0 to 10% by mass.
  • the (meth) acrylic resin containing a lactone ring structure is obtained by polymerizing a monomer component containing at least an alkyl (meth) acrylate having a hydroxyl group and another alkyl (meth) acrylate to form a hydroxyl group in the molecular chain. It can be produced through a step of obtaining a polymer having an ester group; a step of introducing a lactone ring structure by heat-treating the obtained polymer.
  • the weight average molecular weight Mw of the (meth) acrylic resin is preferably in the range of 8.0 ⁇ 10 4 to 5.0 ⁇ 10 5 , more preferably 9.0 ⁇ 10 4 to 4.5 ⁇ 10 5 . Within the range, more preferably within the range of 1.0 ⁇ 10 5 to 4.0 ⁇ 10 5 . If the weight average molecular weight Mw of the (meth) acrylic resin is less than 8.0 ⁇ 10 4 , the resulting film may be too brittle, and if it exceeds 5.0 ⁇ 10 5 , the viscosity of the melt It is too high or the resulting film has a high haze.
  • the weight average molecular weight Mw of the (meth) acrylic resin can be measured by gel permeation chromatography.
  • the measurement conditions are as follows. Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three products manufactured by Showa Denko KK) Column temperature: 25 ° C Sample concentration: 0.1% by mass Detector: RI Model 504 (manufactured by GL Sciences) Pump: L6000 (manufactured by Hitachi, Ltd.) Flow rate: 1.0ml / min
  • (Meth) acrylic resin can be produced by a known method such as suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization.
  • the polymerization initiator a normal peroxide compound, azo compound, or redox compound can be used.
  • the polymerization temperature can be about 30 to 100 ° C. for suspension polymerization or emulsion polymerization; it can be about 80 to 160 ° C. for solution polymerization or bulk polymerization.
  • alkyl mercaptan or the like may be used as a chain transfer agent.
  • Examples of commercially available (meth) acrylic resins include Delpet 60N, 80N (Asahi Kasei Chemicals Corporation), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electricity). Chemical Industry Co., Ltd.).
  • (Meth) acrylic resin may be one kind or a mixture of two or more kinds.
  • Cellulose ester is a compound obtained by esterifying cellulose with aliphatic carboxylic acid or aromatic carboxylic acid.
  • the acyl group contained in the cellulose ester is an aliphatic acyl group or an aromatic acyl group, preferably an aliphatic acyl group.
  • the aliphatic acyl group may be linear or branched and may further have a substituent. The portion that is not substituted with an acyl group usually exists as a hydroxyl group.
  • the cellulose ester has a total acyl group substitution degree (Dall) of 2.0 to 3.0 from the viewpoint of enhancing compatibility with the (meth) acrylic resin or imparting brittleness of the resulting film. Is more preferable, and 2.5 to 3.0 is more preferable.
  • the total substitution degree of the acyl group of the cellulose ester is less than 2.0, the (meth) acrylic resin and the cellulose ester may not be sufficiently compatible, and the resulting film may have high haze.
  • the substitution degree of the acyl group having 3 to 7 carbon atoms is preferably 1.2 to 3.0, more preferably 2.0 to 3.0.
  • the substitution degree of the acyl group having 3 to 7 carbon atoms is less than 1.2, the (meth) acrylic resin and the cellulose ester are not sufficiently compatible with each other, and the resulting film has high haze or high brittleness. Because it does.
  • the degree of acyl group substitution can be measured by the method prescribed in ASTM-D817-96.
  • cellulose esters examples include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, cellulose butyrate, preferably cellulose acetate propionate, cellulose propionate. It is.
  • the weight average molecular weight Mw of the cellulose ester resin is preferably 7.5 ⁇ 10 4 or more from the viewpoint of enhancing the compatibility with the (meth) acrylic resin, and 7.5 ⁇ 10 4 to 2.4 ⁇ 10 5. Is more preferably in the range of 1.0 ⁇ 10 5 to 2.4 ⁇ 10 5 , further preferably in the range of 1.6 ⁇ 10 5 to 2.4 ⁇ 10 5. Particularly preferred.
  • the weight average molecular weight Mw is less than 7.5 ⁇ 10 4 , the resulting film has low flexibility and heat resistance may be insufficient.
  • the melt has a high viscosity and is difficult to melt and extrude, and has a low compatibility with the (meth) acrylic resin. Haze tends to rise.
  • the Tg of the cellulose ester is preferably 100 ° C. or higher, and more preferably 120 ° C. or higher.
  • the upper limit of the Tg of the cellulose ester can be about 190 ° C.
  • the Tg of cellulose ester can be measured by a method based on JIS K7121.
  • Cellulose ester can be synthesized by a known method. Specifically, cellulose is esterified with an organic acid having at least 3 carbon atoms containing acetic acid or an anhydride thereof or an anhydride thereof in the presence of a catalyst to synthesize a triester of cellulose. The cellulose triester is then hydrolyzed to synthesize a cellulose ester resin having the desired degree of acyl substitution. After the obtained cellulose ester resin is filtered, precipitated, washed with water, dehydrated and dried, a cellulose ester resin can be obtained (see the method described in JP-A-10-45804).
  • cellulose used as a raw material for example, cotton linter, wood pulp (derived from coniferous tree, derived from broadleaf tree), kenaf and the like can be used.
  • the cellulose used as a raw material may be only one type or a mixture of two or more types.
  • the total content of the (meth) acrylic resin and the cellulose ester in the optical film of the present invention is preferably 55% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass with respect to the optical film. That's it.
  • the content ratio of the (meth) acrylic resin is more than 95% by mass with respect to the total of the (meth) acrylic resin and the cellulose ester, the effect due to the cellulose ester is not sufficiently obtained, and is less than 30% by mass, The resulting film may have sufficient heat and humidity resistance.
  • the optical film of the present invention may further contain other resins other than the (meth) acrylic resin and cellulose ester as long as the effects of the present invention are not impaired.
  • styrene resins include styrene resins.
  • the styrenic resin is a homopolymer of styrene monomer (polystyrene), a copolymer of a styrene monomer and another copolymerizable monomer, or a modified product of these polymers, preferably styrene monomer and other It is a copolymer with a copolymerizable monomer.
  • the content of the structural unit derived from the styrene monomer in the copolymer is preferably in the range of 0 to 20% by mass.
  • Examples of the copolymerizable monomer with the styrene monomer include maleic anhydride, acrylonitrile, maleimide and the like, preferably acrylonitrile.
  • the styrene / acrylonitrile copolymer can impart flexibility to a film containing the copolymer.
  • composition constituting the optical film of the present invention further contains an acid trap agent.
  • the acid trapping agent include alkyl phosphate metal salts and compounds containing an epoxy group.
  • the alkyl phosphate metal salt is a metal salt of an alkyl phosphate having 2 to 20 carbon atoms.
  • the metal atom constituting the alkyl phosphate metal salt is a Group 2 or Group 12 metal atom, and preferably includes zinc, calcium, magnesium and the like.
  • alkyl phosphoric acid having 2 to 20 carbon atoms constituting the alkyl phosphoric acid metal salt examples include ethyl phosphoric acid, butyl phosphoric acid, lauryl phosphoric acid, stearyl phosphoric acid and the like, preferably stearyl phosphoric acid.
  • alkyl phosphate metal salts examples include LBT-1830 manufactured by Sakai Chemical.
  • Examples of the compound containing an epoxy group include epoxidized vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid alkyl ester, and epoxidized 1,2 polybutadiene.
  • Examples of the epoxidized fatty acid alkyl ester include epoxidized fatty acid octyl ester (Adekasizer D-32 manufactured by Asahi Denka Co., Ltd.), epoxidized fatty acid isobutyl ester (Adekasizer D-55 manufactured by Asahi Denka Co., Ltd.), and the like.
  • Examples of the epoxidized 1,2 polybutadiene include Adekasizer BF-1000 (average molecular weight 10,000).
  • Examples of the compound containing an epoxy group include compounds containing an epoxy group described in US Pat. No. 4,137,201.
  • the optical film of the present invention can be obtained through a step of extruding after melt-kneading a resin composition containing a (meth) acrylic resin and an acid trapping agent.
  • a resin composition containing a (meth) acrylic resin and an acid trapping agent In order to obtain an optical film having high reworkability; that is, to obtain an optical film having high flexibility, it is effective to increase the resin fluidity by increasing the melting temperature when melt-kneading the resin composition.
  • the melting temperature is increased, the monomer remaining in the raw material (meth) acrylic resin is thermally decomposed to generate an acid, or the ester portion of the cellulose ester is hydrolyzed to generate an acid. Acid tends to cause thermal degradation of the resin.
  • the acid trapping agent can trap these acids, thermal degradation of the resin can be suppressed even if the melting temperature is increased.
  • the content of the acid trapping agent is preferably 0.1% by mass or more, preferably 0.5% by mass or more with respect to the composition in order to suppress thermal decomposition of the resin during melt kneading described later. More preferably, it is more preferably 1.0% by mass or more.
  • the content of the acid trapping agent is preferably 5.0% by mass or less.
  • the optical film of the present invention further contains additives such as a lubricant, an antioxidant, a thermal degradation inhibitor, an ultraviolet absorber, a colorant, and fine particles (matting agent) as long as the effects of the present invention are not impaired. Also good.
  • additives such as a lubricant, an antioxidant, a thermal degradation inhibitor, an ultraviolet absorber, a colorant, and fine particles (matting agent) as long as the effects of the present invention are not impaired. Also good.
  • the composition constituting the optical film of the present invention may further contain a lubricant in order to improve transparency and surface quality.
  • the lubricant can not only lower the melt viscosity of the resin composition described later and improve the kneadability, but also can suppress the retention of the molten resin in the extruder or the die during the melt extrusion.
  • Lubricants can be ester waxes or polyhydric alcohol fatty acid esters.
  • Ester waxes are compounds obtained by esterifying all hydroxyl groups of a polyhydric alcohol with a fatty acid.
  • Polyhydric alcohol fatty acid esters are compounds obtained by esterifying a part of hydroxyl groups of a polyhydric alcohol with a fatty acid.
  • the fatty acid constituting the ester wax or the polyhydric alcohol fatty acid ester has 12 carbon atoms from the viewpoint of suppressing contamination of the process due to volatilization under heating and increasing the compatibility with the cellulose ester.
  • a fatty acid of ⁇ 22 is preferred.
  • the fatty acid may be a saturated fatty acid or an unsaturated fatty acid, but a saturated fatty acid is preferable from the viewpoint of deodorization and prevention of discoloration during storage.
  • saturated fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, erucic acid, 12-hydroxyoleic acid, etc.
  • Stearic acid is preferred.
  • One type of fatty acid may be used, or a mixture of two or more types may be used.
  • polyhydric alcohols constituting ester waxes or polyhydric alcohol fatty acid esters include adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propane Diol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol 1,6-hexanediol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, glycerin, diglycerin, galactitol, inositol, mannitol, 3-methylpentane-1,3,5-triol , Nakoru, sorbitol, trimethylol propane, trimethylol ethane, pen
  • ester wax examples include pentaerythritol tetrafatty acid ester, dipentaerythritol hexafatty acid ester, glycerin trifatty acid ester and the like.
  • Preferred examples of the polyhydric alcohol fatty acid esters include glycerin or diglycerin fatty acid monoester or diester; sorbitol fatty acid monoester, diester or triester; sorbitan fatty acid monoester, diester or triester, more preferably Is fatty acid monoester or diester of glycerin or diglycerin, fatty acid monoester, diester or triester of sorbitan, more preferably glycerin fatty acid monoester.
  • ester waxes can reduce friction between the inner wall surface (metal surface) of the extruder, which will be described later, and the molten resin, and can reduce shearing heat generation.
  • ester waxes have low compatibility with (meth) acrylic resins and cellulose esters, the effect of lowering the melt viscosity is small, and the resulting film tends to bleed out.
  • Polyhydric alcohol fatty acid esters have a smaller effect on reducing the friction between the inner wall (metal surface) of the extruder and the molten resin than ester waxes, but the effect of lowering the melt viscosity is great, so shear heat generation can be reduced. .
  • polyhydric alcohol fatty acid esters are highly compatible with (meth) acrylic resins and cellulose esters, the resulting film is less likely to bleed out. Therefore, it is preferable to use polyhydric alcohol fatty acid esters.
  • the esterification reaction of ester waxes or polyhydric alcohol fatty acid esters is beef tallow, pork tallow, chicken tallow, fish oil, soybean oil, corn oil, rapeseed oil, palm oil, sunflower oil, safflower oil, castor oil or their hydrogen.
  • One or a mixture of two or more of the additive oils and glycerin, diglycerin or sorbitol are subjected to a transesterification reaction, and then the resulting reaction product can be purified.
  • the purification method may be a method such as molecular distillation, solvent fractionation, recrystallization, column chromatography, or supercritical gas extraction, and molecular distillation is generally used from the viewpoint of ease of production, quality, and price.
  • the content of the ester wax or polyhydric alcohol fatty acid ester is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass with respect to the optical film. . If these contents are less than 0.05% by mass, the effect of the lubricant is difficult to obtain, and if the content is more than 2.0% by mass, the heat-and-moisture resistance of the resulting film decreases and the haze increases. Cheap.
  • the ultraviolet absorber is a compound that absorbs ultraviolet light having a wavelength of 400 nm or less, preferably a compound having a transmittance at a wavelength of 370 nm of 10% or less, more preferably 5% or less, and even more preferably 2% or less. is there.
  • the light transmittance of the ultraviolet absorber can be measured with a spectrophotometer by a conventional method using a solution obtained by dissolving the ultraviolet absorber in a solvent (for example, dichloromethane, toluene, etc.).
  • the spectrophotometer is, for example, a spectrophotometer UVIDFC-610 manufactured by Shimadzu Corporation, a 330-type self-recording spectrophotometer, a U-3210-type self-recording spectrophotometer, a U-3410-type self-recording spectrophotometer, manufactured by Hitachi, Ltd. -4000 self-recording spectrophotometer or the like can be used.
  • Ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex salts, inorganic powders, and polymer ultraviolet absorbers.
  • benzotriazole-based UV absorbers and benzophenone-based UV absorbers are preferable, and benzotriazole-based UV absorbers are more preferable.
  • UV absorbers include 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl)- 6- (linear and side chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone and the like are included.
  • Examples of commercially available ultraviolet absorbers include TINUVIN109, TINUVIN171, TINUVIN326, TINUVIN327, TINUVIN328, TINUVIN900, TINUVIN928, and LA-31 manufactured by ADEKA Corporation, manufactured by Ciba Japan.
  • polymer ultraviolet absorbers examples include polymer type ultraviolet absorbers described in JP-A-6-148430.
  • the ultraviolet absorber may be one kind or a mixture of two or more kinds.
  • the content of the ultraviolet absorber is preferably 0.5 to 4% by mass, more preferably 0.6 to 3.5% by mass with respect to the optical film, although it depends on the type of the ultraviolet absorber. preferable.
  • the composition constituting the optical film of the present invention preferably further contains an antioxidant as a stabilizer.
  • antioxidant examples include sulfur compounds, phenol compounds, hindered amine compounds, phosphorus compounds, compounds containing unsaturated double bonds, and the like.
  • sulfur compounds examples include Sumitizer TPL-R, Sumilizer TP-D, etc. manufactured by Sumitomo Chemical Co., Ltd.
  • phenolic compounds include compounds having a 2,6-dialkylphenol structure (for example, 2,6-di-t-butyl-p-cresol).
  • examples of commercially available phenolic compounds include Irganox 1076 and Irganox 1010 manufactured by BASF Japan Ltd.
  • Examples of phosphorus compounds include tris (2,4-di-t-butylphenyl) phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, and the like.
  • Examples of commercially available phosphorus compounds include Sumitizer GP manufactured by Sumitomo Chemical Co., Ltd., ADK STAB PEP-24G manufactured by ADEKA Co., Ltd., ADK STAB PEP-36 and ADK STAB 3010, IRGAFOS P-EPQ manufactured by BASF Japan K.K. This includes GSY-P101 manufactured by Kogyo Corporation.
  • hindered amine compounds examples include Tinuvin 144 and Tinuvin 770 manufactured by BASF Japan, and ADK STAB LA-52 manufactured by ADEKA.
  • Examples of the compound containing an unsaturated double bond include Sumitizer GM and Sumilizer GS manufactured by Sumitomo Chemical Co., Ltd.
  • the antioxidant may be only one kind or a mixture of two or more kinds, but is preferably a mixture of two or more kinds.
  • the content of the antioxidant is preferably 0.05 to 5% by mass, more preferably 0.1 to 4% by mass with respect to the resin component (total of (meth) acrylic resin and cellulose ester). preferable.
  • the composition constituting the optical film of the present invention contains a colorant for imparting bluishness to the color tone of the liquid crystal display screen, adjusting the yellow index (yellowness), and reducing haze. Furthermore, you may contain.
  • the colorant include dyes such as anthraquinone dyes and azo dyes, and pigments such as phthalocyanine pigments.
  • the composition constituting the optical film of the present invention may further contain fine particles (matting agent) in order to enhance the slipperiness of the surface of the obtained optical film.
  • the layer on the outermost surface preferably contains fine particles.
  • the fine particles may be inorganic fine particles or organic fine particles.
  • inorganic fine particles include silicon dioxide (silica), titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples include magnesium silicate and calcium phosphate. Of these, silicon dioxide and zirconium oxide are preferable, and silicon dioxide is more preferable in order to reduce an increase in haze of the obtained film.
  • Examples of fine particles of silicon dioxide include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600, NAX50 (manufactured by Nippon Aerosil Co., Ltd.), Sea Hoster KE-P10, KE-P30, KE-P50, KE-P100 (manufactured by Nippon Shokubai Co., Ltd.) and the like are included.
  • zirconium oxide fine particles examples include Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.).
  • the types of polymers constituting the polymer fine particles include silicone resins, fluororesins, and acrylic resins, preferably silicone resins, and more preferably silicone resins having a three-dimensional network structure.
  • Examples of the polymer fine particles include Tospearl 103, 105, 108, 120, 145, 3120 and 240 (manufactured by Toshiba Silicone Co., Ltd.).
  • Aerosil R972V, NAX50, Seahoster KE-P30 and the like are particularly preferable because the friction coefficient can be reduced while keeping the turbidity of the obtained film low.
  • the fine particles are preferably subjected to a surface treatment in order to improve dispersibility and reduce an increase in the haze of the resulting film.
  • a surface treatment agent include halosilanes, alkoxysilanes, silazane, siloxane and the like.
  • the primary particle diameter of the fine particles is preferably 5 to 50 nm, more preferably 7 to 20 nm.
  • a larger primary particle size has a greater effect of increasing the slipperiness of the resulting film, but transparency tends to decrease. Therefore, the fine particles may be contained as secondary aggregates having a particle diameter of 0.05 to 0.3 ⁇ m.
  • the size of the primary particles or secondary aggregates of the fine particles was determined by observing the primary particles or secondary aggregates at a magnification of 500,000 to 2,000,000 times with a transmission electron microscope, and measuring 100 primary particles or secondary aggregates. It can be determined as an average value of the particle diameter.
  • the content of the fine particles is preferably 0.05 to 1.0% by mass, more preferably 0.1 to 0.8% by mass with respect to the resin component described above.
  • the optical film may be a single-layer film made of a composition containing the above-mentioned (meth) acrylic resin and an acid trapping agent; or made of a composition containing the above-mentioned (meth) acrylic resin and an acid trapping agent. It may be a laminated film including layers.
  • the thickness of the optical film is not particularly limited, but is preferably 20 to 200 ⁇ m, more preferably 25 to 100 ⁇ m, further preferably 30 to 80 ⁇ m, and more preferably 10 to 45 ⁇ m. It is particularly preferred. If the thickness of the film is too small, it is difficult to obtain a desired retardation. On the other hand, if the thickness of the film is too large, the retardation tends to fluctuate due to the influence of humidity and the like.
  • the residual solvent amount of the optical film is preferably 0.01% by mass or less.
  • the amount of residual solvent in the optical film can be measured by the following method. 1) Prepare a calibration curve of the solvent used in the optical film production process by the following gas chromatography. 2) 20 ml of a sample obtained by pulverizing the optical film is placed in a sealed glass container and heat-treated under headspace heating conditions. 3) The volatile component obtained by the heat treatment of 2) is quantified by gas chromatography with reference to a calibration curve, and the amount of residual solvent in the optical film is measured. The residual solvent amount is expressed as a part by mass with respect to the total mass of the optical film.
  • the breaking stress of the optical film of the present invention under an atmosphere of 23 ° C. and 55% RH is preferably 70 MPa or more, and more preferably 80 MPa or more, in order to enhance the reworkability of the polarizing plate containing the optical film. .
  • the breaking stress of the optical film is preferably 200 MPa or less.
  • the breaking stress by the following procedure. That is, the optical film is cut into a size of 10 mm ⁇ 150 mm to obtain a sample piece. This sample piece was subjected to a tensile test with a tensile tester (Strograph-R2 (manufactured by Toyo Seiki)) at a chuck distance of 100 mm, a temperature of 25 ° C., and a stretching speed of 10 mm / min. Let it be stress.
  • a tensile tester Strograph-R2 (manufactured by Toyo Seiki)
  • the elongation at break in at least one direction measured in accordance with JIS-K7127-1999 of the optical film of the present invention is 30% or more, more preferably 50% or more.
  • the upper limit of the elongation at break is practically about 250%.
  • the melting temperature is increased, the flexibility of the film is increased, or defects in the film due to foreign matter or foaming are reduced.
  • the tear strength of the optical film of the present invention in an atmosphere of 23 ° C. and 55% RH is preferably 10 mN or more, more preferably 20 mN or more in order to improve the reworkability of the polarizing plate containing the optical film. .
  • the tear strength of the optical film is preferably 100 mN or less.
  • Tear strength can be measured as follows. That is, the optical film is cut into a size of 65 mm ⁇ 50 mm to obtain a sample piece. The tear load of this sample piece by the Elmendorf method is measured with a light load tear device manufactured by Toyo Seiki Co., Ltd. according to JIS K-7128-1991.
  • the retardation Ro in the in-plane direction measured at a wavelength of 590 nm under the environment of 23 ° C. and 55% RH of the optical film is preferably in the range of ⁇ 5 nm to 5 nm, and in the range of ⁇ 3 nm to 3 nm. It is more preferable.
  • the retardation Rth in the thickness direction is preferably in the range of ⁇ 5 nm to 5 nm, and more preferably in the range of ⁇ 3 nm to 3 nm.
  • Retardation R0 and Rth are each represented by the following formula.
  • Formula (I) R 0 (nx ⁇ ny) ⁇ d
  • Formula (II) Rth ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d
  • Nx refractive index in the slow axis direction in the film plane
  • ny refractive index in the direction perpendicular to the slow axis in the film plane
  • nz refractive index of the film in the thickness direction
  • d film thickness (Nm))
  • the retardations R0 and Rth can be determined by the following method, for example. 1) The average refractive index of the film is measured with a refractometer. 2) The retardation R 0 in the in-plane direction when light having a wavelength of 590 nm from the normal direction of the film is incident is measured by KOBRA-21ADH manufactured by Oji Scientific Instruments. 3) The retardation value R ( ⁇ ) when light having a wavelength of 590 nm is incident from the angle ⁇ (incident angle ( ⁇ )) with respect to the normal direction of the film is measured with KOBRA-21ADH manufactured by Oji Scientific Instruments. . ⁇ is larger than 0 °, preferably 30 ° to 50 °.
  • nx, ny and nz are calculated by KOBRA-21ADH manufactured by Oji Scientific Instruments, and Rth is calculated.
  • the measurement of retardation can be performed under conditions of 23 ° C. and 55% RH.
  • the angle ⁇ 1 (orientation angle) formed by the in-plane slow axis of the optical film and the width direction of the film is preferably ⁇ 5 ° or more and + 5 ° or less, and more preferably ⁇ 1 ° or more and + 1 ° or less. .
  • the orientation angle ⁇ 1 of the optical film can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
  • the haze of the optical film measured according to JIS K-7136 is more preferably 0.5% or less in order to obtain sufficient brightness and high contrast in a liquid crystal display device, and 0.35% More preferably, it is more preferably 0.05% or less.
  • the melting temperature may be increased or the substitution degree of the acyl group having 3 to 7 carbon atoms of the cellulose ester may be increased.
  • the haze of the optical film can be measured by a method according to JIS K-7136; specifically, the following method. 1) The obtained optical film is conditioned at 23 ° C. and 55% RH for 5 hours or more. Thereafter, dust attached to the surface of the film is removed with a blower or the like. 2) Next, the haze of the optical film is measured with a haze meter (turbidimeter) (model: NDH 2000, manufactured by Nippon Denshoku Co., Ltd.) under the condition of 23 ° C. and 55% RH.
  • the light source of the haze meter may be a 5V9W halogen sphere, and the light receiving part may be a silicon photocell (with a relative visibility filter).
  • the visible light transmittance of the optical film is preferably 90% or more, and more preferably 92% or more.
  • the optical film of the present invention preferably has no streak-like defects.
  • a streak-like defect is a streak extending in the longitudinal direction of the film on the optical film surface, and the height of the streak in the film width direction cross section (height from the top of the streak peak to the bottom of the valley) is 300 nm or more.
  • the streak slope is 300 nm / mm or more.
  • the shape of the streak defect can be measured by the following procedure. 1) Using Mitutoyo SV-3100S4, film is applied at a measuring speed of 1.0 mm / sec while applying a measuring force of 0.75 mN to a stylus (diamond needle) having a tip shape of 60 ° cone and a radius of curvature of 2 ⁇ m. Scan in the width direction and measure the cross-sectional curve in the film width direction with a Z-axis (thickness direction) resolution of 0.001 ⁇ m. 2) From the obtained cross-sectional curve, the vertical distance (H) between the top of the streak peak and the bottom point of the trough is read and set as the streak height. Also, the horizontal distance (L) between the peak of the mountain and the bottom of the valley is read, and the value obtained by dividing the vertical distance (H) by the horizontal distance (L) is defined as the slope of the stripe.
  • the (meth) acrylic resin and cellulose ester contained in the optical film of the present invention are preferably compatible with each other. Whether or not the (meth) acrylic resin and the cellulose ester are compatible can be confirmed by, for example, the glass transition temperature Tg of the optical film. For example, as for the glass transition temperature of the optical film in which the (meth) acrylic resin and the cellulose ester are compatible, the glass transition temperature derived from each resin is not confirmed, and only one glass transition temperature is confirmed.
  • the glass transition temperature is measured as a midpoint glass transition temperature (Tmg) by a method based on JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer).
  • the heating rate can be 20 ° C./min.
  • the optical film of the present invention may further have other functional layers (an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorption layer, a polarizing layer, etc.) as necessary.
  • the optical film of the present invention is a polarizing plate protective film, a retardation film, an antireflection film, a brightness enhancement film, a hard coat film, an antiglare film, an antistatic film, an optical compensation film for widening the viewing angle, etc. for liquid crystal display devices. It can be preferably used.
  • the polarizing plate protective film include a protective film further having a retardation adjustment function, an optical compensation function, and the like.
  • the optical film of the present invention is a method in which the resin composition containing the (meth) acrylic resin and the acid trapping agent is heated and melted, and then cast and formed (melting film forming method).
  • the melt film forming method include a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, and a stretch molding method.
  • a melt extrusion method is preferred. That is, the optical film of the present invention can be obtained through a step of extruding after melt-kneading a resin composition containing a (meth) acrylic resin and an acid trapping agent.
  • FIG. 1 is a schematic diagram illustrating an example of a film manufacturing apparatus.
  • a film manufacturing apparatus 10 includes an extruder 12 that melts and kneads a resin, a die 14 that discharges the molten resin into a film, and multi-stage cooling of the high-temperature resin discharged from the die 14.
  • the extruder 12 is a melt-kneading extruder, and has a cylinder and a screw rotatably provided therein.
  • a hopper (not shown) for supplying film material is provided at the supply port of the cylinder.
  • the shape of the screw may be full flight, mudock, dull mage, etc., and is selected according to the viscosity of the molten resin and the required shearing force.
  • the extruder 12 may be a single screw extruder or a twin screw extruder.
  • a filter 28 for filtering the molten resin may be further provided between the extruder 12 and the die 14.
  • the filter 28 is, for example, a leaf disk type filter, and is preferably a stainless fiber sintered filter.
  • the filtration accuracy of the filter is preferably 3 to 15 ⁇ mm.
  • the filter 28 is preferably a multilayer body of filtration media having different filtration accuracy from the viewpoint of increasing the accuracy of capturing foreign substances or gels.
  • a mixing device such as a static mixer 30 for uniformly mixing the resin, a gear pump (not shown) for stabilizing the extrusion flow rate, and the like may be further provided. Good.
  • the die 14 may be a known one, such as a T die.
  • the material of the die 14 body is sprayed or plated with hard chromium, chromium carbide, chromium nitride, titanium carbide, titanium carbonitride, titanium nitride, super steel, ceramic (tungsten carbide, aluminum oxide, chromium oxide), etc .; buff, It may further be subjected to surface processing such as plane cutting or electrolytic polishing.
  • the material of the lip portion of the die 14 can be the same as that of the die body.
  • the surface accuracy of the lip portion of the die 14 is preferably 0.5S or less, and more preferably 0.2S or less.
  • the slit of the die 14 is configured such that the gap can be adjusted.
  • the pair of lips forming the slit of the die 14 one is a flexible lip having low rigidity and is easily deformed, and the other is preferably a fixed lip because the slit gap can be easily adjusted.
  • the slit gap (die lip clearance) is preferably 900 ⁇ m or more, and more preferably 1 mm or more and 2 mm or less. When the die lip clearance is out of the above range, spotted unevenness tends to occur in the obtained film.
  • the inner wall surface from the extruder 12 to the tip of the die 14 should have a structure in which a resin staying portion is difficult to adhere; for example, from the extruder 12 to the tip of the die 14 It is preferable that the inner wall surface is not scratched.
  • the inner wall surfaces of the extruder 12 and the die 14 are preferably subjected to surface processing for reducing the surface roughness or reducing the surface energy in order to make the molten resin difficult to adhere.
  • surface processing include processing for polishing to have a surface roughness of 0.2 S or less after hard chrome plating or ceramic spraying.
  • the first cooling roll 16, the second cooling roll 18, and the third cooling roll 20 are high-rigidity metal rolls, and have a structure in which a temperature-controllable medium can be circulated.
  • the material of the surface of the cooling rolls 16, 18 and 20 can be stainless steel, aluminum, titanium or the like.
  • the surface of the cooling rolls 16, 18 and 20 may be subjected to a surface treatment such as hard chrome plating in order to make the resin easy to peel off.
  • the surface roughness Ra of the cooling rolls 16, 18, and 20 is preferably 0.1 ⁇ m or less, and more preferably 0.05 ⁇ m or less, in order to keep the haze of the resulting film low.
  • the elastic touch roll 32 is disposed to face the cooling roll 16.
  • the molten resin extruded from the die 14 is nipped between the cooling roll 16 and the elastic touch roll 32.
  • As the elastic touch roll 32 a silicon rubber roll covered with a thin metal sleeve as described in JP-A-03-124425, JP-A-08-224772, JP-A-07-1000096 and the like is used.
  • the stretching device 24 is not particularly limited, but a roll stretching machine, a tenter stretching machine or the like is preferably used. A roll stretching machine and a tenter stretching machine may be combined.
  • the tenter stretching machine preferably has a preheating zone, a stretching zone, a holding zone, and a cooling zone, and preferably has a neutral zone for insulating between the zones.
  • the various rolls in the manufacturing apparatus 10 may be further provided with a mechanism for cleaning the roll surface.
  • the roll cleaning method may include a method of niping a brush roll, a water absorption roll, an adhesive roll, a wiping roll, an air blow method of spraying clean air, a laser incineration method, or a combination thereof.
  • the optical film of the present invention is, for example, a step of preparing pellets made of the resin composition described above (pelletizing step); It can be obtained through a step of cooling and solidifying the extruded molten resin to obtain a film (cooling and solidifying step); a step of stretching the film (stretching step).
  • the resin composition containing the (meth) acrylic resin and the acid trapping agent is previously kneaded and pelletized.
  • Pelletization can be performed by a known method.
  • the above resin composition is melt-kneaded with an extruder and then extruded from a die in a strand shape.
  • the molten resin extruded in a strand shape can be cooled with water or air, and then cut to obtain pellets.
  • the ultraviolet absorber or fine particles (matting agent) may be contained in the main pellet made of the above resin composition, or may be contained in a high concentration master pellet different from the above resin composition.
  • the raw material of the pellet is preferably dried before being supplied to the extruder in order to prevent decomposition.
  • the cellulose ester easily absorbs moisture, it is preferable to dry it at 70 to 140 ° C. for 3 hours or more so that the water content is 200 ppm or less, preferably 100 ppm or less.
  • the plural types of additives supplied to the extruder may be mixed in advance or may not be mixed.
  • a small amount of an additive such as an antioxidant is preferably mixed in advance before being supplied to the extruder in order to mix uniformly.
  • the raw materials are preferably mixed with a vacuum nauter mixer.
  • the atmosphere near the hopper of the extruder or the exit of the die is preferably an atmosphere of dehumidified air or N 2 gas in order to prevent deterioration of the raw material of the pellet.
  • the hopper of the extruder is preferably kept warm to prevent moisture absorption of the raw materials.
  • the extruder 12 is preferably kneaded at a low shearing force or at a low temperature so as not to cause deterioration of the resin (decrease in molecular weight, coloring, generation of gel-like foreign matters, etc.).
  • a twin screw extruder it is preferable to use a deep groove type screw and to rotate the two screws in the same direction.
  • two screw shapes mesh with each other.
  • the b * value as an index of yellowness is preferably in the range of -5 to 10, more preferably in the range of -1 to 8, and preferably in the range of -1 to 5. More preferred.
  • the b * value can be measured with a spectrocolorimeter CM-3700d (manufactured by Konica Minolta Sensing Co., Ltd.) with a light source of D65 (color temperature 6504K) and a viewing angle of 10 °.
  • an optical film may be produced by melting and kneading the resin composition not melt-kneaded as a raw material with the extruder 12 as it is.
  • the film material containing pellets is supplied to the extruder 12 from a hopper (not shown).
  • the supply of pellets is preferably performed under vacuum, reduced pressure, or an inert gas atmosphere in order to prevent oxidative decomposition of the pellets.
  • the film material containing a pellet is melt-kneaded in the extruder 12.
  • the melting temperature of the film material in the extruder 12 depends on the type of the film material, the viscosity and discharge amount of the melt, the thickness of the obtained film, etc., but preferably when the glass transition temperature of the film is Tg ° C. It is in the range of Tg ° C. to (Tg + 150) ° C., more preferably in the range of (Tg + 50) ° C. to (Tg + 130) ° C. Specifically, in the case of a (meth) acrylic resin / cellulose ester mixture, the melting temperature is about 150 to 300 ° C, preferably 200 to 270 ° C, more preferably 240 to 270 ° C, The temperature is preferably 260 to 270 ° C. If the melting temperature is too low, the film material may not be sufficiently kneaded, and if the melting temperature is too high, the film material may be thermally deteriorated.
  • Highly reworkable optical film Specifically, in order to obtain a highly flexible optical film, it is considered effective to increase the melt temperature and increase the fluidity of the molten resin. However, if the melting temperature is increased, the resin is likely to be thermally deteriorated, so that the resulting film is colored, becomes brittle, or does not satisfy desired optical properties.
  • the mechanism of thermal degradation of the resin when the melting temperature is increased is not necessarily clear, but the monomer remaining in the raw material (meth) acrylic resin is thermally decomposed to generate an acid, and this acid is the resin. This is presumed to cause thermal degradation of the material. Thermal degradation of the resin when the melting temperature is increased is particularly likely to occur particularly when the resin composition contains a (meth) acrylic resin and a cellulose ester. It is presumed that the ester portion of the cellulose ester is hydrolyzed to generate an acid, which also causes the resin to thermally deteriorate.
  • the resin composition containing a (meth) acrylic resin further contains an acid trapping agent.
  • the acid trapping agent can trap an acid that decomposes the resin component, particularly when the melting temperature is increased. Thereby, even if the melting temperature is increased, the resin can be melt-kneaded without causing thermal degradation.
  • the melt viscosity of the film material in the extruder 12 is preferably 1 to 10,000 Pa ⁇ s, and more preferably 10 to 1000 Pa ⁇ s. When the melt viscosity of the melt is too high, the pressure rises, so that the residence time in the extruder 12 tends to be long.
  • the residence time of the film material in the extruder 12 is preferably short, preferably within about 5 minutes, preferably within 3 minutes, and more preferably within 2 minutes.
  • the residence time can be adjusted by the supply amount of the film material, L / D which is the ratio of the cylinder length (L) to the cylinder inner diameter (D), the number of rotations of the screw or the depth of the groove of the screw. .
  • the screw rotation speed and shape of the extruder 12 are appropriately selected depending on the melt viscosity and the discharge amount of the film material.
  • the shear rate in the extruder 12 is 1 / second to 10,000 / second, preferably 5 / second to 1000 / second, more preferably 10 / second to 100 / second.
  • the molten resin extruded from the extruder 12 is filtered with a filter 28 or the like as necessary, and further mixed with a static mixer 30 or the like, and extruded from the die 14 into a film.
  • the melting temperature Tm of the resin at the exit portion of the die 14 can be about 200 to 300.degree.
  • Cooling and solidifying step The resin extruded from the die is nipped between the cooling roll 16 and the elastic touch roll 32 so that the film-like molten resin has a predetermined thickness. Then, the film-like molten resin is cooled stepwise with a plurality of cooling rolls 18 and 20 and solidified.
  • the surface temperature Tr1 of the first cooling roll 16 and the surface temperature Tr2 of the second cooling roll 18 can be independently set to (Tg-50) ° C. or more and Tg or less. Further, Tr2> Tr1 is preferable, and 0 ⁇ Tr2-Tr1 ⁇ 50 is more preferable. This is because by setting Tr2> Tr1, the condensation of the additive on the second cooling roll 18 is suppressed and the film is easily remelted.
  • the re-dissolution of the additive into the film can be adjusted by the contact time between the film and the second cooling roll 18, and specifically, it is preferably 1.0 to 3.0 seconds.
  • the contact time is a second obtained by dividing the distance between the point where the film and the second cooling roll 18 start to contact and the point where the second cooling roll 18 starts to peel by the film conveyance speed. Is a number.
  • the peripheral speed R2 of the second cooling roll 18 is preferably larger than the peripheral speed R1 of the first cooling roll 16. Tension is applied to the film between these two cooling rolls, thereby improving the adhesion between the film and the first cooling roll 16.
  • the ratio of the peripheral speeds is preferably in the range of 1.00 to 1.05. If the ratio of the peripheral speeds exceeds 1.05, the film may be broken.
  • the peripheral speed of the third cooling roll 20 is preferably larger than the peripheral speed of the second cooling roll 18.
  • the draw ratio is preferably 5-30.
  • the draw ratio is a value obtained by dividing the lip clearance of the die 14 by the average film thickness of the film obtained by cooling and solidifying on the first, second and third cooling rolls 16, 18 and 20. By setting the draw ratio within the above range, it is easy to obtain a film with few failures that cause bright and dark stripes and spotted unevenness when an image is displayed on a liquid crystal display device.
  • the draw ratio can be adjusted by the die lip clearance and the take-up speed of the cooling roll.
  • the discharge of the molten resin from the lip (opening) of the die 14 to the surface of the first cooling roll 16 is preferably performed at a reduced pressure of 70 kPa or less, more preferably 50 to 70 kPa. This is because die lines are less likely to occur in the obtained film.
  • the method of reducing the pressure between the lip (opening) of the die 14 and the surface of the first cooling roll 16 is, for example, covering the space including the die 14 and the first cooling roll 16 with a pressure-resistant member and reducing the pressure inside the space. There are methods.
  • the surface temperature Tr0 of the elastic touch roll 32 is preferably equal to or lower than the glass transition temperature (Tg) of the film, and more preferably Tg-50 ⁇ Tr0 ⁇ Tg. If the surface temperature Tr0 of the elastic touch roll 32 exceeds Tg, the film and the first cooling roll 16 may be difficult to peel off.
  • the linear pressure of the elastic touch roll 32 when pressed by the elastic touch roll 32 is 9.8 to 147 N / cm.
  • the linear pressure is less than 9.8 N / cm, it is difficult to sufficiently suppress the die line.
  • the surface temperature Tt of the film-like molten resin extruded from the die 14 immediately before being nipped by the elastic touch roll 32 is preferably Tg ⁇ Tt ⁇ Tg + 110 ° C., more preferably Tg + 10 ° C. ⁇ Tt ⁇ Tg + 90 ° C., and further preferably Tg + 20 ° C. ⁇ Tt ⁇ Tg + 70 ° C.
  • the adjustment of the surface temperature Tt on the elastic touch roll 32 immediately before being nipped by the elastic touch roll 32 of the film-like molten resin shortens the air gap (distance) between the die 14 and the first cooling roll 16. Then, the method of suppressing the cooling between the die 14 and the first cooling roll 16, the method of keeping the temperature between the die 14 and the first cooling roll 16 with a heat insulating material or the method of heating or the like. it can.
  • the heating can be heating with hot air, an infrared heater or microwave.
  • the film surface temperature and roll surface temperature can be measured with a non-contact infrared thermometer. Specifically, the surface temperature of the film or roll is determined by using a non-contact handy thermometer (IT2-80, manufactured by Keyence Co., Ltd.), the surface temperature at any 10 locations in the width direction of the film or roll, Or it measures at the position 0.5m away from the surface of the roll.
  • IT2-80 non-contact handy thermometer
  • the film solidified by the cooling rolls 16, 18 and 20 is peeled off by the peeling roll 22.
  • peeling the film it is preferable to adjust the tension applied to the film in order to prevent deformation.
  • Stretching step The obtained film is stretched by a stretching device 24 to obtain an optical film.
  • the stretching may be performed in at least one of the width direction of the film (TD direction), the transport direction (MD direction), or the oblique direction, and both in the film width direction (TD direction) and the transport direction (MD direction). It is preferable to stretch.
  • stretching in both the width direction (TD direction) and the transport direction (MD direction) of the film stretching in the width direction (TD direction) of the film and stretching in the transport direction (MD direction) may be performed sequentially. You may do it simultaneously.
  • the draw ratio may be 1.01 to 3.0 times, preferably 1.1 to 2.0 times in each direction.
  • TD direction width direction
  • MD direction conveyance direction
  • it is finally 1.01 to 3.0 times, preferably 1.1 to 2.0 times in each direction. Is preferred.
  • the stretching temperature is preferably Tg to (Tg + 50) ° C., more preferably Tg to (Tg + 40) ° C.
  • the stretching temperature can be about 100 to 190 ° C.
  • the stretching temperature is too high, the tear strength of the obtained optical film is high, but the breaking stress may be low.
  • the stretching temperature is too low, the obtained optical film has a high breaking stress but may have a low tear strength.
  • the stretching temperature is preferably uniform in the width direction (TD direction) or the transport direction (MD direction) of the film, and the variation in the width direction or transport direction of the film stretching temperature is preferably ⁇ 2 ° C. or less, The temperature is more preferably ⁇ 1 ° C. or less, and further preferably ⁇ 0.5 ° C. or less.
  • the film obtained after stretching is shrunk in the transport direction (MD direction) or the width direction (TD direction) as necessary. May be.
  • MD direction transport direction
  • TD direction width direction
  • the distance between adjacent clips in the film transport direction is driven by the pantograph method or linear drive method. Then it should be smooth and narrow.
  • the width of the obtained optical film may be 0.5 to 4.0 m, preferably 1.0 to 3.0 m, although it depends on the width of the polarizer.
  • the film thickness variation of the optical film is preferably ⁇ 3% or less, and more preferably ⁇ 1% or less.
  • knurl processing embossing processing
  • the knurling can be performed with a knurling apparatus having an embossing ring and a back roll.
  • the optical film thus obtained is wound up by a winder.
  • the optical film of the present invention can be obtained through a step of extruding after melt-kneading a resin composition containing a (meth) acrylic resin and an acid trapping agent.
  • the acid trapping agent contained in this resin composition is produced when the monomer remaining in the (meth) acrylic resin is thermally decomposed and the ester part of cellulose ester is hydrolyzed when the melting temperature is increased. Since the acid can be trapped, the thermal deterioration of the resin can be suppressed. Therefore, it is possible to obtain an optical film that is not colored, satisfies desired optical characteristics, has high flexibility, and has high reworkability.
  • Polarizing plate The polarizing plate of the present invention comprises a polarizer and the optical film of the present invention disposed on at least one surface thereof.
  • a polarizer is an element that allows only light of a polarization plane in a certain direction to pass through.
  • a typical example of the polarizer is a polyvinyl alcohol-based polarizing film, and there are one in which a polyvinyl alcohol-based film is dyed with iodine and one in which a dichroic dye is dyed.
  • the polarizer may be a film obtained by uniaxially stretching a polyvinyl alcohol film and then dyeing with iodine or a dichroic dye, or after dyeing a polyvinyl alcohol film with iodine or a dichroic dye, A uniaxially stretched film (preferably a film further subjected to durability treatment with a boron compound) may be used.
  • the thickness of the polarizer is preferably 5 to 30 ⁇ m, more preferably 10 to 20 ⁇ m.
  • the polyvinyl alcohol film may be a film formed from a polyvinyl alcohol aqueous solution.
  • the polyvinyl alcohol film is preferably an ethylene-modified polyvinyl alcohol film because it is excellent in polarizing performance and durability performance and has few color spots.
  • Examples of the ethylene-modified polyvinyl alcohol film include an ethylene unit content of 1 to 4 mol%, a degree of polymerization of 2000 to 4000, and a degree of saponification of 99.0, as described in JP-A Nos. 2003-248123 and 2003-342322. ⁇ 99.99 mol% film is included.
  • dichroic dyes examples include azo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes and anthraquinone dyes.
  • the optical film of the present invention may be disposed directly on at least one surface of the polarizer, or may be disposed via another film or layer.
  • the optical film of the present invention may be disposed on the other surface of the polarizer, or a protective film other than that may be disposed.
  • the protective film is not particularly limited, and may be a normal cellulose ester film or the like.
  • commercially available cellulose ester films include commercially available cellulose ester films (for example, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UE, KC4UE, KC4FR-3, KC4FR-4, KC4HR-1, KC8UY-HA, KC8UX-RHA, manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.
  • the polarizing plate can be usually obtained through a step of bonding a polarizer and the optical film of the present invention.
  • adhesives used for pasting include saponified polyvinyl alcohol aqueous solutions, curable adhesives such as urethane adhesives, epoxy adhesives, aqueous polymer-isocyanate adhesives, thermosetting acrylic adhesives, etc.
  • a fully saponified polyvinyl alcohol aqueous solution is preferable.
  • the liquid crystal display device of the present invention includes a liquid crystal cell and a pair of polarizing plates that sandwich the liquid crystal cell. And at least one is a polarizing plate which has an optical film of this invention among a pair of polarizing plates, Preferably both of a pair of polarizing plates are polarizing plates which have an optical film of this invention.
  • FIG. 2 is a schematic diagram showing a basic configuration of an embodiment of the liquid crystal display device 110 according to the present invention.
  • the liquid crystal display device 110 includes a liquid crystal cell 120, a first polarizing plate 140 and a second polarizing plate 160 that sandwich the liquid crystal cell 120, and a backlight 180.
  • the display method of the liquid crystal cell 120 is not particularly limited, and is a TN (Twisted Nematic) method, an STN (Super Twisted Nematic) method, an IPS (In-Plane Switching) method (including an FFS method), an OCB (OpticallyalCompensating Bensing method).
  • VA Vertical Alignment
  • MVA Multi-domain Vertical Alignment and PVA; Patterned Vertical Alignment also included
  • HAN Hybrid Aligned Nematic
  • the first polarizing plate 140 is disposed on the viewing side of the liquid crystal cell 120, and the first polarizer 142 and the protective film 144 (F1) disposed on the viewing side of the first polarizer 142. And a protective film 146 (F2) disposed on the surface of the first polarizer 142 on the liquid crystal cell side.
  • the second polarizing plate 160 is disposed on the backlight 180 side, the second polarizer 162, a protective film 164 (F3) disposed on the liquid crystal cell side surface of the second polarizer 162, And a protective film 166 (F4) disposed on the backlight side surface of the second polarizer 162.
  • One of the protective films 146 (F2) and 164 (F3) may be omitted as necessary.
  • the protective films 144 (F1), 146 (F2), 164 (F3), and 166 (F4) at least one of the protective films 146 (F2) and 164 (F3) arranged on the liquid crystal cell side of the present invention is used.
  • An optical film is preferred.
  • the size of the liquid crystal display device is preferably 30 or more, more preferably 30 to 54.
  • the liquid crystal display device is preferably used also for outdoor applications such as digital signage.
  • the liquid crystal display device can be manufactured through a step of bonding a liquid crystal cell and a polarizing plate together with an adhesive.
  • the pressure-sensitive adhesive is preferably a curable pressure-sensitive adhesive, and more preferably a curable pressure-sensitive adhesive having a cured elastic modulus at 25 ° C. of 1.0 ⁇ 10 4 to 1.0 ⁇ 10 9 Pa. Examples of such an adhesive include those similar to the above-mentioned curable adhesive.
  • the optical film of the present invention is obtained through a step of melt-kneading a resin composition containing an acid trapping agent at a high melting temperature. Therefore, the optical film of the present invention is not colored and has high flexibility (reworkability) while satisfying desired optical characteristics. Therefore, even after the polarizing plate including the optical film of the present invention is once bonded to the liquid crystal cell, it can be easily peeled off from the liquid crystal cell without tearing the polarizing plate. Moreover, the liquid crystal display device containing the optical film of this invention has a favorable display characteristic.
  • the obtained mixture was melt-kneaded at 235 ° C. with a twin-screw extruder and extruded into a strand shape.
  • the resin composition extruded in a strand form was cooled with water and then cut to obtain pellets.
  • an optical film was produced with the film production apparatus 10 shown in FIG.
  • the obtained pellets were put into a single screw extruder (extruder 12), and melt kneaded at 260 ° C. in a nitrogen atmosphere. Then, it extruded from the die
  • the slit gap of the die 14 was 0.5 mm within 30 mm from the end in the film width direction, and 1 mm at other locations.
  • the surface temperature of the elastic touch roll 32 was 80 ° C.
  • the film obtained by cooling and solidifying the resin extruded from the die 14 on the first, second and third cooling rolls was peeled off by the peeling roll 22.
  • the obtained film was stretched 1.3 times at 145 ° C. in the width direction by a tenter stretching machine, and then cooled to 30 ° C. while relaxing 3% in the width direction.
  • the clip was removed, and the portions held by the clips at both ends of the film were cut off, and then knurling with a width of 10 mm and a height of 5 ⁇ m was applied to both ends of the film.
  • the obtained film was wound up at a winding tension of 220 N / m.
  • the obtained film had a thickness of 40 ⁇ m and a width of 1430 mm, and the glass transition temperature measured by the DSC method was 125 ° C.
  • Example 2 An optical film was obtained in the same manner as in Example 1 except that the type of the acid trapping agent or the melting temperature was changed as shown in Table 1.
  • Example 5 An optical film was obtained in the same manner as in Example 4 except that the content of the acid trapping agent was changed as shown in Table 1.
  • Example 9 to 12 An optical film was obtained in the same manner as in Example 3 except that the content ratio A / B of (A) (meth) acrylic resin and (B) cellulose ester was changed as shown in Table 1.
  • Example 15 An optical film was obtained in the same manner as in Example 1 except that the film thickness was changed as shown in Table 3.
  • Retardation Rth i) The average refractive index of the film was measured with a refractometer. ii) Retardation R 0 in the in-plane direction when light having a wavelength of 590 nm from the film normal direction was incident was measured by KOBRA-21ADH manufactured by Oji Scientific Instruments. iii) With KOBRA-21ADH manufactured by Oji Scientific Instruments, the retardation value R ( ⁇ ) was measured when light having a wavelength of 590 nm was incident from the angle ⁇ (incident angle ( ⁇ )) with respect to the film normal direction. . ⁇ was 30 ° to 50 °.
  • nx, ny and nz were calculated by KOBRA-21ADH manufactured by Oji Scientific Instruments, and Rth was calculated. The retardation was measured under the conditions of 23 ° C. and 55% RH.
  • the Rth of the obtained film is preferably ⁇ 3 nm or less.
  • the obtained optical film was alkali saponified, then washed with water, neutralized and washed with water. Thereafter, the obtained optical film was dried at 80 ° C. Saponification process 2M-NaOH 50 ° C. 90 seconds Water washing process Water 30 ° C. 45 seconds Neutralization process 10% by mass HCl 30 ° C. 45 seconds Water washing process Water 30 ° C. 45 seconds
  • KC4UY manufactured by Konica Minolta Opto Co., Ltd. was also alkali saponified. Then, KC4UY subjected to alkali saponification treatment was bonded to one surface of the above polarizer using a 5% aqueous solution of completely saponified polyvinyl alcohol as an adhesive. Similarly, an alkali film saponified optical film was bonded to the other surface of the polarizer using a 5% aqueous solution of completely saponified polyvinyl alcohol as an adhesive. The bonding was performed so that the transmission axis of the polarizer and the in-plane slow axis of the optical film were parallel. The laminated laminate was dried to obtain a polarizing plate.
  • n-BA n-butyl acrylate
  • MA methyl acrylate
  • 2-HEA 2-hydroxy acrylate
  • AIBN azobisiso 0.2 parts by mass of butyronitrile
  • the obtained pressure-sensitive adhesive composition was applied onto the peeled film so as to have a dry thickness of 25 ⁇ m to form a pressure-sensitive adhesive layer, thereby obtaining a pressure-sensitive adhesive sheet.
  • the aforementioned polarizing plate was punched into a size of 100 ⁇ 100 mm.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was transferred to one surface of the obtained polarizing plate to obtain a pressure-sensitive adhesive-attached polarizing plate.
  • the polarizing plate with an adhesive was bonded to the glass substrate.
  • the polarizing plate was slightly peeled from the glass substrate from one of the four corners, and was peeled diagonally while holding the peeled polarizing plate and holding the glass substrate. The same operation was performed on a total of 10 samples, and evaluation was performed according to the following criteria.
  • ⁇ All 10 sheets were able to be completely peeled without tearing.
  • ⁇ The optical film was torn with 1 to 5 sheets, and part of the film remained on the glass substrate. Torn and part of it remained on the glass substrate, resulting in peeling residue
  • ⁇ Change in total light transmittance is 5% or less.
  • ⁇ Change in total light transmittance is more than 5% and 10% or less.
  • X Change in total light transmittance is more than 10%. If it is ⁇ level, there is no practical problem.
  • the evaluation results of the optical films of Examples 1 to 14 are shown in Table 1, the evaluation results of the optical films of Comparative Examples 1 to 13 are shown in Table 2, and the evaluation results of the optical films of Examples 15 to 16 and Comparative Example 14 are shown.
  • Table 4 shows the evaluation results of Comparative Examples 15 to 18.
  • the films of Examples 1 to 16 containing LBT1830 or Adekasizer D-32 which are acid trapping agents have higher breaking stress and tear strength than the films of Comparative Examples 1 to 13 containing no acid trapping agent, and are colored. It turns out that it does not occur.
  • the films of Examples 1 and 2 formed at a high melting temperature have higher reworkability and no coloration than the films of Examples 3 and 4 formed at a low melting temperature.
  • the reason why the films of Examples 1 and 2 were not colored is considered to be that the thermal deterioration of the resin when the melting temperature was increased could be suppressed by containing an acid trapping agent.
  • the high reworkability of the films of Examples 1 and 2 is that the fluidity of the resin composition containing (meth) acrylic resin and cellulose ester can be increased by increasing the melting temperature, and the flexibility of the resulting film This is thought to be due to the improvement in performance.
  • Example 3 The comparison between Example 3 and 9 to 12 suggests that if the content ratio of the (meth) acrylic resin is too large, the resulting film tends to be slightly brittle and the tear strength tends to decrease slightly. On the other hand, when the content ratio of the cellulose ester is too large, it can be seen that the resulting film is slightly colored.
  • the film containing the (meth) acrylic resin containing the lactone ring has higher film strength and higher reworkability than the film containing the (meth) acrylic resin containing no lactone ring.
  • the strength of the film containing the (meth) acrylic resin containing the lactone ring is high because the structural units derived from the uncyclized hydroxyl group-containing monomer contained in the main chain of the (meth) acrylic resin containing the lactone ring are hydrogen. It is considered that this is because a bond is formed and the compatibility between the (meth) acrylic resin and the cellulose ester is high.
  • Example 16 it can be seen that even a thin film having a film thickness of about 10 ⁇ m has a tear strength of a certain level or more and exhibits good reworkability by including an acid trapping agent.
  • the resulting film is colored or the Rth is slightly increased. Since the film of Comparative Example 1 does not contain an acid trapping agent, it is considered that the resin was thermally deteriorated due to a high melting temperature. Moreover, it is considered that the Rth of the film containing the thermally deteriorated resin is high because the side chain of the cellulose ester is decomposed. Moreover, since the film containing the resin which carried out heat deterioration is weak, it turns out that rework property is also low.
  • the optical film of the present invention contains (meth) acrylic resin as a main component, is not colored, has a thin film thickness, and is excellent in reworkability.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Le but de l'invention est de fournir un film optique contenant une résine (méth)acrylique en qualité de composant principal, qui est dépourvu de coloration, qui possède une épaisseur de film fin, et qui possède une excellente aptitude au refaçonnage. Le film optique de la présente invention comprend une composition qui contient une résine (méth)acrylique et un agent de piégeage acide, qui possède une résistance à la rupture de 70 MPa ou plus, une résistance au déchirement de 10 mN ou plus, et une épaisseur de film de 10-45 μm.
PCT/JP2012/007578 2011-11-28 2012-11-27 Film optique, procédé de fabrication, plaque de polarisation et dispositif d'affichage à cristaux liquides Ceased WO2013080514A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013546988A JP6123677B2 (ja) 2011-11-28 2012-11-27 光学フィルムとその製造方法、偏光板および液晶表示装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-258919 2011-11-28
JP2011258919 2011-11-28

Publications (1)

Publication Number Publication Date
WO2013080514A1 true WO2013080514A1 (fr) 2013-06-06

Family

ID=48535009

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/007578 Ceased WO2013080514A1 (fr) 2011-11-28 2012-11-27 Film optique, procédé de fabrication, plaque de polarisation et dispositif d'affichage à cristaux liquides

Country Status (2)

Country Link
JP (1) JP6123677B2 (fr)
WO (1) WO2013080514A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014240906A (ja) * 2013-06-12 2014-12-25 コニカミノルタ株式会社 偏光板とその製造方法、及びそれを具備した有機エレクトロルミネッセンス表示装置
CN105467652A (zh) * 2014-09-30 2016-04-06 住友化学株式会社 偏振片、液晶显示装置和有机电致发光显示装置
JP2016071351A (ja) * 2014-09-30 2016-05-09 住友化学株式会社 偏光板、粘着剤付き偏光板及び液晶表示装置
JP2016126346A (ja) * 2014-12-26 2016-07-11 住友化学株式会社 偏光板
US20180265680A1 (en) * 2015-02-27 2018-09-20 Island Polymer Industries Gmbh Multifunctional optically highly transparent films and method for their production
JPWO2020184657A1 (fr) * 2019-03-14 2020-09-17
TWI735459B (zh) * 2015-08-27 2021-08-11 日商住友化學股份有限公司 切縫加工延伸薄膜的製造方法及製造裝置

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07216179A (ja) * 1994-01-26 1995-08-15 Asahi Chem Ind Co Ltd 熱安定性に優れた帯電防止性アクリル系樹脂組成物
JP2002120244A (ja) * 2000-10-18 2002-04-23 Konica Corp 光学用セルロースエステルフィルム、その製造方法及び偏光板
JP2006195407A (ja) * 2004-12-13 2006-07-27 Konica Minolta Opto Inc 光学フィルム、光学フィルムの製造方法、偏光板保護フィルム、位相差フィルム、及びそれらを用いた偏光板、液晶表示装置
JP2007056216A (ja) * 2005-08-26 2007-03-08 Fujifilm Corp ポリアリレート、光学フィルム、および、画像表示装置
JP2007231157A (ja) * 2005-03-10 2007-09-13 Konica Minolta Opto Inc 光学フィルム、光学フィルムの製造方法、光学補償フィルム、光学補償フィルムの製造方法、偏光板及び液晶表示装置
WO2008117577A1 (fr) * 2007-03-26 2008-10-02 Konica Minolta Opto, Inc. Film optique, procédé de fabrication d'un film optique, polariseur et dispositif d'affichage à cristaux liquides
JP2009294262A (ja) * 2008-06-02 2009-12-17 Fujifilm Corp 偏光板および液晶表示装置
JP2010243935A (ja) * 2009-04-09 2010-10-28 Konica Minolta Opto Inc 光学フィルム、光学フィルムの製造方法、それを用いた偏光板、及び液晶表示装置
JP2011022188A (ja) * 2009-07-13 2011-02-03 Konica Minolta Opto Inc 分極遮蔽型スメクチック液晶表示装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004191906A (ja) * 2002-10-18 2004-07-08 Konica Minolta Holdings Inc 光学補償フィルム、一体型視野角補償偏光板及び液晶表示装置
JP2008058893A (ja) * 2006-09-04 2008-03-13 Konica Minolta Opto Inc セルロースエステルフィルム、偏光板保護フィルム、偏光板、セルロースエステルフィルムの製造方法および液晶表示装置
JP4974971B2 (ja) * 2007-06-14 2012-07-11 株式会社日本触媒 熱可塑性樹脂組成物とそれを用いた樹脂成形品および偏光子保護フィルムならびに樹脂成形品の製造方法
JP2009292870A (ja) * 2008-06-02 2009-12-17 Fujifilm Corp アクリルフィルムおよびその製造方法、並びに、偏光板、光学補償フィルム、反射防止フィルムおよび液晶表示装置
JP5255918B2 (ja) * 2008-06-10 2013-08-07 富士フイルム株式会社 セルロース誘導体、セルロース誘導体フィルム、及びその用途
JP5557517B2 (ja) * 2009-12-09 2014-07-23 株式会社日本触媒 位相差フィルム

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07216179A (ja) * 1994-01-26 1995-08-15 Asahi Chem Ind Co Ltd 熱安定性に優れた帯電防止性アクリル系樹脂組成物
JP2002120244A (ja) * 2000-10-18 2002-04-23 Konica Corp 光学用セルロースエステルフィルム、その製造方法及び偏光板
JP2006195407A (ja) * 2004-12-13 2006-07-27 Konica Minolta Opto Inc 光学フィルム、光学フィルムの製造方法、偏光板保護フィルム、位相差フィルム、及びそれらを用いた偏光板、液晶表示装置
JP2007231157A (ja) * 2005-03-10 2007-09-13 Konica Minolta Opto Inc 光学フィルム、光学フィルムの製造方法、光学補償フィルム、光学補償フィルムの製造方法、偏光板及び液晶表示装置
JP2007056216A (ja) * 2005-08-26 2007-03-08 Fujifilm Corp ポリアリレート、光学フィルム、および、画像表示装置
WO2008117577A1 (fr) * 2007-03-26 2008-10-02 Konica Minolta Opto, Inc. Film optique, procédé de fabrication d'un film optique, polariseur et dispositif d'affichage à cristaux liquides
JP2009294262A (ja) * 2008-06-02 2009-12-17 Fujifilm Corp 偏光板および液晶表示装置
JP2010243935A (ja) * 2009-04-09 2010-10-28 Konica Minolta Opto Inc 光学フィルム、光学フィルムの製造方法、それを用いた偏光板、及び液晶表示装置
JP2011022188A (ja) * 2009-07-13 2011-02-03 Konica Minolta Opto Inc 分極遮蔽型スメクチック液晶表示装置

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014240906A (ja) * 2013-06-12 2014-12-25 コニカミノルタ株式会社 偏光板とその製造方法、及びそれを具備した有機エレクトロルミネッセンス表示装置
CN105467652A (zh) * 2014-09-30 2016-04-06 住友化学株式会社 偏振片、液晶显示装置和有机电致发光显示装置
JP2016071351A (ja) * 2014-09-30 2016-05-09 住友化学株式会社 偏光板、粘着剤付き偏光板及び液晶表示装置
JP2018124573A (ja) * 2014-09-30 2018-08-09 住友化学株式会社 偏光板、粘着剤付き偏光板及び液晶表示装置
KR101924160B1 (ko) * 2014-09-30 2018-11-30 스미또모 가가꾸 가부시키가이샤 편광판, 점착제를 구비한 편광판 및 액정 표시 장치
KR20180128378A (ko) * 2014-09-30 2018-12-03 스미또모 가가꾸 가부시키가이샤 편광판, 점착제를 구비한 편광판 및 액정 표시 장치
KR102314053B1 (ko) 2014-09-30 2021-10-15 스미또모 가가꾸 가부시키가이샤 편광판, 점착제를 구비한 편광판 및 액정 표시 장치
JP2016126346A (ja) * 2014-12-26 2016-07-11 住友化学株式会社 偏光板
US20180265680A1 (en) * 2015-02-27 2018-09-20 Island Polymer Industries Gmbh Multifunctional optically highly transparent films and method for their production
TWI735459B (zh) * 2015-08-27 2021-08-11 日商住友化學股份有限公司 切縫加工延伸薄膜的製造方法及製造裝置
JPWO2020184657A1 (fr) * 2019-03-14 2020-09-17
JP7394112B2 (ja) 2019-03-14 2023-12-07 株式会社クラレ 接着剤及び偏光板

Also Published As

Publication number Publication date
JPWO2013080514A1 (ja) 2015-04-27
JP6123677B2 (ja) 2017-05-10

Similar Documents

Publication Publication Date Title
KR101677777B1 (ko) 편광판의 제조 방법, 그 제조 방법으로 제조한 편광판 및 그 편광판을 사용한 액정 표시 장치
JP6123677B2 (ja) 光学フィルムとその製造方法、偏光板および液晶表示装置
WO2013080847A1 (fr) Procédé de fabrication d'un film à teneur en résine acrylique
JP5262256B2 (ja) セルロースエステルフィルム、偏光板および液晶表示装置
JP5392092B2 (ja) セルロースエステルフィルムの製膜方法
JP5120071B2 (ja) 光学フィルム、偏光板、及び液晶表示装置
JP2013119200A (ja) 熱可塑性樹脂フィルムの製造方法
KR101361251B1 (ko) 위상차 필름, 그것을 사용한 편광판 및 액정 표시 장치
JP2013119201A (ja) 熱可塑性樹脂フィルムの製造方法
WO2010082397A1 (fr) Film optique, polariseur, et dispositif d'affichage à cristaux liquides
JP2009173818A (ja) セルロースエステルフィルム、偏光板、及び液晶表示装置
JP5167646B2 (ja) セルロースエステルフィルムの製造方法
JP5381924B2 (ja) 光学フィルム
JP5590116B2 (ja) 光学フィルム、偏光板および液晶表示装置
JP5594348B2 (ja) セルロースエステルフィルムの製造方法
JP5494331B2 (ja) 溶融流延フィルム、偏光板及び液晶表示装置
WO2012023331A1 (fr) Film optique, plaque polarisante et dispositif d'affichage à cristaux liquides
JP2013120278A (ja) 偏光板保護フィルムの製造方法
JP5251973B2 (ja) 光学フィルム、偏光板
TW201033269A (en) Cellulose ester film, process for producing cellulose ester film, polarizing plate, and liquid crystal display device
JP5691865B2 (ja) 光学フィルム、及び光学フィルムの製造方法
JPWO2009119122A1 (ja) 偏光板、偏光板保護フィルムの製造方法および液晶表示装置
WO2013080568A1 (fr) Procédé de production d'un film optique, film optique, lame polarisante et dispositif d'affichage à cristaux liquides
JP2008149653A (ja) セルロースエステルフィルム、その製造装置および製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12852734

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013546988

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12852734

Country of ref document: EP

Kind code of ref document: A1