WO2009084295A1 - Film contenant une résine acrylique, plaque polarisante l'utilisant et dispositif d'affichage - Google Patents

Film contenant une résine acrylique, plaque polarisante l'utilisant et dispositif d'affichage Download PDF

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Publication number
WO2009084295A1
WO2009084295A1 PCT/JP2008/067920 JP2008067920W WO2009084295A1 WO 2009084295 A1 WO2009084295 A1 WO 2009084295A1 JP 2008067920 W JP2008067920 W JP 2008067920W WO 2009084295 A1 WO2009084295 A1 WO 2009084295A1
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Prior art keywords
acrylic resin
resin
containing film
film
acrylic
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PCT/JP2008/067920
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English (en)
Japanese (ja)
Inventor
Nobuo Kubo
Masataka Takimoto
Takashi Takebe
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Konica Minolta Opto, Inc.
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Priority to JP2009547940A priority Critical patent/JP5532927B2/ja
Priority to KR1020107013950A priority patent/KR101502196B1/ko
Publication of WO2009084295A1 publication Critical patent/WO2009084295A1/fr

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    • 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
    • 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
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • G02F1/133528—Polarisers
    • 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

Definitions

  • the present invention relates to an acrylic resin-containing film, a polarizing plate and a display device using the same, and more specifically, by blending acrylic resin and cellulose ester resin, and further using acrylic particles dispersed in a state incompatible with the resin.
  • the present invention relates to an acrylic resin film that is transparent, highly heat resistant, and has markedly improved brittleness.
  • PMMA Polymethyl methacrylate
  • the PMMA film has poor heat resistance and has a problem that its shape changes, brittleness, and inferior bending resistance when used at high temperatures or for long-term use.
  • This problem was an important issue not only as a physical property of a single film but also in a polarizing plate and a display device using such a film.
  • the polarizing plate curls with the deformation of the film, the entire panel is warped, and the design phase difference changes even when used at the position on the viewing side surface. There was a problem that the viewing angle fluctuated and the color changed.
  • PC polycarbonate
  • a method of introducing an alicyclic alkyl group as a copolymerization component of an acrylic resin, a method of forming a cyclic structure in a molecular main chain by carrying out an intramolecular cyclization reaction, and the like are disclosed.
  • Patent Documents 2, 3, and 4. For example, see Patent Documents 2, 3, and 4.
  • the heat resistance is improved, the brittleness of the film is remarkably deteriorated, and the deterioration of the brittleness promotes the deformation of the liquid crystal panel and the polarizing plate itself, and eventually suppresses the change of the birefringence phase difference. It was not possible to solve the problems of fluctuation in viewing angle and change in color.
  • This brittle deterioration has a problem of promoting the generation of dust even in the film cutting process.
  • the present invention has been made in view of the above problems, and an object thereof is to provide an acrylic resin-containing film that is transparent, has high heat resistance, and has markedly improved brittleness.
  • Another object of the present invention is to provide a polarizing plate and a liquid crystal display device in which the acrylic resin-containing film is improved in cutting properties, brittleness, bending resistance, physical properties such as surface hardness, and optical properties.
  • An acrylic resin-containing film comprising at least one curable resin layer, having a haze value of less than 1%, a tension softening point of 105 to 145 ° C., and no ductile fracture.
  • the acrylic resin-containing film contains the acrylic resin (A) and the cellulose ester resin (B) in a mass ratio of 95: 5 to 30:70, and the total substitution degree of acyl groups of the cellulose ester resin (B) (T ) Is 2.00 to 3.00, the acetyl group substitution degree (ac) is 0 to 1.89, the number of carbons of the acyl group other than the acetyl group is 3 to 7, and the weight average molecular weight (Mw) is 75000 to 280000. 2.
  • the acrylic resin-containing film as described in 1 above, wherein
  • a polarizing plate comprising the acrylic resin-containing film according to any one of 1 to 4 on at least one surface.
  • At least one curable resin layer containing acrylic resin (A) and cellulose ester resin (B) in a mass ratio of 95: 5 to 30:70, and the total of acyl groups of cellulose ester resin (B)
  • the degree of substitution (T) is 2.00 to 3.00
  • the degree of substitution of acetyl group (ac) is 0 to 1.89
  • the number of carbons of acyl groups other than acetyl groups is 3 to 7
  • the weight average molecular weight (Mw) Acrylic resin-containing film characterized by having an A of 75,000 to 280000.
  • an acrylic resin-containing film that is transparent, highly heat resistant, brittle, and has significantly improved surface hardness.
  • the present invention is a disadvantage of the conventional acrylic resin film, in that it has poor heat resistance, is used at high temperatures, is used for a long period of time, and the like, its shape is easily changed, is inferior in brittleness, and cannot be compatible with high surface hardness. It is an improvement.
  • the tension softening point is 105 to 145 ° C. and that ductile fracture does not occur is heat resistance as an optical film used for liquid crystal display devices and the like, and as one means for achieving it. It has been found that by blending the acrylic resin (A) and the cellulose ester resin (B), an acrylic resin-containing film that is transparent, has high heat resistance, is brittle, and has significantly improved surface hardness can be obtained.
  • the effect is further improved by having at least one curable resin layer.
  • the invention of claim 1 is characterized by having at least one curable resin layer, having a haze value of less than 1%, a tension softening point of 105 to 145 ° C., and no ductile fracture. It has been found that an acrylic resin-containing film that is transparent, has high heat resistance, and has significantly improved brittleness can be obtained by the acrylic resin-containing film.
  • the acrylic resin-containing film comprises 95: 5 to 30:70 of acrylic resin (A) and cellulose ester resin.
  • the cellulose ester resin (B) has a total substitution degree (T) of 2.00 to 3.00, an acetyl group substitution degree (ac) of 0 to 1.89, and other than acetyl groups.
  • T total substitution degree
  • ac acetyl group substitution degree
  • Mw weight average molecular weight
  • the invention according to claim 3 is the acrylic resin-containing film according to claim 2, wherein the acrylic resin (A) has a weight average molecular weight Mw of 80000 to 1000000.
  • the invention according to claim 4 is characterized in that the acrylic resin-containing film contains 0.5 to 45% by mass of acrylic particles (C) with respect to the total mass of the resin constituting the film. It is an acrylic resin-containing film according to any one of 1 to 3, and preferably takes the constitution of claims 2 to 3 in order to obtain the effects of the present invention.
  • the inventions of claim 5 and claim 6 use the polarizing plate characterized in that the acrylic resin-containing film is used on at least one surface, and the polarizing plate is used on at least one surface of a liquid crystal cell.
  • This is a liquid crystal display device characterized in that the acrylic resin-containing film of the present invention, which is transparent, has high heat resistance, and remarkably improves brittleness, is applied to a polarizing plate and a liquid crystal display device as an optical film.
  • the acrylic resin-containing film of the present invention is characterized in that the haze value is less than 1%, the tension softening point is 105 to 145 ° C., and ductile fracture does not occur.
  • the ductile fracture is caused by a stress that is greater than the strength of a certain material, and is defined as a fracture accompanied by significant elongation or squeezing of the material before the final fracture.
  • the fracture surface is characterized by numerous indentations called dimples.
  • the “acrylic resin-containing film that does not cause ductile fracture” is characterized in that no fracture such as fracture is observed even when a large stress is applied to bend the film in two at 23 ° C. and 55% RH. .
  • Forming an acrylic resin-containing film that does not cause ductile fracture is achieved by selecting the material configuration of the acrylic resin, cellulose ester, and other additives used as described below.
  • the acrylic resin-containing film according to the present invention has a low haze, a high temperature device such as a projector, and a use in a high temperature environment such as an in-vehicle display device.
  • the temperature is preferably 105 ° C to 145 ° C, and more preferably controlled to 110 ° C to 130 ° C.
  • the acrylic resin-containing film is 120 mm (length) ⁇ 10 mm (width).
  • the temperature is increased at a rate of temperature increase of 30 ° C./min while pulling at a tension of 10 N, and the temperature at the time of 9 N is measured three times, and the average value can be obtained.
  • the acrylic resin-containing film of the present invention preferably has a glass transition temperature (Tg) of 110 ° C. or higher. More preferably, it is 120 ° C. or higher. Especially preferably, it is 150 degreeC or more.
  • Tg glass transition temperature
  • the glass transition temperature referred to here is an intermediate value determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a heating rate of 20 ° C./min. Point glass transition temperature (Tmg).
  • the acrylic resin-containing film of the present invention has a defect of 5 ⁇ m or more in diameter in the film plane of 1 piece / 10 cm square. More preferably, it is 0.5 piece / 10 cm square or less, more preferably 0.1 piece / 10 cm square or less.
  • the diameter of the defect indicates the diameter when the defect is circular, and when it is not circular, the range of the defect is determined by observing with a microscope according to the following method, and the maximum diameter (diameter of circumscribed circle) is determined.
  • the range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object.
  • the defect is a change in the surface shape, such as transfer of a roll flaw or an abrasion
  • the size is confirmed by observing the defect with the reflected light of a differential interference microscope.
  • the film breaks with the defect as a starting point, and the productivity may be significantly reduced.
  • the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
  • the coating agent may not be formed uniformly, resulting in defects (coating defects).
  • the defect is a void in the film (foaming defect) generated due to the rapid evaporation of the solvent in the drying process of the solution casting, a foreign matter in the film forming stock solution, or a foreign matter mixed in the film forming. This refers to the foreign matter (foreign matter defect) in the film.
  • the acrylic resin-containing film of the present invention preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more, as measured in accordance with JIS-K7127-1999.
  • the upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.
  • the thickness of the acrylic resin-containing film of the present invention is preferably 20 ⁇ m or more. More preferably, it is 30 ⁇ m or more.
  • 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 thickness of the film can be appropriately selected depending on the application.
  • the acrylic resin-containing film of the present invention preferably has a total light transmittance of 90% or more, more preferably 93% or more.
  • the practical upper limit is about 99%.
  • 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 acrylic resin-containing film of the present invention is characterized in that the haze value (turbidity), which is one of the indices indicating transparency, is 1.0% or less, but the luminance when incorporated in a liquid crystal display device, From the viewpoint of contrast, it is preferably 0.5% or less.
  • the particle diameter and addition amount of the acrylic particles (C) should be suppressed within the above range, or the surface roughness of the film contact portion during film formation should be reduced. Is also effective.
  • the total light transmittance and haze value of the acrylic resin-containing film are values measured according to JIS-K7361-1-1997 and JIS-K7136-2000.
  • the acrylic resin-containing film of the present invention can be preferably used as an optical acrylic resin-containing film as long as it satisfies the physical properties as described above, but is excellent in workability and heat resistance by having the following composition. Film can be obtained.
  • the acrylic resin-containing film contains the acrylic resin (A) and the cellulose ester resin in a mass ratio of 95: 5 to 30:70, and the cellulose ester resin (B ) Has a total substitution degree (T) of 2.00 to 3.00, an acetyl group substitution degree (ac) of 0 to 1.89, and an acyl group other than the acetyl group has 3 to 7 carbon atoms,
  • T total substitution degree
  • ac acetyl group substitution degree
  • acyl group other than the acetyl group has 3 to 7 carbon atoms
  • the acrylic resin (A) and the cellulose ester resin are contained in a mass ratio of 95: 5 to 30:70, preferably the acrylic resin (A) is 50% by mass or more. .
  • the acrylic resin-containing film of the present invention may contain a resin other than the acrylic resin (A) and the cellulose ester resin (B).
  • the total mass of the acrylic resin (A) and the cellulose ester resin (B) is 55 to 100% by mass, preferably 60 to 99% by mass of the acrylic resin-containing film.
  • the acrylic resin 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 from the viewpoint of thermal decomposition resistance and fluidity of the copolymer.
  • n-Butyl acrylate is particularly preferably used.
  • the acrylic resin (A) used in the acrylic resin-containing film of the present invention preferably has a weight average molecular weight (Mw) of 80,000 to 1,000,000 from the viewpoint of mechanical strength as a film and fluidity when producing the film. .
  • the weight average molecular weight of the acrylic resin of the present invention can be measured by gel permeation chromatography.
  • the measurement conditions are as follows.
  • the production method of the acrylic resin (A) in the present invention is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used.
  • a polymerization initiator a normal peroxide type and an azo type can be used, and a redox type can also be used.
  • the polymerization temperature may be 30 to 100 ° C. for suspension or emulsion polymerization, and 80 to 160 ° C. for bulk or solution polymerization.
  • polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.
  • acrylic resins can be used as the acrylic resin of the present invention.
  • Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dialal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned. .
  • the cellulose ester resin of the present invention may be substituted with either an aliphatic acyl group or an aromatic acyl group, but is preferably substituted with an acetyl group.
  • the aliphatic acyl group has 2 to 7 carbon atoms, and specifically includes acetyl, propionyl, butyryl, isobutyryl and the like.
  • the aliphatic acyl group is meant to include those further having a substituent.
  • the aromatic ring is a benzene ring in the above-described aromatic acyl group
  • the substituent of the benzene ring are exemplified.
  • the number of substituents X substituted on the aromatic ring is 0 or 1 to 5, preferably 1 to 3, and particularly preferably One or two.
  • the cellulose ester resin has a structure having a structure selected from at least one of a substituted or unsubstituted aliphatic acyl group and a substituted or unsubstituted aromatic acyl group. Used, these may be single or mixed acid esters of cellulose.
  • the substitution degree of the cellulose ester resin of the present invention is such that the total substitution degree (T) of the acyl group is 2.00 to 3.00 and the substitution degree (ac) of the acetyl group is 0 to 1.89. More preferably, the acyl group substitution degree (r) other than the acetyl group is 2.00 to 2.89.
  • the acyl group other than the acetyl group preferably has 3 to 7 carbon atoms.
  • cellulose ester resin of the present invention those having an acyl group having 2 to 7 carbon atoms as a substituent, that is, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate It is preferably at least one selected from benzoate and cellulose benzoate.
  • particularly preferable cellulose ester resins include cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate.
  • the mixed fatty acid is a lower fatty acid ester of cellulose acetate propionate or cellulose acetate butyrate having an acyl group having 2 to 4 carbon atoms as a substituent.
  • the portion not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.
  • the degree of substitution of the acetyl group and the degree of substitution of other acyl groups were determined by the method prescribed in ASTM-D817-96. If the weight average molecular weight (Mw) of the cellulose ester resin of the present invention is 75000 or more, the object of the present invention can be achieved even if the weight average molecular weight is about 1000000, but considering productivity, it is 75000 to 280000. Those of 100,000 to 240,000 are more preferred.
  • the acrylic resin-containing film may contain acrylic particles.
  • the acrylic particles (C) according to the present invention are characterized by being present in the state of particles in the acrylic resin (A) and the cellulose ester resin (B) and the acrylic resin-containing film (also referred to as an incompatible state). .
  • the acrylic particles (C) are, for example, collected a predetermined amount of the prepared acrylic resin-containing film, dissolved in a solvent, stirred, and sufficiently dissolved / dispersed. It is preferable that the weight of the insoluble matter filtered and collected using a PTFE membrane filter having a pore size is 90% by mass or more of the acrylic particles (C) added to the acrylic resin-containing film.
  • the acrylic particles (C) used in the present invention are not particularly limited, but are preferably acrylic particles (C) having a layer structure of two or more layers, particularly the following multilayer structure acrylic granular composite. It is preferable.
  • the multilayer structure acrylic granular composite is formed by laminating an innermost hard layer polymer, a cross-linked soft layer polymer exhibiting rubber elasticity, and an outermost hard layer polymer from the center to the outer periphery.
  • Preferred embodiments of the multilayer structure acrylic granular composite used in the acrylic resin composition of the present invention include the following.
  • (c) the innermost hard In the presence of a polymer comprising a layer and a crosslinked soft layer, a monomer mixture comprising 80 to 99% by mass of methyl methacrylate and 1 to 20% by mass
  • Outermost hard layer weight And the obtained three-layer structure polymer is an innermost hard layer polymer (a) 5 to 40% by mass, a soft layer polymer (b) 30 to 60% by mass, and An outermost hard layer polymer (c) comprising 20 to 50% by mass, having an insoluble part when fractionated with acetone, and an acrylic granular composite having a methyl ethyl ketone swelling degree of 1.5 to 4.0 at the insoluble part .
  • the innermost hard layer polymer (a) constituting the multilayer structure acrylic granular composite is 80 to 98.9% by mass of methyl methacrylate and 1 to 20 mass of alkyl acrylate having 1 to 8 carbon atoms in the alkyl group. % And a monomer mixture consisting of 0.01 to 0.3% by mass of a polyfunctional grafting agent is preferred.
  • examples of the alkyl acrylate having 1 to 8 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like. And n-butyl acrylate are preferably used.
  • the proportion of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1 to 20% by mass.
  • the thermal decomposability of the polymer is increased, while the unit is 20% by mass. If it exceeds 50%, the glass transition temperature of the innermost hard layer polymer (c) is lowered, and the impact resistance imparting effect of the three-layer structure acrylic granular composite is lowered.
  • polyfunctional grafting agent examples include polyfunctional monomers having different polymerizable functional groups, such as allyl esters of acrylic acid, methacrylic acid, maleic acid, and fumaric acid, and allyl methacrylate is preferably used.
  • the polyfunctional grafting agent is used to chemically bond the innermost hard layer polymer and the soft layer polymer, and the ratio used during the innermost hard layer polymerization is 0.01 to 0.3% by mass. .
  • the crosslinked soft layer polymer (b) constituting the acrylic granular composite is an alkyl acrylate having from 9 to 8 carbon atoms having an alkyl group of 1 to 8 in the presence of the innermost hard layer polymer (a). What is obtained by polymerizing a monomer mixture consisting of 10% by mass, 0.01 to 5% by mass of a multifunctional crosslinking agent and 0.5 to 5% by mass of a multifunctional grafting agent is preferred.
  • n-butyl acrylate or 2-ethylhexyl acrylate is preferably used as the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group.
  • Examples of other monofunctional monomers that can be copolymerized include styrene and substituted styrene derivatives. As the ratio of the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group and styrene increases, the glass transition temperature of the produced polymer (b) decreases as the former increases, that is, it can be softened.
  • the refractive index of the soft layer polymer (b) at room temperature is set to the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the hard heat. It is more advantageous to make it closer to the plastic acrylic resin, and the ratio between them is selected in consideration of these.
  • polyfunctional grafting agent those mentioned in the section of the innermost layer hard polymer (a) can be used.
  • the polyfunctional grafting agent used here is used to chemically bond the soft layer polymer (b) and the outermost hard layer polymer (c), and the proportion used during the innermost hard layer polymerization is impact resistance. From the viewpoint of the effect of imparting properties, 0.5 to 5% by mass is preferable.
  • polyfunctional crosslinking agent generally known crosslinking agents such as divinyl compounds, diallyl compounds, diacrylic compounds, dimethacrylic compounds and the like can be used, but polyethylene glycol diacrylate (molecular weight 200 to 600) is preferably used.
  • the polyfunctional cross-linking agent used here is used to generate a cross-linked structure during the polymerization of the soft layer (b) and to exhibit the effect of imparting impact resistance.
  • the polyfunctional crosslinking agent is not an essential component because the crosslinked structure of the soft layer (b) is generated to some extent. Is preferably 0.01 to 5% by weight from the viewpoint of imparting impact resistance.
  • the outermost hard layer polymer (c) constituting the multi-layer structure acrylic granular composite has a methyl methacrylate of 80 to 99 mass in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). % And a monomer mixture comprising 1 to 20% by mass of an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is preferred.
  • the acrylic alkylate those described above are used, but methyl acrylate and ethyl acrylate are preferably used.
  • the proportion of the alkyl acrylate unit in the outermost hard layer (c) is preferably 1 to 20% by mass.
  • an alkyl mercaptan or the like can be used as a chain transfer agent to adjust the molecular weight for the purpose of improving the compatibility with the acrylic resin (A).
  • the outermost hard layer with a gradient such that the molecular weight gradually decreases from the inside toward the outside in order to improve the balance between elongation and impact resistance.
  • the monomer mixture for forming the outermost hard layer is divided into two or more, and the molecular weight is increased from the inside by a method of sequentially increasing the amount of chain transfer agent added each time. It is possible to make it smaller toward the outside.
  • the molecular weight formed at this time can also be examined by polymerizing the monomer mixture used each time under the same conditions, and measuring the molecular weight of the obtained polymer.
  • the particle diameter of the acrylic granular composite which is a multilayer structure polymer preferably used in the present invention is not particularly limited, but is preferably 10 nm or more and 1000 nm or less, and more preferably 20 nm or more and 500 nm or less. More preferably, it is most preferably 50 nm or more and 400 nm or less.
  • the mass ratio of the core and the shell is not particularly limited, but when the entire multilayer structure polymer is 100 parts by mass,
  • the core layer is preferably 50 parts by mass or more and 90 parts by mass or less, and more preferably 60 parts by mass or more and 80 parts by mass or less.
  • Examples of such commercially available multilayered acrylic granular composites include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., “Kane Ace” manufactured by Kaneka Chemical Co., Ltd., “Paralloid” manufactured by Kureha Chemical Co., Ltd., Rohm and Haas “Acryloid” manufactured by KK, “Staffyroid” manufactured by Ganz Kasei Kogyo Co., Ltd., “Parapet SA” manufactured by Kuraray Co., Ltd., and the like can be used alone or in combination.
  • acrylic particles (c-1) which are graft copolymers preferably used as the acrylic particles (C) preferably used in the present invention include unsaturated carboxylic acids in the presence of a rubbery polymer.
  • a monomer mixture comprising an acid ester monomer, an unsaturated carboxylic acid monomer, an aromatic vinyl monomer, and, if necessary, other vinyl monomers copolymerizable therewith A polymerized graft copolymer may be mentioned.
  • the rubbery polymer used for the acrylic particles (c-1) as the graft copolymer is not particularly limited, but diene rubber, acrylic rubber, ethylene rubber, and the like can be used. Specific examples include polybutadiene, styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer.
  • the acrylic resin (A) and the acrylic particles (C) have similar refractive indexes because the transparency of the acrylic resin-containing film of the present invention can be obtained.
  • the refractive index difference between the acrylic particles (C) and the acrylic resin (A) is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less.
  • a method of adjusting the monomer unit composition ratio of the acrylic resin (A) and / or a rubbery polymer or monomer used for the acrylic particles (C) The difference in refractive index can be reduced by a method of adjusting the composition ratio, and an acrylic resin-containing film excellent in transparency can be obtained.
  • the difference in refractive index referred to here is a solution in which the acrylic resin-containing film of the present invention is sufficiently dissolved in a solvent in which the acrylic resin (A) is soluble to obtain a cloudy solution, which is subjected to an operation such as centrifugation.
  • the measured refractive index 23 ° C., measurement wavelength: 550 nm.
  • the method of blending the acrylic particles (C) with the acrylic resin (A) is not particularly limited. After the acrylic resin (A) and other optional components are previously blended, usually at 200 to 350 ° C. A method of uniformly melt-kneading with a single-screw or twin-screw extruder while adding acrylic particles (C) is preferably used.
  • a solution in which acrylic particles (C) are dispersed in advance is added to and mixed with a solution (dope solution) in which acrylic resin (A) and cellulose ester resin (B) are dissolved, acrylic particles (C) and A method such as in-line addition of a solution obtained by dissolving or mixing other optional additives can be used.
  • acrylic particles can also be used as the acrylic particles of the present invention.
  • metabrene W-341 (manufactured by Mitsubishi Rayon Co., Ltd.)
  • Chemisnow MR-2G (C3)
  • MS-300X (manufactured by Soken Chemical Co., Ltd.) and the like can be mentioned.
  • the acrylic resin-containing film of the present invention preferably contains 0.5 to 45% by mass of acrylic particles (C) with respect to the total mass of the resin constituting the film.
  • a plasticizer can be used in combination in order to improve the fluidity and flexibility of the composition.
  • the plasticizer include phthalate ester, fatty acid ester, trimellitic ester, phosphate ester, polyester, and epoxy.
  • polyester-based and phthalate-based plasticizers are preferably used.
  • Polyester plasticizers are superior in non-migration and extraction resistance compared to phthalate ester plasticizers such as dioctyl phthalate, but are slightly inferior in plasticizing effect and compatibility.
  • the polyester plasticizer is a reaction product of a monovalent or tetravalent carboxylic acid and a monovalent or hexavalent alcohol, and is mainly obtained by reacting a divalent carboxylic acid with a glycol.
  • Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like.
  • glycol examples include glycols such as ethylene, propylene, 1,3-butylene, 1,4-butylene, 1,6-hexamethylene, neopentylene, diethylene, triethylene, and dipropylene. These divalent carboxylic acids and glycols may be used alone or in combination.
  • the ester plasticizer may be any of ester, oligoester and polyester types, and the molecular weight is preferably in the range of 100 to 10000, but preferably in the range of 600 to 3000, the plasticizing effect is large.
  • the viscosity of the plasticizer has a correlation with the molecular structure and molecular weight, but in the case of an adipic acid plasticizer, the range of 200 to 5000 mPa ⁇ s (25 ° C.) is preferable because of compatibility and plasticization efficiency. Furthermore, some polyester plasticizers may be used in combination.
  • the plasticizer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the composition containing the acrylic resin (A). If the added amount of the plasticizer exceeds 30 parts by mass, the surface becomes sticky, which is not preferable for practical use.
  • the composition containing the acrylic resin (A) of the present invention preferably contains an ultraviolet absorber, and examples of the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
  • the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
  • benzotriazole 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3 Triazoles such as 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone And benzophenones.
  • ultraviolet absorbers having a molecular weight of 400 or more are less likely to volatilize at a high boiling point and are difficult to disperse even during high-temperature molding, so that the weather resistance is effectively improved with a relatively small amount of addition. be able to.
  • the UV absorber does not easily migrate from the inside of the film to the thin coating layer and is difficult to deposit on the surface, the amount of the UV absorber contained is maintained for a long time, and the durability of the weather resistance improvement effect is maintained. It is preferable from the point of being excellent.
  • Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( Hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Such as til] -4- [3- (3,5-di-tert-butyl
  • 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3- Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.
  • antioxidants can be added to the acrylic resin (A) used in the acrylic resin-containing film of the present invention in order to improve the thermal decomposability and thermal colorability during molding.
  • an antistatic agent can be added to impart antistatic performance to the acrylic resin-containing film.
  • a flame retardant acrylic resin composition containing a phosphorus flame retardant may be used.
  • Phosphorus flame retardants used here include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonate compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphorus. Examples thereof include one or a mixture of two or more selected from acid esters, halogen-containing condensed phosphates, halogen-containing condensed phosphonates, halogen-containing phosphites, and the like.
  • triphenyl phosphate 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris ( ⁇ -chloroethyl) phosphate, tris (dichloropropyl) Examples thereof include phosphate and tris (tribromoneopentyl) phosphate.
  • the acrylic resin-containing film of the present invention is characterized by having at least one curable resin layer.
  • This curable resin layer exhibits an improvement effect not only on the surface hardness but also on brittleness, particularly flex resistance.
  • the curable resin layer of the present invention may be a single layer or two or more layers depending on the degree of use. From the point of productivity, it is preferable that it is 1 layer or more and 4 layers or less. Moreover, you may provide on both surfaces of an acrylic resin film.
  • the refractive index of the transparent resin constituting the curable resin layer of the present invention is preferably 1.47 or more, more preferably 1.47 to 1.70.
  • the type and amount ratio of the transparent resin may be selected as appropriate. If the refractive index is less than 1.47, it is difficult to obtain a resin with high hardness. If the refractive index is greater than 1.70, unevenness of the film tends to be noticeable.
  • the refractive index of the transparent resin can be quantitatively evaluated by, for example, directly measuring with an Abbe refractometer at 23 ° C. or measuring a spectral reflection spectrum or spectral ellipsometry.
  • the curable resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain.
  • the curable resin a resin that is cured by heat or actinic radiation can be used, and a resin that is cured by a crosslinking reaction or the like by actinic radiation such as ultraviolet rays or electron beams is particularly preferable.
  • the curable resin examples include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin.
  • the ultraviolet curable acrylate resin is preferably used.
  • the UV curable urethane acrylate resin generally contains 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate as methacrylate) obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It is easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate.
  • JP-A-59-151110 can be used.
  • a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.
  • UV curable polyester acrylate resins include those that are easily formed by reacting polyester polyols with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, generally as disclosed in JP-A-59-151112. Those described in the publication can be used.
  • ultraviolet curable epoxy acrylate resin examples include those produced by reacting epoxy acrylate with an oligomer, a reactive diluent and a photopolymerization initiator added thereto. Those described in Japanese Patent No. 105738 can be used.
  • UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.
  • photopolymerization initiators for these curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.
  • a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.
  • the photopolymerization initiator or photosensitizer used in the curable resin composition is 0.1 to 25 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the composition.
  • acrylate resins include methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyl dimethyl adiacrylate , Trimethylolpropane triacrylate, pentaerythritol tetraacrylic ester and the like.
  • Adekaoptomer KR / BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka Co., Ltd.); -101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG -1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20, DP -30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo); KRM7033, KRM70 9, KRM 7130, KRM 7131, UV
  • trimethylolpropane triacrylate ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dioxane glycol acrylate, ethoxylated acrylate, alkyl-modified dipentaerythritol pentaacrylate, etc.
  • trimethylolpropane triacrylate ditrimethylolpropane tetraacrylate
  • pentaerythritol triacrylate pentaerythritol tetraacrylate
  • dipentaerythritol hexaacrylate dioxane glycol acrylate
  • ethoxylated acrylate alkyl-modified dipentaerythritol pentaacrylate, etc.
  • the curable resin layer of the present invention may contain particles in order to impart antiglare properties. That is, it may have a function as an antiglare hard coat layer.
  • a transparent resin for example, a binder layer mainly composed of an active energy ray curable resin can contain particles having an average particle size of 0.5 to 6 ⁇ m, but preferably has a structure containing fluorine-containing acrylic resin particles. . Further, particles having an average particle diameter of 0.01 to 1.0 ⁇ m may be further contained.
  • the fluorine-containing acrylic resin particles of the present invention are, for example, particles formed from a fluorine-containing acrylic ester or methacrylic ester polymer.
  • fluorine-containing acrylic acid esters or methacrylic acid esters include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H- Dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2-perfluorodecylethyl
  • fluorine-containing acrylic resin particles particles made of 2- (perfluorobutyl) ethyl- ⁇ -fluoroacrylate, fluorine-containing polymethyl methacrylate particles, and fluorine-containing methacrylic acid in the presence of a crosslinking agent are vinyl monomers. Particles copolymerized with are preferred, and fluorine-containing polymethyl methacrylate particles are more preferred.
  • a vinyl monomer copolymerizable with a fluorine-containing (meth) acrylic acid ester may be copolymerized.
  • These may be those having a vinyl group, specifically, methacrylic acid alkyl esters such as methyl methacrylate and butyl methacrylate, alkyl acrylates such as methyl acrylate and ethyl acrylate, styrene, ⁇ -Styrenes such as methylstyrene can be used, and these can be used alone or in combination.
  • the crosslinking agent used in the polymerization reaction is not particularly limited, but those having two or more unsaturated groups are preferably used.
  • bifunctional dimethacrylates such as ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate are used.
  • the polymerization reaction for producing the fluorine-containing polymethyl methacrylate particles may be either random copolymerization or block copolymerization. Specifically, for example, the method described in JP-A No. 2000-169658 can also be mentioned.
  • state of these fluorine-containing acrylic resin particles may be added in any state such as powder or emulsion.
  • fluorine-containing crosslinked particles described in paragraphs 0028 to 0055 of JP-A-2004-83707 may be used.
  • the refractive index of the fluorine-containing acrylic resin particles of the present invention is preferably 1.38 to 1.46.
  • the content of the fluorine-containing acrylic resin particles of the present invention is preferably 0.01 to 500 parts by weight, more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the transparent resin constituting the antiglare hard coat layer. Part by mass, particularly preferably 1 to 60 parts by mass.
  • the average particle size of the fluorine-containing acrylic resin particles of the present invention is 0.5 to 6 ⁇ m, preferably 0.55 to 4.0 ⁇ m.
  • the average particle diameter was taken with a scanning electron micrograph of the particles (1000 particles or more), and the diameter of the particles shown in this photograph was 100 using an image processing device LUZEX-III (manufactured by Nireco). The average value was measured and the average value was calculated.
  • examples of the particles preferably having an average particle size of 0.01 to 1 ⁇ m that are contained in the present invention include acrylic particles and inorganic particles mainly composed of silica.
  • silica particles examples include trade names such as Nippon Aerosil Co., Ltd., Aerosil 200, 200V, 300, Degussa, Aerosil OX50, TT600, etc., Nippon Shokubai Co., Ltd., KEP-10, KEP-50, KEP-100 and the like.
  • colloidal silica may be used. Colloidal silica is obtained by dispersing silicon dioxide in water or an organic solvent in a colloidal form, and is not particularly limited, and is spherical, acicular or beaded.
  • colloidal silica is commercially available, and examples thereof include the Snow-Tex series from Nissan Chemical Industries, the Cataloid-S series from Catalytic Chemical Industries, and the Rebacil series from Bayer.
  • colloidal silica cation-modified with alumina sol or aluminum hydroxide, or bead-like colloidal silica in which primary particles of silica are connected with each other with metal ions having a valence of 2 or more and connected in a bead shape is also preferably used.
  • beaded colloidal silica examples include Snowtex-AK series, Snowtex-PS series, Snowtex-UP series, etc., manufactured by Nissan Chemical Industries, Ltd. Specifically, IPS-ST-L (isopropanol silica sol, particle size 40-50 nm) , Silica concentration 30%), MEK-ST-MS (methyl ethyl ketone silica sol, particle size 17-23 nm, silica concentration 35%), etc.
  • MEK-ST methyl ethyl ketone silica sol, particle size 10-15 nm, silica concentration 30%
  • MEK- ST-L methyl ethyl ketone silica sol, particle diameter 40 to 50 nm, silica concentration 30%
  • MEK-ST-UP methyl ethyl ketone silica sol, particle diameter 9 to 15 nm (chain structure), silica concentration 20%
  • acrylic particles examples include fluorine-containing acrylic resin particles.
  • Nippon Paint S-4000 and FS-701.
  • acrylic-styrene particles examples include Nippon Paint: S-1200, MG-251. .
  • fluorine-containing acrylic resin particles are preferable.
  • the particles having an average particle diameter of 0.01 to 1 ⁇ m constitute the antiglare cured resin layer as the content thereof from the stability of the coating liquid forming the antiglare cured resin layer and the dispersibility of the dispersion.
  • the amount is preferably 0.01 to 500 parts by weight, more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the transparent resin.
  • the content ratio with the particles having an average particle diameter of 0.01 to 1 ⁇ m can be appropriately selected within the range of 0 to 500 mass% with respect to the particles having an average particle diameter of 1.5 to 6 ⁇ m.
  • the particles may be added in any state such as powder or emulsion.
  • the density of the translucent particles is preferably 10 to 1000 mg / m 2 , more preferably 100 to 700 mg / m 2 .
  • ⁇ Other substances contained in the antiglare cured resin layer other organic particles include silicone resin powder, polystyrene resin powder, polycarbonate resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or poly An ultraviolet curable resin composition such as an ethylene fluoride resin powder can also be added.
  • the refractive index of the other particles is preferably 1.45 to 1.70, more preferably 1.45 to 1.65.
  • the refractive index of the particles is measured by measuring the turbidity by dispersing the same amount of particles in a solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes.
  • the refractive index of the solvent can be measured by measuring with an Abbe refractometer.
  • the antiglare curable resin layer preferably contains the following silicone surfactant, fluorine compound, polyoxyether compound or the like as the surfactant.
  • fluorine-based compound is a fluoroaliphatic group-containing copolymer, and specifically, it can be used in the compounds and description methods described in paragraphs 0053 to 0082 of JP-A-2007-45142.
  • a copolymer polymer obtained by grafting siloxane (including polysiloxane) and / or organosiloxane (including organopolysiloxane) to a fluororesin can also be preferably used.
  • ZX-022H, ZX-007C, ZX-049, ZX-047-D manufactured by Fuji Kasei Kogyo Co., Ltd. can be exemplified. These compounds may be used as a mixture.
  • Emulgen 1108 Emulgen 1118S-70
  • commercially available products of polyoxyethylene lauryl ether include Emulgen 103, Emulgen 104P, Emulgen 105, and Emulgen 106.
  • Emulgen 108P, Emulgen 109P, Emulgen 120P, Emulgen 123P, Emulgen 147, Emulgen 150, Emulgen 130K (above, manufactured by Kao Corporation), polyoxyethylene cetyl ether as commercially available products, Emulgen 210P, Emulgen 220 (above, As a commercial product of polyoxyethylene stearyl ether), Emulgen 220, Emulgen 306P (above, manufactured by Kao Corporation), polyoxyalkylene alkyl ether
  • Emulgen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen MS-110 (manufactured by Kao Corporation) polyoxyethylene higher alcohol ethers are commercially available: Emulgen 705, Emulgen 707 , Emulgen 709 and the like.
  • Polyoxyether compounds may be used alone or in combination of two or more. Moreover, you may use together an acetylene glycol type compound, a nonionic surfactant, a radically polymerizable nonionic surfactant, etc.
  • the antiglare cured resin layer may contain a color tone adjusting agent (dye or pigment, etc.) having a color tone adjusting function as a color correction filter for various display elements.
  • a color tone adjusting agent die or pigment, etc.
  • an electromagnetic wave blocking agent or an infrared absorbing agent may be included to have each function.
  • the antiglare cured resin layer may contain other functional thiol compounds as curing aids, such as 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate). 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.
  • functional thiol compounds such as curing aids, such as 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate). 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.
  • the other functional thiol compound is preferably added in the range of 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, with respect to 100 parts by mass of the active energy ray curable resin.
  • the antiglare cured resin layer is made of titanium, zirconium, aluminum, indium, zinc, tin, antimony in addition to the organic particles of the present invention in order to improve hardness, prevent static charge, and adjust the refractive index of the layer.
  • the main component is an oxide of at least one metal selected from among them, and the average particle size is 10 ⁇ m or less, for example, 2 ⁇ m or less, preferably 0.2 ⁇ m or less, particularly preferably 0.1 ⁇ m or less, more preferably 0.06 ⁇ m or less. You may contain the inorganic particle which is.
  • titanium and zirconium are preferable.
  • the surface of the inorganic particles used in the antiglare hard coat layer is preferably subjected to silane coupling treatment or titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
  • the surface treatment agent can be used by mixing it in the coating composition without coupling treatment in advance.
  • the addition amount is preferably 10 to 90% of the total mass of the antiglare hard coat layer, more preferably 20 to 80%, particularly preferably 30 to 75%. It is.
  • Such inorganic particles have a particle size sufficiently smaller than the wavelength of light and therefore do not scatter, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.
  • production methods such as an 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. From the viewpoints of suppressing foreign matter defects and optical defects such as die lines, solution casting by casting is preferred.
  • Organic solvent useful for forming the dope when the acrylic resin-containing film of the present invention is produced by the solution casting method dissolves the acrylic resin (A), the cellulose ester resin (B), and other additives at the same time. Anything can be used without limitation.
  • 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, etc.
  • Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.
  • the dope preferably contains 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.
  • the ratio of alcohol in the dope increases, the web gels and peeling from the metal support becomes easy.
  • acrylic resin (A) and cellulose ester in non-chlorine organic solvent system There is also a role of promoting dissolution of the resin (B).
  • an acrylic resin (A), a cellulose ester resin (B), and acrylic particles (C) 3 A dope composition in which at least 15 to 45% by mass of the seed is dissolved is 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.
  • 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
  • Various dissolution methods such as a method of performing a cooling dissolution method as described in JP-A-9-95557 or JP-A-9-95538, a method of performing at a high pressure as described in JP-A-11-21379, and the like.
  • a method in which pressure is applied at a temperature equal to or higher than the boiling point of the main solvent is particularly preferable.
  • the acrylic resin (A) and cellulose ester resin (B) in the dope are preferably in the range of 15 to 45% by mass in total.
  • An additive is added to the dope during or after dissolution to dissolve and disperse, then filtered through a filter medium, defoamed, and sent to the next step with a liquid feed pump.
  • a filter medium having a collected particle diameter of 0.5 to 5 ⁇ m and a drainage time of 10 to 25 sec / 100 ml.
  • agglomerates remaining at the time of particle dispersion and agglomerates generated upon addition of the main dope are only aggregated by using a filter medium having a collected particle diameter of 0.5 to 5 ⁇ m and a drainage time of 10 to 25 sec / 100 ml. Can be removed.
  • the concentration of particles is sufficiently thinner than that of the additive solution, so that aggregates do not stick together at the time of filtration and the filtration pressure does not increase suddenly.
  • FIG. 1 is a diagram schematically showing a dope preparation step, a casting step, and a drying step of a solution casting film forming method preferable for the present invention.
  • the main dope solution is filtered by the main filter 3, and an ultraviolet absorbent additive solution is added in-line from 16 to this.
  • the main dope may contain about 10 to 50% by weight of recycled material.
  • the return material may contain acrylic particles. In that case, it is preferable to control the addition amount of the acrylic particle addition liquid in accordance with the addition amount of the return material.
  • the additive solution containing acrylic particles preferably contains 0.5 to 10% by mass of acrylic particles, more preferably 1 to 10% by mass, and more preferably 1 to 5% by mass. Most preferably.
  • Recycled material is a finely pulverized acrylic resin-containing film that is generated when an acrylic resin-containing film is formed.
  • the original fabric is used.
  • an acrylic resin, a cellulose ester resin, and in some cases, acrylic particles kneaded into pellets can be preferably used.
  • An endless metal belt 31 such as a stainless steel belt or a rotating metal drum, which feeds the dope through a liquid feed pump (for example, a pressurized metering gear pump) to the pressure die 30 and transfers it infinitely. This is a step of casting the dope from the pressure die slit to the casting position on the support.
  • a liquid feed pump for example, a pressurized metering gear pump
  • the pressure die includes 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 residual solvent amount at the time of peeling of the web on the metal support at the time of peeling is preferably peeled in the range of 50 to 120% by mass depending on the strength of drying conditions, the length of the metal support, and the like.
  • the amount of residual 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 from 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 alternately conveys the web through a plurality of rolls arranged in the drying device and / or a tenter stretching device 34 that clips and conveys both ends of the web with a clip are used. 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, drying is generally performed at 40-250 ° C. In particular, drying at 40 to 160 ° C. is preferable.
  • tenter stretching apparatus When using a tenter stretching apparatus, it is preferable to use an apparatus capable of independently controlling the film gripping length (distance from the start of gripping to the end of gripping) by the left and right gripping means of the tenter. In the tenter process, it is also preferable to intentionally create sections 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 150 ° C, more preferably 50 to 120 ° C, and most preferably 70 to 100 ° 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 step This is a step of winding up the acrylic resin-containing film by the winder 37 after the residual solvent amount in the web is 2% by mass or less, and by setting the residual solvent amount to 0.4% by mass or less. A film having good dimensional stability can be obtained.
  • 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 acrylic resin-containing film of the present invention is preferably a long film. Specifically, the acrylic resin-containing film is about 100 m to 5000 m, and is usually in the form of a roll.
  • the film width is preferably 1.3 to 4 m, more preferably 1.4 to 2 m.
  • the film thickness of the acrylic resin-containing film of the present invention is not particularly limited, but when used for a polarizing plate protective film described later, it is preferably 20 to 200 ⁇ m, more preferably 25 to 100 ⁇ m, and 30 to 80 ⁇ m. It is particularly preferred that ⁇ Method for producing cured resin layer>
  • the cured resin layer is coated by applying a coating composition for forming the cured resin layer on the acrylic-containing resin film using a known method such as a gravure coater, dip coater, reverse coater, wire bar coater, die coater, and inkjet method. Then, it is preferable to heat-dry and to perform UV curing treatment.
  • the coating amount is suitably 0.1 to 40 ⁇ m, preferably 0.5 to 30 ⁇ m, as the wet film thickness.
  • the dry film thickness is an average film thickness of 0.1 to 30 ⁇ m, preferably 1 to 20 ⁇ m. Within this range, lack of hardness, deterioration of curling and brittleness, and deterioration of workability are prevented.
  • any light source that generates ultraviolet rays can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • the irradiation conditions vary depending on individual lamps, irradiation of active rays, usually 5 ⁇ 500mJ / cm 2, preferably 5 ⁇ 150mJ / cm 2.
  • irradiating active rays when irradiating active rays, it is preferably performed while applying tension in the film transport direction, more preferably while applying tension in the width direction.
  • the tension to be applied is preferably 30 to 300 N / m.
  • the method for applying tension is not particularly limited, and tension may be applied in the conveying direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.
  • the coating composition for forming the antiglare hard coat layer may contain a solvent.
  • the organic solvent contained in the coating composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). , Esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents may be appropriately selected or mixed for use.
  • the organic solvent propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is preferable.
  • the content of the organic solvent is preferably 5 to 80% by mass in the coating composition.
  • the polarizing plate used in the present invention can be produced by a general method. It is preferable that an adhesive layer is provided on the side opposite to the curable resin layer of the acrylic resin-containing film of the present invention, and is bonded to at least one surface of a polarizer produced by immersion and stretching in an iodine solution.
  • the film may be used on the other surface, or another polarizing plate protective film may be used.
  • cellulose ester films for example, Konica Minoltack KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KV8UY-HA, KV8UX-RHA, KV8UX-RHA Etc.
  • cellulose ester films for example, Konica Minoltack KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KV8UY-HA, KV8UX-RHA, KV8UX-RHA Etc.
  • a polarizer which is a main component of a polarizing plate, is an element that transmits only light having a plane of polarization in a certain direction.
  • a typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol. There are one in which 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 Pa to 1.0 ⁇ 10 Pa in at least a part of the pressure-sensitive adhesive layer is preferably used.
  • a curable pressure-sensitive adhesive that forms a high molecular weight body or a crosslinked structure by various chemical reactions after applying and bonding the pressure-sensitive adhesive is suitably used.
  • 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 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 solvent type.
  • the 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.
  • ⁇ Liquid crystal display device> By incorporating the polarizing plate bonded with the acrylic resin-containing film of the present invention into a liquid crystal display device, various liquid crystal display devices with excellent visibility can be produced.
  • 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 type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. Preferably used.
  • a large-screen display device having a screen of 30 or more, especially 30 to 54 there is no white spot at the periphery of the screen and the effect is maintained for a long time.
  • Example 1 The following acrylic resins A1-A5 were produced by a known method.
  • a methyl methacrylate / acrylamide copolymer suspension was prepared as follows.
  • the above was charged into the reactor and the reactor was replaced with nitrogen gas.
  • the reaction was allowed to proceed at 70 ° C. until converted to coalescence.
  • the obtained aqueous solution was used as a suspending agent.
  • a solution in which 0.05 part by mass of the above suspending agent is dissolved in 165 parts by mass of ion-exchanged water is supplied to a stainless steel autoclave having a capacity of 5 liters and equipped with a baffle and a foudra-type stirring blade, and the system is filled with nitrogen gas. It stirred at 400 rpm, replacing.
  • Methacrylic acid 27 parts by weight Methyl methacrylate 73 parts by weight t-dodecyl mercaptan 1.2 parts by weight 2,2′-azobisisobutyronitrile 0.4 part by weight
  • the temperature was raised to 70 ° C. and the internal temperature was 70 The time when the temperature reached 0 ° C. was set as the polymerization start time, and the polymerization was allowed to proceed for 180 minutes.
  • the reaction system was cooled, the polymer was separated, washed, and dried according to the usual method to obtain a bead-shaped copolymer.
  • the polymerization rate of this copolymer was 97%, and the weight average molecular weight was 130,000.
  • Formation of acrylic resin film 1 The produced dope solution 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 solvent was evaporated from the peeled acrylic resin web at 35 ° C., slit to 1.6 m width, and then dried at a drying temperature of 135 ° C. while stretching 1.1 times in the width direction with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 10%.
  • 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 acrylic resin-containing film 1 described in Tables 1 and 2 was 0.1%, the film thickness was 60 ⁇ m, and the winding length was 4000 m.
  • acrylic resin-containing films were prepared in the same manner as the acrylic resin-containing film 1 except that the types and composition ratios of the acrylic resin (A) and the cellulose ester resin (B) were changed as shown in Tables 1 and 2. Produced.
  • Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 0.7 parts by weight 11: LA-31 (manufactured by ADEKA) 1.5 parts by mass Part
  • p represents a propionyl group
  • b represents a butyryl group
  • bz represents a benzoyl group
  • ph represents a phthalyl group.
  • acrylic resin film 34 a sample formed by a melt casting method was produced by a usual method as described below.
  • Acrylic resin Dianal BR85 (manufactured by Mitsubishi Rayon Co., Ltd.) and CAP482-20 (manufactured by Eastman Chemical Co., Ltd.) are mixed at a ratio of 70:30, and 2 at 90 ° C. using a hot air dryer in which air is circulated. After drying for a long time and sufficiently removing moisture, a T-die film melt extrusion machine (T-die width 500 mm) having a resin melt kneader equipped with a 65 mm ⁇ screw was used. An acrylic resin film 34 was formed by extrusion under molding conditions of a temperature of 240 ° C. The formed film had a thickness of 60 ⁇ m.
  • a hard coat layer which is the following curable resin layer, was provided on the acrylic resin-containing film, and a back coat layer was provided on the back surface to prepare an example sample and a comparative example sample.
  • the acrylic resin film is die-coated with the hard coat layer coating composition 1 and dried at 80 ° C., and then irradiated with 0.30 J / cm 2 of ultraviolet light with a high-pressure mercury lamp so that the film thickness after curing becomes 5 ⁇ m. A hard coat layer was applied.
  • the refractive index of only the transparent resin was 1.49.
  • the following coating solution 1 for back coat layer is die-coated so as to have a wet film thickness of 6 ⁇ m, a back coat layer is provided, a hard coat layer on the cellulose ester film, A hard coat film example sample provided with a back coat layer was prepared.
  • Particle 1 Particle A 5 parts by mass
  • Particle 2 Particle B 20 parts by mass
  • Other particles used in Examples and Comparative Examples are as follows.
  • Particle A Fluorine-containing polymethyl methacrylate particles (F-191 average particle diameter 0.55 ⁇ m, refractive index 1.42 manufactured by Nippon Paint Co., Ltd.)
  • Particle B Silica particle (Seahoster KE-P100, average particle size 1.10 ⁇ m, refractive index 1.43, manufactured by Nippon Shokubai Co., Ltd.)
  • Sample 35 Comparative Example, the hard coat layer and the following back coat layer were not applied to the acrylic resin film sample 1.
  • Example 1 (Coating composition 1 for back coat layer) Acetone 30 parts by weight Ethyl acetate 45 parts by weight Isopropyl alcohol 10 parts by weight Diacetylcellulose 0.6 part by weight Silica particles having an average particle diameter of 16 nm 2% acetone dispersion 0.2 part by weight
  • JP 2007-191706 A was implemented.
  • a thermoplastic copolymer described in Example 1 was prepared, a pellet composition according to Example 7 was prepared, and a comparative sample film 37 having a thickness of 60 ⁇ m was obtained in the same manner as in Example 34 of the present application.
  • An acrylic resin-containing film conditioned for 24 hours in an air-conditioned room at 23 ° C. and 55% RH is cut out at 120 mm (length) ⁇ 10 mm (width) and heated at a rate of temperature increase of 30 ° C./min while being pulled with a tension of 10 N. Then, the temperature at 9 N was measured three times, and the average was obtained.
  • the tearing surface is very smooth and is torn straight.
  • Dimensional change rate (%) [(a1-a2) / a1] ⁇ 100 a1: Distance before heat treatment a2: Distance after heat treatment ⁇ ⁇ ⁇ ⁇ less than 0.3% ⁇ ⁇ ⁇ ⁇ 0.3 to 0.5% ⁇ ... 0.5% ⁇ The following evaluation was implemented about the acrylic resin containing film sample and comparative sample which provided the obtained hard-coat layer.
  • the transparent film was examined under the conditions of 23 ° C. and 55% RH for the minimum bending diameter at which two or more of the three samples were not cracked when the cured resin layer was inside, and evaluated according to the following criteria.
  • a pencil with a known hardness is applied to the sample with a pencil hardness tester (HA-301, Clemens type scratch hardness tester, Tester Sangyo Co., Ltd.) was scratched with a load of 1 kg and visually evaluated for the presence or absence of scratches.
  • a pencil hardness tester HA-301, Clemens type scratch hardness tester, Tester Sangyo Co., Ltd.
  • 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 form a polarizing film.
  • KC8UCR-5 manufactured by Konica Minolta Opto Co., Ltd., which is a retardation film subjected to alkali saponification treatment, was bonded to the other surface of the polarizing film and dried to prepare a polarizing plate P.
  • the polarizing plate using the acrylic resin-containing film of the present invention was excellent in film cutting property and easy to process.
  • the viewing angle of the liquid crystal display device was measured using EZ-Contrast 160D manufactured by ELDIM in an environment of 23 ° C. and 55% RH. Subsequently, the polarizing plate treated at 60 ° C. and 90% RH for 1000 hours was measured in the same manner, and evaluated according to the following criteria in four stages.
  • the acrylic resin film of the present invention heat resistance as an optical film is improved, and not only film deformation and cutting properties but also bending resistance and hardness are improved.
  • the polarizing plate produced using the acrylic resin containing film of this invention and a liquid crystal display device show the characteristic excellent in visibility and a color shift.
  • Example 2 Preparation of acrylic particles (C1)> A reactor with a reflux condenser with an internal volume of 60 liters was charged with 38.2 liters of ion-exchanged water and 111.6 g of sodium dioctylsulfosuccinate, and the temperature was raised to 75 ° C. under a nitrogen atmosphere while stirring at a rotational speed of 250 rpm. The effect of oxygen was virtually eliminated. 0.36 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of 1657 g of MMA, 21.6 g of BA, and 1.68 g of ALMA was added all at once. Completed.
  • a small amount of the polymer latex thus obtained was collected, and the flat particle size was determined by the absorbance method, which was 0.10 ⁇ m.
  • the remaining latex was put into a 3% by mass sodium sulfate warm aqueous solution, salted out and coagulated, and then dried after repeated dehydration and washing to obtain acrylic particles (C1) having a three-layer structure.
  • acrylic resin-containing film 25 described in Example 1 except that the acrylic resin (A), the cellulose ester resin (B), the acrylic particles (C), and the composition ratio were changed as shown in Table 5. Similarly, acrylic resin-containing films 25-1 to 25-6 were produced.
  • the acrylic resin-containing film 25-5 was prepared by adding the following ultraviolet absorber.
  • Tinuvin 109 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass Tinuvin 171 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.7 parts by mass
  • the acrylic resin-containing film 25-4 is replaced with C2 instead of acrylic particles C1.
  • METABLEN W-341 (manufactured by Mitsubishi Rayon Co., Ltd.), acrylic resin-containing film 25-5 as single-layer MR-2G (manufactured by Soken Chemical Co., Ltd.) as C3, acrylic resin-containing film 25-6 as MS-300X ( Soken Chemical Co., Ltd.) was used as C4.
  • Example 1 The hard coat layer described in Example 1 was applied to the acrylic resin film in the same manner as in Example 1.
  • the polarizing plate and the liquid crystal display device produced using the acrylic resin-containing film containing the particles of the present invention showed further excellent properties in visibility and color shift.

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  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
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  • Polymers & Plastics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne un film contenant une résine acrylique transparent, qui est très résistant à la chaleur et qui est remarquablement amélioré en termes de fragilité. Elle concerne également une plaque polarisante employant ce film contenant une résine acrylique, dont les caractéristiques optiques et les propriétés physiques, telles que les propriétés de découpage, sont améliorées, et un dispositif d'affichage à cristaux liquides. Elle concerne spécifiquement un film contenant une résine acrylique qui se caractérise en ce qu'il contient au moins une couche de résine durcissable et présente une valeur de voile inférieure à 1 % et un point de ramollissement en tension de 105-145 ˚C. Ce film contenant une résine acrylique se caractérise également en ce qu'il est exempt de fracture ductile.
PCT/JP2008/067920 2007-12-28 2008-10-02 Film contenant une résine acrylique, plaque polarisante l'utilisant et dispositif d'affichage WO2009084295A1 (fr)

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JP2009179731A (ja) * 2008-01-31 2009-08-13 Konica Minolta Opto Inc アクリル樹脂含有フィルム、それを用いた偏光板及び表示装置
JP2009227735A (ja) * 2008-03-19 2009-10-08 Fujifilm Corp 防眩性フィルム及びその製造方法
WO2009150910A1 (fr) * 2008-06-10 2009-12-17 コニカミノルタオプト株式会社 Procédé pour produire un film acrylique et film acrylique produit par le procédé de production
WO2011045991A1 (fr) * 2009-10-13 2011-04-21 コニカミノルタオプト株式会社 Film optique
WO2011055590A1 (fr) * 2009-11-04 2011-05-12 コニカミノルタオプト株式会社 Bobine de film protecteur pour plaque de polarisation à cristaux liquides et son procédé de fabrication
JP5463914B2 (ja) * 2008-01-30 2014-04-09 コニカミノルタ株式会社 アクリル樹脂含有フィルム、それを用いた偏光板及び液晶表示装置
JP5521552B2 (ja) * 2008-01-30 2014-06-18 コニカミノルタ株式会社 アクリル樹脂含有フィルム、それを用いた偏光板及び液晶表示装置
JPWO2013035289A1 (ja) * 2011-09-05 2015-03-23 コニカミノルタ株式会社 光学フィルムの製造方法
JP2017097352A (ja) * 2016-12-05 2017-06-01 コニカミノルタ株式会社 光学フィルムおよびその製造方法、並びにこれを用いた偏光板

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KR101498397B1 (ko) * 2010-09-14 2015-03-03 코니카 미놀타 어드밴스드 레이어즈 인코포레이티드 수지 필름, 수지 필름의 제조 방법, 편광판, 및 액정 표시 장치
KR101627975B1 (ko) * 2015-07-20 2016-06-07 주식회사 엘지화학 인성이 우수한 아크릴계 광학 필름 및 이를 포함하는 박형 편광판
JPWO2017104308A1 (ja) * 2015-12-14 2018-09-27 コニカミノルタ株式会社 偏光板及び前記偏光板を含む画像表示装置

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JP5463914B2 (ja) * 2008-01-30 2014-04-09 コニカミノルタ株式会社 アクリル樹脂含有フィルム、それを用いた偏光板及び液晶表示装置
JP5521552B2 (ja) * 2008-01-30 2014-06-18 コニカミノルタ株式会社 アクリル樹脂含有フィルム、それを用いた偏光板及び液晶表示装置
JP2009179731A (ja) * 2008-01-31 2009-08-13 Konica Minolta Opto Inc アクリル樹脂含有フィルム、それを用いた偏光板及び表示装置
JP2009227735A (ja) * 2008-03-19 2009-10-08 Fujifilm Corp 防眩性フィルム及びその製造方法
WO2009150910A1 (fr) * 2008-06-10 2009-12-17 コニカミノルタオプト株式会社 Procédé pour produire un film acrylique et film acrylique produit par le procédé de production
JP5333447B2 (ja) * 2008-06-10 2013-11-06 コニカミノルタ株式会社 アクリルフィルムの製造方法およびその製造方法によって製造したアクリルフィルム
WO2011045991A1 (fr) * 2009-10-13 2011-04-21 コニカミノルタオプト株式会社 Film optique
JP5652401B2 (ja) * 2009-10-13 2015-01-14 コニカミノルタ株式会社 光学フィルム
WO2011055590A1 (fr) * 2009-11-04 2011-05-12 コニカミノルタオプト株式会社 Bobine de film protecteur pour plaque de polarisation à cristaux liquides et son procédé de fabrication
JPWO2013035289A1 (ja) * 2011-09-05 2015-03-23 コニカミノルタ株式会社 光学フィルムの製造方法
JP2017097352A (ja) * 2016-12-05 2017-06-01 コニカミノルタ株式会社 光学フィルムおよびその製造方法、並びにこれを用いた偏光板

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