WO2009090900A1 - Film contenant une résine acrylique et procédé de production du film - Google Patents

Film contenant une résine acrylique et procédé de production du film Download PDF

Info

Publication number
WO2009090900A1
WO2009090900A1 PCT/JP2009/050059 JP2009050059W WO2009090900A1 WO 2009090900 A1 WO2009090900 A1 WO 2009090900A1 JP 2009050059 W JP2009050059 W JP 2009050059W WO 2009090900 A1 WO2009090900 A1 WO 2009090900A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylic resin
film
mass
acrylic
resin
Prior art date
Application number
PCT/JP2009/050059
Other languages
English (en)
Japanese (ja)
Inventor
Takashi Takebe
Masataka Takimoto
Nobuo Kubo
Original Assignee
Konica Minolta Opto, 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 Opto, Inc. filed Critical Konica Minolta Opto, Inc.
Priority to KR1020107015577A priority Critical patent/KR101497751B1/ko
Priority to JP2009550000A priority patent/JPWO2009090900A1/ja
Publication of WO2009090900A1 publication Critical patent/WO2009090900A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0088—Blends of polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0026—Transparent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/14—Mixed esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the present invention relates to an acrylic resin-containing film that is transparent, has high heat resistance, and remarkably improves brittleness, and a method for producing the same.
  • PMMA Polymethyl methacrylate
  • the PMMA film has poor heat resistance and has a problem that its shape changes 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. That is, in the liquid crystal display device, because 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.
  • an acrylic resin is industrially produced by a solution casting film forming method, it is generally cast on a metal base material such as a steel belt as a support, and a film-like material called a web is formed.
  • a method is generally known in which the solvent contained in the web is volatilized to some extent and then peeled off from the support.
  • Patent Document 2 discloses the addition of a release agent, coating treatment on the metal belt surface, etc., but the former may cause the release agent to bleed and impair the appearance, while the latter is produced. There was a problem that the performance decreased. JP-A-5-306344 JP 2007-176982 A
  • the present invention has been made in view of the above-mentioned problems and situations, and a solution to that problem is to provide an acrylic resin-containing film that is transparent, has high heat resistance, and has markedly improved brittleness, and a method for producing the same. .
  • An acrylic resin-containing film containing an acrylic resin as a main constituent, containing an acrylic resin and a cellulose ester resin in a mass ratio of 95: 5 to 30:70, and having a total substitution degree of acyl groups of the cellulose ester resin 2.00 to 2.99, acetyl group substitution degree is 0.10 to 1.89, carbon number of acyl group other than acetyl group is 3 to 7, and weight average molecular weight is 75000 to 280000, An acrylic resin-containing film, wherein the resin-containing film has a haze of less than 1%, a tension softening point of 105 to 145 ° C., and does not cause ductile fracture.
  • the method for producing an acrylic resin-containing film as described in 1 or 2 above which comprises a step of casting the dope composition on an endless belt and then peeling the film, wherein the dope composition is methylene chloride and a linear chain having 1 to 4 carbon atoms.
  • a dope composition having a solid content of 15 to 45% by mass containing a branched aliphatic alcohol, an acrylic resin, and a cellulose ester resin, and a ratio of the methylene chloride to the aliphatic alcohol (in the formula (i) below) MA) is 4 to 20, and 30 to 240 seconds after casting the dope composition on an endless belt, the residual solvent concentration represented by the following formula (ii) is 50 to 120%.
  • a method for producing an acrylic resin-containing film characterized by peeling.
  • MA mass of aliphatic alcohol / (mass of aliphatic alcohol + mass of methylene chloride) ⁇ 100
  • Residual solvent concentration (%) (mass of cast film ⁇ mass of dry film) / mass of dry film ⁇ 100 (%)
  • the acrylic resin containing film of this invention can be used suitably for a polarizing plate. Accordingly, it is possible to provide a liquid crystal display device that can improve the yield in operations such as punching of polarizing plates and panel bonding, and can maintain good visibility even in long-term use.
  • the acrylic resin-containing film of the present invention is an acrylic resin-containing film containing an acrylic resin as a main constituent, and contains the acrylic resin and the cellulose ester resin in a mass ratio of 95: 5 to 30:70, and the cellulose ester
  • the total substitution degree of the acyl group of the resin is 2.00 to 2.99
  • the substitution degree of the acetyl group is 0.10 to 1.89
  • the number of carbons of the acyl group other than the acetyl group is 3 to 7
  • the weight average molecular weight is
  • the acrylic resin-containing film has a haze of less than 1%, a tension softening point of 105 to 145 ° C., and no ductile fracture. This feature is a technical feature common to the inventions according to claims 1 to 3.
  • 0.05 to 45 parts by mass of acrylic fine particles are preferably contained with respect to 100 parts by mass of the total mass of the acrylic resin and the cellulose ester resin.
  • 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 until the final fracture.
  • the fracture surface is characterized by numerous indentations called dimples.
  • an acrylic resin-containing film that does not cause ductile fracture is characterized in that fracture such as fracture is not observed even when a large stress is applied to bend the film in two.
  • the demand for the brittleness of optical films is increasing from the viewpoint of reworkability and productivity as optical films become larger and thinner with the recent increase in liquid crystal display devices, and the above ductile fracture does not occur. Is required.
  • Forming an acrylic resin-containing film that does not cause ductile fracture is achieved by appropriately selecting the material configuration of the acrylic resin, cellulose ester, and other additives used.
  • the acrylic resin-containing film of the present invention has a tension softening point of 105 when considering use in a high-temperature environment such as a device having a high haze and a high temperature such as a projector or a vehicle-mounted display device.
  • the temperature is preferably ⁇ 145 ° C., more preferably 110 to 140 ° 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, which may result in a defect (missing coating).
  • 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 viewpoints of applicability, foaming, solvent drying, and the like.
  • the thickness of a film can be suitably selected according to a use.
  • 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 surface roughness also affects the haze value as surface haze, it is also effective to reduce the particle size and addition amount of acrylic particles within the above range, or to reduce the surface roughness of the film contact portion during film formation It is.
  • 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 acrylic resin and cellulose ester resin in a mass ratio of 95: 5 to 30:70, and the total acyl groups of the cellulose ester resin are the same.
  • the degree of substitution (T) is 2.00 to 2.99
  • the degree of acetyl group substitution (ac) is 0.10 to 1.89
  • the number of carbons of the acyl group other than the acetyl group is 3 to 7
  • the weight average molecular weight The excellent effect of the present invention can be obtained by the acrylic resin-containing film characterized in that Mw) is 75000 to 280000.
  • the acrylic resin and the cellulose ester resin are contained in a mass ratio of 95: 5 to 30:70, but the acrylic resin is preferably 50% by mass or more.
  • the acrylic resin-containing film of the present invention may contain a resin other than acrylic resin and cellulose ester resin.
  • the total mass of the acrylic resin and the cellulose ester resin is 55 to 100% by mass, preferably 60 to 99% by mass of the acrylic resin-containing film.
  • the method for producing an acrylic resin-containing film of the present invention is a method for producing an acrylic resin-containing film having a step of peeling a dope composition onto an endless belt and then peeling off, wherein the dope composition contains methylene chloride and carbon number.
  • Formula (i): MA mass of aliphatic alcohol / (mass of aliphatic alcohol + mass of methylene chloride) ⁇ 100
  • Residual solvent concentration (%) (mass of cast film ⁇ mass of dry film) / mass of dry film ⁇ 100 (%)
  • 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 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.
  • Mw weight average molecular weight
  • the weight average molecular weight of a resin such as an acrylic resin according to the present invention can be measured by gel permeation chromatography.
  • the measurement conditions are as follows.
  • the production method of the acrylic resin 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 used in 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 20 carbon atoms, specifically acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, Examples include octanoyl, lauroyl, stearoyl 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.
  • substituents substituted on the aromatic ring when the number of substituents substituted on the aromatic ring is 2 or more, they may be the same or different from each other, but they may be linked together to form a condensed polycyclic compound (for example, naphthalene, indene, indane, phenanthrene, quinoline). , Isoquinoline, chromene, chroman, phthalazine, acridine, indole, indoline, etc.).
  • a condensed polycyclic compound for example, naphthalene, indene, indane, phenanthrene, quinoline.
  • Isoquinoline chromene, chroman, phthalazine, acridine, indole, indoline, etc.
  • 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 according to the present invention is such that the total substitution degree (T) of the acyl group is 2.00 to 2.99, and the substitution degree (ac) of the acetyl group is 0.10 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.
  • substitution degree of the acetyl group and the substitution degree of other acyl groups were determined by the method prescribed in ASTM-D817-96.
  • 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 according to the present invention are characterized by being present in the state of particles in the acrylic resin, cellulose ester resin and acrylic resin-containing film (also referred to as incompatible state).
  • the acrylic particles are obtained by, for example, collecting a predetermined amount of the prepared acrylic resin-containing film, dissolving in a solvent, stirring, and sufficiently dissolving and dispersing the PTFE film having a pore diameter less than the average particle diameter of the acrylic particles. It is preferable that the weight of the insoluble matter filtered and collected using the membrane filter is 90% by mass or more of the acrylic particles added to the acrylic resin-containing film.
  • the acrylic particles used in the present invention are not particularly limited, but are preferably acrylic particles having a layer structure of two or more layers, and particularly preferably the following multilayer structure acrylic granular composite.
  • 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 compatibility with the acrylic resin.
  • 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.
  • fine particles having a large particle size it is possible to obtain a sufficient effect with a smaller addition amount, which is preferable.
  • the transparency of the film may be impaired. Therefore, it is important to approximate the refractive indexes of both.
  • 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.
  • the ratio of the core layer is less than 50 parts by mass, when the film formed is subjected to processing such as stretching, the particles are deformed to cause a refractive index difference between the resin and the particles, resulting in the transparency of the film. There is a risk of damaging sex.
  • 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.
  • a graft copolymer obtained by copolymerizing a monomer mixture comprising a saturated carboxylic acid monomer, an aromatic vinyl monomer, and, if necessary, other vinyl monomers copolymerizable therewith. can be mentioned.
  • the rubbery polymer used for the acrylic particles that are the graft copolymer, 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 refractive indexes of the acrylic resin and the acrylic particles are close to each other because the transparency of the acrylic resin-containing film of the present invention can be obtained.
  • the refractive index difference between the acrylic particles and the acrylic resin 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 and / or a composition ratio of the rubbery polymer or monomer used in the acrylic particles is prepared. Depending on the method, the difference in refractive index can be reduced, and an acrylic resin-containing film excellent in transparency can be obtained.
  • the difference in refractive index referred to here means that the acrylic resin-containing film of the present invention is sufficiently dissolved in a solvent in which the acrylic resin is soluble to obtain a cloudy solution, which is subjected to an operation such as centrifugation. After separating the soluble part and the insoluble part and purifying the soluble part (acrylic resin) and the insoluble part (acrylic particles), the difference in the measured refractive index (23 ° C., measurement wavelength: 550 nm) is shown.
  • the method of blending the acrylic particles with the acrylic resin is not particularly limited, and after blending the acrylic resin and other optional components in advance, usually at 200 to 350 ° C. while adding the acrylic particles, uniaxial or biaxial A method of uniformly melt-kneading with a shaft extruder is preferably used.
  • a method such as in-line addition can be used.
  • acrylic particles can also be used as the acrylic particles of the present invention.
  • Staphyloid AC-3355 manufactured by Ganz Kasei Co., Ltd.
  • Delpet SRB215 manufactured by Asahi Kasei Chemicals Co., Ltd.
  • the like can be mentioned.
  • the acrylic resin-containing film of the present invention preferably contains 0.05 to 45% by mass of acrylic particles based on the total mass of the resin constituting the film.
  • ⁇ Film formation> As a method for producing the acrylic resin-containing film of the present invention, 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 is not limited as long as it dissolves acrylic resin, cellulose ester resin, and other additives simultaneously. Can be used.
  • a chlorinated organic solvent methylene chloride
  • 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.
  • 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 dope composition is dissolved in%.
  • the ratio of methylene chloride to aliphatic alcohol (MA represented by the following formula (i)) is preferably 4-20.
  • MA mass of aliphatic alcohol / (mass of aliphatic alcohol + mass of methylene chloride) ⁇ 100
  • the linear or branched aliphatic alcohol having 1 to 4 carbon atoms 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.
  • the dope is formed by mixing the acrylic resin and the cellulose ester resin solution with the acrylic resin solution and the additive solution.
  • 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 and JP-A-9-
  • Various dissolution methods can be used such as a method performed by a cooling dissolution method as described in JP-A-95557 or JP-A-9-95538, a method performed at high pressure as described in JP-A No. 11-21379,
  • a method of pressurizing at a temperature equal to or higher than the boiling point of the main solvent is preferable.
  • the total of the three types of acrylic resin, cellulose ester resin, and acrylic fine particles in the dope is preferably in the range of 15 to 45% by mass.
  • 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 it is preferable to use.
  • the aggregate remaining when the fine particles are dispersed and the aggregate generated when the main dope is added 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 fine particles is sufficiently thinner than that of the additive solution, aggregates do not adhere to each other during filtration and the filtration pressure does not increase rapidly.
  • 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.
  • Large agglomerates are removed from the acrylic fine particle charging vessel 41 by the filter 44 and fed to the stock vessel 42. Thereafter, the acrylic fine particle additive solution is added from the stock kettle 42 to the main dope dissolving kettle 1. Thereafter, 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 mass of the recycled material. Since the return material contains acrylic fine particles, it is preferable to control the addition amount of the acrylic fine particle addition liquid in accordance with the addition amount of the return material.
  • 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. Moreover, what knead
  • 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 the step of evaporating the solvent by heating the web (the dope is cast on the casting support and the formed dope film is called “web”) on the casting support. is there.
  • 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.
  • the web is preferably peeled from the support in the range of 30 to 240 seconds from the viewpoint of productivity, surface quality, peelability and the like. More preferably, it is 60 to 180 seconds.
  • 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 residual solvent concentration (%) of the web is defined by the following formula (ii).
  • Residual solvent concentration (%) (mass of cast film ⁇ mass of dry film) / mass of dry film ⁇ 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 when peeling the metal support from the film is usually preferably 196 to 245 N / m. However, when wrinkles are likely to occur during peeling, peeling with a tension of 190 N / m or less is preferable. 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. It is also preferable to provide a neutral zone between different temperature zones so that the zones do not interfere with each other.
  • 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 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 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
  • the polarizing plate used in the present invention can be produced by a general method. That is, it is preferable that an adhesive layer is provided on the back side 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. Further, surface treatment such as corona treatment can be performed as necessary. By performing the surface treatment, adhesion with the polarizer can be improved.
  • the film may be used on the other surface, or another polarizing plate protective film may be used.
  • cellulose ester films for example, Konica Minoltac 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 Minoltac 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.
  • iodine is dyed on a system film and one in which dichroic dye is dyed.
  • a polyvinyl alcohol aqueous solution is formed into a film and dyed by uniaxial stretching or dyed or uniaxially stretched and then preferably subjected to a durability treatment with a boron compound.
  • an adhesive layer having a storage elastic modulus at 25 ° C. in the range of 1.0 ⁇ 10 4 to 1.0 ⁇ 10 9 Pa in at least a part of the adhesive layer is used.
  • a curable adhesive that forms a high molecular weight body or a crosslinked structure by various chemical reactions after the adhesive layer is applied and bonded 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 curable urethane adhesives, polyether methacrylate types, Examples include anaerobic adhesives such as ester-based methacrylate type and oxidized polyether methacrylate, cyanoacrylate-based instant adhesives, acrylate-peroxide-based two-component instant adhesives, and the like.
  • the adhesive may be a one-pack type or a mold that uses two or more liquids mixed before use.
  • the 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.
  • concentration of the adhesive solution may be appropriately determined depending on the film thickness after bonding, 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.
  • BR85 acrylic resin, manufactured by Mitsubishi Rayon Co., Ltd.
  • Mw
  • the solvent was evaporated until the residual solvent concentration (residual solvent amount) reached 100%, and the film was peeled off from the stainless steel band support with a peeling tension of 162 N / m. At this time, the time required from casting to peeling was 100 seconds.
  • the peeled acrylic resin web was evaporated at 35 ° C., slit to 1.6 m width, and then dried at a drying temperature of 135 ° C. while being stretched 1.1 times in the width direction by a tenter. At this time, the residual solvent concentration when starting stretching with a tenter was 10% by mass.
  • acrylic resin-containing films A1 to A28 were produced in the same manner as the acrylic resin-containing film A1, except that the composition ratio of the acrylic resin and the cellulose ester resin was changed as shown in Table 1.
  • acrylic resin containing film A8, A11 added the following ultraviolet absorber and produced dope.
  • the acrylic resin-containing film is cut out at 120 mm (length) x 10 mm (width) and continuously heated at a heating rate of 30 ° C./min while being pulled with a tension of 10 N under the conditions of 23 ° C. and 55% RH. The temperature at that time was measured three times and the average was calculated.
  • the film was torn under conditions of 23 ° C. and 55% RH using a light load tear tester (manufactured by Toyo Seiki Co., Ltd.), and evaluated as follows.
  • ⁇ The tear surface is very smooth and is torn straight.
  • Table 2 shows the above evaluation results.
  • the acrylic resin-containing film of the present invention is excellent in evaluation of the tension softening point, ductile fracture, film deformation, cutting property, and film appearance.
  • Example 2 In the production conditions of the films A1, A12, and A14 performed in Example 1, various acrylic resin-containing films A1-1 to A1-18, A12-1 to A12-8, and A14-1 to A14 were used under the conditions shown in Table 3. -4 was prepared and evaluated as follows.
  • A14-5 was produced in the same manner as A14-1 except that 0.05% by mass of zonyl UR (manufactured by DuPont) was added to the dope of A14 as a release agent with respect to the mass of the dope.
  • zonyl UR manufactured by DuPont
  • Table 3 summarizes the contents and evaluation results of various acrylic resin-containing films.
  • Example 3 Film formation was carried out in the same manner except that BR85 was used in place of the acrylic resin (K1) under the production conditions for the A17 film, to produce an acrylic resin-containing film C1.
  • acrylic fine particles AP1 and commercially available acrylic fine particles, Staphyloid AC-3355 (manufactured by Ganz Kasei Co., Ltd.), Delpet SRB215 (manufactured by Asahi Kasei Chemicals Co., Ltd.) are manufactured in the same manner as C1 with the compositions shown in Table 4. Thus, acrylic resin-containing films C2 to C7 were produced.
  • ⁇ Preparation of acrylic fine particle AP1> 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.
  • a small amount of the polymer latex thus obtained was collected, and the particle diameter was measured by an electrophoretic light scattering photometer ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) and found to be 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 fine particles AP1 having a three-layer structure.
  • the acrylic resin-containing film of the present invention is excellent in the evaluation of haze, tension softening point, ductile fracture, film deformation, cutting property, and film appearance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polarising Elements (AREA)
  • Moulding By Coating Moulds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un film contenant une résine acrylique qui est transparent et qui présente une résistance thermique élevée et présente une friabilité remarquablement améliorée. L'invention concerne également un procédé de production du film. L'invention concerne spécifiquement un film contenant une résine acrylique qui contient une résine acrylique comme composant constituant principal, caractérisé en ce que le film contient une résine acrylique et une résine ester de cellulose avec un rapport en poids de 95 : 5 à 30 : 70, que la résine ester de cellulose présente un degré total de substitution par des acyles de 2,00 à 2,99 et un degré de substitution par des acétyles de 0,10 à 1,89, et les groupes substituants acyles de ceux-ci autres que les acétyles ont chacun de 3 à 7 atomes de carbone, que la résine ester de cellulose présente un poids moléculaire moyen en poids de 75 000 à 280 000, et que le film présente un voile inférieur à 1 % et un point de ramollissement de la tension de 105 à 145° et n'entraîne pas de rupture ductile.
PCT/JP2009/050059 2008-01-18 2009-01-07 Film contenant une résine acrylique et procédé de production du film WO2009090900A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020107015577A KR101497751B1 (ko) 2008-01-18 2009-01-07 아크릴 수지 함유 필름 및 그의 제조 방법
JP2009550000A JPWO2009090900A1 (ja) 2008-01-18 2009-01-07 アクリル樹脂含有フィルム及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-009035 2008-01-18
JP2008009035 2008-01-18

Publications (1)

Publication Number Publication Date
WO2009090900A1 true WO2009090900A1 (fr) 2009-07-23

Family

ID=40885291

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/050059 WO2009090900A1 (fr) 2008-01-18 2009-01-07 Film contenant une résine acrylique et procédé de production du film

Country Status (3)

Country Link
JP (1) JPWO2009090900A1 (fr)
KR (1) KR101497751B1 (fr)
WO (1) WO2009090900A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011225691A (ja) * 2010-04-19 2011-11-10 Konica Minolta Opto Inc 光学フィルム及びその製造方法
JP2012016844A (ja) * 2010-07-06 2012-01-26 Konica Minolta Opto Inc 光学フィルムの製造方法、光学フィルム、偏光板及び液晶表示装置
WO2016104460A1 (fr) * 2014-12-25 2016-06-30 コニカミノルタ株式会社 Film fonctionnel, verre d'isolation sonore comprenant du verre auquel est lié ledit film fonctionnel, verre feuilleté, élément de support pour film décoratif et procédé de production du film fonctionnel

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102607480B1 (ko) * 2019-02-27 2023-11-29 코니카 미놀타 가부시키가이샤 광학 필름용의 도프 및 그 제조 방법, 광학 필름, 편광판, 그리고 광학 필름의 제조 방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05119217A (ja) * 1991-10-23 1993-05-18 Kanegafuchi Chem Ind Co Ltd 偏光膜保護用フイルム
JP2002356658A (ja) * 2001-05-31 2002-12-13 Nippon Carbide Ind Co Inc アクリル系オーバーレイフィルム
JP2003012859A (ja) * 2001-06-29 2003-01-15 Konica Corp セルロースエステルフィルム、偏光板用保護フィルム及び偏光板
JP2007062055A (ja) * 2005-08-30 2007-03-15 Konica Minolta Opto Inc セルロースエステルフィルム、該フィルムの製造方法および該フィルムを用いた液晶表示装置
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
WO2008126528A1 (fr) * 2007-03-12 2008-10-23 Konica Minolta Opto, Inc. Procédé pour produire un film anti-reflet et anti-éblouissement, film anti-reflet et anti-éblouissement, polariseur et dispositif d'affichage

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7815823B2 (en) * 2005-03-10 2010-10-19 Konica Minolta Opto, Inc. Optical film, manufacturing method of optical film, optical compensating film, manufacturing method of optical compensating film, polarizing plate, and liquid crystal display
KR101437703B1 (ko) * 2006-06-21 2014-09-03 코니카 미놀타 어드밴스드 레이어즈 인코포레이티드 편광판 보호 필름, 편광판, 액정 표시 장치
CN101821324B (zh) * 2007-10-13 2012-06-27 柯尼卡美能达精密光学株式会社 光学薄膜

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05119217A (ja) * 1991-10-23 1993-05-18 Kanegafuchi Chem Ind Co Ltd 偏光膜保護用フイルム
JP2002356658A (ja) * 2001-05-31 2002-12-13 Nippon Carbide Ind Co Inc アクリル系オーバーレイフィルム
JP2003012859A (ja) * 2001-06-29 2003-01-15 Konica Corp セルロースエステルフィルム、偏光板用保護フィルム及び偏光板
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
JP2007062055A (ja) * 2005-08-30 2007-03-15 Konica Minolta Opto Inc セルロースエステルフィルム、該フィルムの製造方法および該フィルムを用いた液晶表示装置
WO2008126528A1 (fr) * 2007-03-12 2008-10-23 Konica Minolta Opto, Inc. Procédé pour produire un film anti-reflet et anti-éblouissement, film anti-reflet et anti-éblouissement, polariseur et dispositif d'affichage

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011225691A (ja) * 2010-04-19 2011-11-10 Konica Minolta Opto Inc 光学フィルム及びその製造方法
JP2012016844A (ja) * 2010-07-06 2012-01-26 Konica Minolta Opto Inc 光学フィルムの製造方法、光学フィルム、偏光板及び液晶表示装置
WO2016104460A1 (fr) * 2014-12-25 2016-06-30 コニカミノルタ株式会社 Film fonctionnel, verre d'isolation sonore comprenant du verre auquel est lié ledit film fonctionnel, verre feuilleté, élément de support pour film décoratif et procédé de production du film fonctionnel
CN107108924A (zh) * 2014-12-25 2017-08-29 柯尼卡美能达株式会社 功能性膜、其贴合于玻璃的隔音玻璃、夹层玻璃、装饰膜用基材及功能性膜的制造方法

Also Published As

Publication number Publication date
JPWO2009090900A1 (ja) 2011-05-26
KR101497751B1 (ko) 2015-03-02
KR20100103584A (ko) 2010-09-27

Similar Documents

Publication Publication Date Title
JP4379547B2 (ja) 光学フィルムの製造方法
JP5040688B2 (ja) 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
JP5521552B2 (ja) 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
JP5463914B2 (ja) 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
WO2009150926A1 (fr) Procédé de production de film acrylique, et film acrylique produit selon le procédé
JP5402925B2 (ja) 偏光板及び液晶表示装置
JP5333447B2 (ja) 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) Film optique
JP5533858B2 (ja) 光学フィルム、それを用いた偏光板及び液晶表示装置
JP5397382B2 (ja) 光学フィルム、光学フィルムの製造方法、偏光板および液晶表示装置
WO2009090900A1 (fr) Film contenant une résine acrylique et procédé de production du film
JP2013028676A (ja) アクリル樹脂含有フィルムの製造方法及びアクリル樹脂含有フィルム、偏光板、液晶表示装置
JP5533857B2 (ja) 光学フィルム、それを用いた偏光板及び液晶表示装置
WO2011055590A1 (fr) Bobine de film protecteur pour plaque de polarisation à cristaux liquides et son procédé de fabrication
WO2009119268A1 (fr) Film contenant une résine acrylique, procédé de production du film contenant une résine acrylique, et plaque de polarisation et dispositif d’affichage à cristaux liquides utilisant le film contenant une résine acrylique
WO2010116830A1 (fr) Film optique
WO2013035273A1 (fr) Procédé de fabrication d'un film contenant une résine acrylique, film contenant une résine acrylique, plaque de polarisation et dispositif d'affichage à cristaux liquides
WO2010116823A1 (fr) Film optique, procédé pour produire un film optique, panneau à cristaux liquides et dispositif d'affichage d'image
JP2012016844A (ja) 光学フィルムの製造方法、光学フィルム、偏光板及び液晶表示装置
JP2012016845A (ja) 光学フィルムの製造方法、光学フィルム、偏光板及び液晶表示装置
JP2011123402A (ja) 偏光板及びそれを用いた液晶表示装置

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: 09702020

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2009550000

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20107015577

Country of ref document: KR

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: 09702020

Country of ref document: EP

Kind code of ref document: A1