WO2015186629A1 - メタクリル樹脂組成物 - Google Patents
メタクリル樹脂組成物 Download PDFInfo
- Publication number
- WO2015186629A1 WO2015186629A1 PCT/JP2015/065579 JP2015065579W WO2015186629A1 WO 2015186629 A1 WO2015186629 A1 WO 2015186629A1 JP 2015065579 W JP2015065579 W JP 2015065579W WO 2015186629 A1 WO2015186629 A1 WO 2015186629A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- resin
- group
- mass
- resin composition
- Prior art date
Links
- 0 CNC(C(O*)=O)=N Chemical compound CNC(C(O*)=O)=N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
-
- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
-
- 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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
-
- 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
-
- 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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
Definitions
- the present invention relates to a methacrylic resin composition. More specifically, the present invention is a methacrylic resin that is excellent in heat resistance and transparency, has a small absolute value of retardation in the thickness direction, has a uniform thickness, and is excellent in surface smoothness. And a resin composition comprising a polycarbonate resin.
- MMA-CHMA resin methyl methacrylate resin
- PC resin polycarbonate resin
- a resin composition comprising MMA-CHMA resin and PC resin has a low glass transition temperature and a large shrinkage under high temperature and high humidity. Even if the resin composition is molded by a known method, it is difficult to obtain a film having a good balance of various properties.
- the object of the present invention is to easily produce a film having excellent heat resistance and transparency, small absolute value of retardation in the thickness direction, small shrinkage under high temperature and high humidity, uniform thickness and excellent surface smoothness. It is another object of the present invention to provide a resin composition comprising a methacrylic resin and a polycarbonate resin.
- X is a polycyclic aliphatic hydrocarbon group having 10 or more carbon atoms.
- [6] The resin composition according to any one of [1] to [5], wherein the total content of the methacrylic resin (A) and the polycarbonate resin (B) is 80 to 100% by mass.
- a film comprising the resin composition according to any one of [1] to [6].
- the film according to [7] having a thickness of 10 to 50 ⁇ m.
- the film according to [7] or [8] which is at least uniaxially stretched.
- a polarizer protective film comprising the film according to any one of [7] to [10].
- [12] A retardation film comprising the film according to any one of [7] to [10].
- a polarizing plate having a polarizer and the film according to any one of [7] to [10] laminated on the polarizer.
- the resin composition of the present invention has a high glass transition temperature, a high light transmittance, and a low haze.
- a polarizer By laminating the film according to the present invention with a polarizer, a polarizing plate for producing a liquid crystal display device having functions such as high chromatic color, wide viewing angle, and low color distortion can be provided.
- the resin composition according to an embodiment of the present invention contains a methacrylic resin (A) and a polycarbonate resin (B).
- the methacrylic resin (A) contains the structural unit (a1), the structural unit (a2), and the structural unit (a3).
- the structural unit (a1) is derived from a methacrylic acid polycyclic aliphatic hydrocarbon ester, preferably formed by an addition reaction of a methacryloyl group in the methacrylic acid polycyclic aliphatic hydrocarbon ester.
- the structural unit (a1) is preferably a unit represented by the formula (2).
- Cy in the formula (2) is a polycyclic aliphatic hydrocarbon group.
- the polycyclic aliphatic hydrocarbon group is not particularly limited, and examples thereof include an octahydropentalen-1-yl group, an octahydropentalen-2-yl group, and an octahydro-1-H-inden-4-yl group.
- the methacrylic acid polycyclic aliphatic hydrocarbon ester is preferably a compound represented by the formula (1).
- X in the formula (1) is a polycyclic aliphatic hydrocarbon group having 10 or more carbon atoms, preferably a bridged cyclic aliphatic hydrocarbon group having 10 or more carbon atoms.
- the bridged cyclic aliphatic hydrocarbon is an alicyclic hydrocarbon having a structure in which two non-adjacent carbon atoms constituting a ring are connected by a carbon chain composed of one or more carbon atoms.
- Such a bridged cyclic aliphatic hydrocarbon may have a condensed ring structure or a spiro ring structure in addition to the structure linked by carbon chains.
- the number of carbon atoms constituting the polycyclic aliphatic hydrocarbon group is more preferably 10-20.
- Examples of the polycyclic aliphatic hydrocarbon group having 10 or more carbon atoms include octahydrocyclopenta [c, d] pentalen-2A-2a (2H) -yl group, 3a, 6a-dimethyloctahydropentalen-2-yl Group, tetradecahydroanthracen-9-yl group, androstan-4-yl group, cholestan-2-yl group, cholestane-5-yl group, 1,3,3-trimethylnorbornan-2-yl group, 1, 2,3,3-tetramethylnorbornan-2-yl group, 1,3,3-trimethylnorbornan-2-yl group, isobornan-2-yl group, 2-methylisobornan-2-yl group, 2- An ethylisobornan-2-yl group, a decahydro-2,5-methano-7,10-methanonaphthalen-1-yl group, a tricyclo [5.2.1.0
- the structural unit (a2) is derived from a methacrylic acid ester (a2), preferably formed by an addition reaction of a methacryloyl group in the methacrylic acid ester (a2).
- the methacrylic acid ester (a2) is a methacrylic acid ester other than the methacrylic acid polycyclic aliphatic hydrocarbon ester.
- methacrylic acid ester (a2) examples include methacrylic acid monocyclic aliphatic hydrocarbon esters such as cyclohexyl methacrylate, cyclopentyl methacrylate, and cycloheptyl methacrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, Methacrylic acid chain aliphatic hydrocarbon esters such as dodecyl methacrylate: 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate
- methacrylic acid chain aliphatic hydrocarbon ester or methacrylic acid monocyclic aliphatic hydrocarbon ester is preferable, and methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methacrylic acid are preferred. More preferred are n-butyl acid, t-butyl methacrylate and cyclohexyl methacrylate, and most preferred is methyl methacrylate.
- the structural unit (a3) is derived from an acrylate ester, preferably formed by an addition reaction of an acryloyl group in the acrylate ester.
- Acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid chain aliphatic hydrocarbon esters such as 2-ethylhexyl acrylate; acrylic acrylates such as phenyl acrylate Hydrocarbon esters; acrylate cycloaliphatic hydrocarbon esters such as cyclohexyl acrylate and norbornenyl acrylate.
- methyl acrylate, ethyl acrylate, and butyl acrylate are preferable, and methyl acrylate is particularly preferable because thermal decomposition can be suppressed and film formation is easy.
- the methacrylic resin (A) used in the present invention may contain a structural unit (a4) in addition to the structural units (a1), (a2) and (a3).
- the structural unit (a4) is derived from monomers other than methacrylic acid esters and acrylic acid esters. Examples of such monomers include monomers having only one polymerizable carbon-carbon double bond in one molecule such as acrylamide; methacrylamide; acrylonitrile; methacrylonitrile, styrene.
- the methacrylic resin (A) used in the present invention usually has 10 to 50% by mass of the structural unit (a1) and the structural unit (a2) from the viewpoint of high glass transition temperature and small shrinkage at high temperature and high humidity. 50 to 90% by mass and 0 to 20% by mass of structural unit (a3), preferably 15 to 40% by mass of structural unit (a1), 60 to 85% by mass of structural unit (a2), and structural unit 0 to 10% by mass of (a3), more preferably 20 to 30% by mass of structural unit (a1), 70 to 80% by mass of structural unit (a2), and 0 to 5% of structural unit (a3) %contains.
- the content of the structural unit (a4) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and still more preferably 0 to 2% by mass.
- the methacrylic resin (A) used in the present invention has a weight average molecular weight (hereinafter sometimes referred to as “Mw”), preferably 60,000 to 200,000, more preferably 80,000 to 160,000, still more preferably. 90,000 to 150,000, particularly preferably 100,000 to 130,000.
- Mw weight average molecular weight
- the resulting film has high strength, is difficult to break, and is easy to stretch. Therefore, the film can be made thinner.
- Mw is 200,000 or less
- the methacryl resin (A) has improved moldability, the thickness of the resulting film tends to be uniform and excellent in surface smoothness.
- the methacrylic resin (A) used in the present invention is the ratio of Mw to the number average molecular weight (hereinafter sometimes referred to as “Mn”) (Mw / Mn: hereinafter, this value may be referred to as “molecular weight distribution”). Is preferably 1.2 to 5.0, more preferably 1.5 to 3.5. When the molecular weight distribution is 1.2 or more, the fluidity of the methacrylic resin (A) is improved, and the resulting film tends to be excellent in surface smoothness. A film obtained by having a molecular weight distribution of 5.0 or less tends to be excellent in impact resistance and toughness.
- Mw and Mn are values obtained by converting a chromatogram measured by gel permeation chromatography (GPC) into a molecular weight of standard polystyrene.
- the methacrylic resin (A) used in the present invention has a melt flow rate of preferably 0.1 to 15 g / 10 min, measured at 230 ° C. under a load of 3.8 kg in accordance with JIS K7210.
- the amount is preferably 0.5 to 5 g / 10 minutes, and more preferably 0.8 to 3 g / 10 minutes.
- the glass transition temperature of the methacrylic resin (A) used in the present invention is preferably 120 ° C. or higher, more preferably 123 ° C. or higher, further preferably 124 ° C. or higher, and particularly preferably 125 ° C. or higher.
- the upper limit of the glass transition temperature of the methacrylic resin (A) is usually 140 ° C.
- the glass transition temperature can be controlled by adjusting the proportion of structural units derived from methacrylic acid polycyclic aliphatic hydrocarbon ester. When the glass transition temperature is in this range, the heat resistance of the resulting film is improved and deformation such as heat shrinkage hardly occurs.
- the glass transition temperature is an intermediate glass transition temperature measured according to JIS K7121 (temperature increase rate 20 ° C./min).
- the method for producing the methacrylic resin (A) used in the present invention is not particularly limited.
- it can be produced by a known polymerization method such as a radical polymerization method or an anionic polymerization method.
- the adjustment of the methacrylic resin (A) to the above-mentioned characteristic values is performed by adjusting the polymerization conditions, specifically, the polymerization temperature, the polymerization time, the type and amount of the chain transfer agent, the type and amount of the polymerization initiator, etc. Can be done by adjusting. Adjustment of resin characteristics by adjusting polymerization conditions is a technique well known to those skilled in the art.
- the methacrylic resin (A) used in the present invention when a radical polymerization method is used, it is possible to select a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or an emulsion polymerization method. In such a polymerization method, it is preferable to carry out by a suspension polymerization method or a bulk polymerization method from the viewpoint of productivity and thermal decomposition resistance.
- the bulk polymerization method is preferably performed by a continuous flow method.
- the polymerization reaction is performed using a polymerization initiator, the above-described monomer, and a chain transfer agent as necessary.
- the polymerization initiator used in the radical polymerization method for producing the methacrylic resin (A) used in the present invention is not particularly limited as long as it generates a reactive radical.
- the polymerization initiator used in the present invention has a one-hour half-life temperature of preferably 60 to 140 ° C, more preferably 80 to 120 ° C.
- polymerization initiator examples include t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t -Butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy Neodecanoate, 1,1-bis (t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2'-azobis (2-methylpro Pionitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl 2,2'- And azobis (2-methylpropionate).
- t-hexylperoxy 2-ethylhexanoate 1,1-bis (t-hexylperoxy) cyclohexane, and dimethyl 2,2′-azobis (2-methylpropionate) are preferable.
- polymerization initiators can be used alone or in combination of two or more.
- the addition amount and addition method of the polymerization initiator are not particularly limited as long as they are appropriately set according to the purpose.
- the amount of the polymerization initiator used in the suspension polymerization method is preferably 0.0001 to 0.1 parts by mass, more preferably 100 parts by mass of the total amount of monomers to be subjected to the polymerization reaction. 0.001 to 0.07 parts by mass.
- the chain transfer agent used in the radical polymerization method for producing the methacrylic resin (A) used in the present invention is not particularly limited.
- n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropionate, butanediol bisthioglycolate, butanediol bisthiol Alkyl mercaptans such as propionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tris- ( ⁇ -thiopropionate), pentaerythritol tetrakisthiopropionate; ⁇ -methylstyrene Dimer; terpinolene and the like can be mentioned.
- alkyl mercaptans such as n-octyl mercaptan and pentaerythritol tetrakisthiopropionate are preferred.
- chain transfer agents can be used alone or in combination of two or more.
- the amount of the chain transfer agent used is preferably 0.1 to 1 part by weight, more preferably 0.15 to 0.8 part by weight, based on 100 parts by weight of the total amount of monomers to be subjected to the polymerization reaction. More preferably, it is 0.2 to 0.6 parts by mass, and most preferably 0.2 to 0.5 parts by mass.
- the amount of the chain transfer agent used is preferably 2500 to 10,000 parts by mass, more preferably 3000 to 9000 parts by mass, and further preferably 3500 to 6000 parts by mass with respect to 100 parts by mass of the polymerization initiator. When the amount of the chain transfer agent used is in the above range, the resin composition can have good moldability and high mechanical strength.
- Each monomer, polymerization initiator and chain transfer agent used in the production of the methacrylic resin (A) used in the present invention may be mixed together and supplied to the reaction vessel, or they may be separated separately. You may supply to a reaction tank. In the present invention, a method of mixing all and supplying the mixture to the reaction vessel is preferable.
- the solvent is not limited as long as it can dissolve the monomer and the methacrylic resin (A), but benzene, toluene, ethylbenzene Aromatic hydrocarbons such as are preferred. These solvents can be used alone or in combination of two or more.
- the usage-amount of a solvent can be suitably set from a viewpoint of the viscosity and productivity of a reaction liquid.
- the amount of the solvent used is, for example, preferably 100 parts by mass or less, more preferably 50 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerization reaction raw materials.
- the temperature during the radical polymerization reaction for producing the methacrylic resin (A) used in the present invention is preferably 50 to 180 ° C, more preferably 60 to 140 ° C.
- the temperature is preferably 100 to 200 ° C, more preferably 110 to 180 ° C.
- productivity tends to be improved due to an increase in the polymerization rate, a decrease in the viscosity of the polymerization solution, and the like.
- the methacrylic resin (A) used in the present invention is produced by suspension polymerization, a granular polymer can be obtained by washing, dehydrating and drying by a well-known method after completion of the polymerization.
- Radical polymerization may be performed using a batch type reaction apparatus or a continuous flow type reaction apparatus.
- a polymerization reaction raw material (mixed solution containing a monomer, a polymerization initiator, a chain transfer agent, etc.) is prepared under a nitrogen atmosphere, and the mixture is supplied to the reactor at a constant flow rate. The liquid in the reactor is withdrawn at a flow rate corresponding to the amount.
- a tubular reactor that can be in a state close to plug flow and / or a tank reactor that can be in a state close to complete mixing can be used.
- continuous flow polymerization may be performed in one reactor, or continuous flow polymerization may be performed by connecting two or more reactors.
- the amount of liquid in the tank reactor during the polymerization reaction is preferably 1/4 to 3/4, more preferably 1/3 to 2/3 with respect to the volume of the tank reactor.
- the reactor is usually equipped with a stirring device.
- the stirring device include a static stirring device and a dynamic stirring device.
- the dynamic agitation device include a Max blend type agitation device, an agitation device having a lattice-like blade rotating around a vertical rotation shaft arranged in the center, a propeller type agitation device, a screw type agitation device, and the like. .
- a Max blend type stirring apparatus is preferably used from the point of uniform mixing property.
- the removal method is not particularly limited, but heating devolatilization is preferable.
- the devolatilization method include an equilibrium flash method and an adiabatic flash method.
- the devolatilization temperature by the adiabatic flash method is preferably 200 to 280 ° C, more preferably 220 to 260 ° C.
- the time for heating the resin by the adiabatic flash method is preferably 0.3 to 5 minutes, more preferably 0.4 to 3 minutes, and further preferably 0.5 to 2 minutes.
- a methacrylic resin (A) with little coloring is easily obtained.
- the removed unreacted monomer can be recovered and used again for the polymerization reaction.
- the yellow index of the recovered monomer may be high due to heat applied during the recovery operation.
- the recovered monomer is preferably purified by an appropriate method to reduce the yellow index.
- Examples of the method for producing the methacrylic resin (A) used in the present invention by anionic polymerization include an anion in the presence of a mineral acid salt such as an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator.
- a method of polymerizing see Japanese Patent Publication No. 7-25859
- a method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound see JP-A-11-335432
- Examples of the polymerization initiator include anionic polymerization (see JP-A-6-93060).
- an alkyl lithium such as n-butyllithium, sec-butyllithium, isobutyllithium or t-butyllithium is used as a polymerization initiator.
- an organoaluminum compound coexist from a viewpoint of productivity.
- the organoaluminum compound include compounds represented by AlR 1 R 2 R 3 . (In the formula, R 1 , R 2 and R 3 each independently have an alkyl group which may have a substituent, an optionally substituted cycloalkyl group or an optionally substituted group.
- R 2 and R 3 may be an aryleneoxy group which may have a substituent formed by bonding.
- organoaluminum compound examples include isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutyl bis (2,6-di-t-butylphenoxy) aluminum, isobutyl [2,2 And '-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum.
- anionic polymerization method an ether or a nitrogen-containing compound can coexist in order to control the polymerization reaction.
- the polycarbonate resin (B) used in the present invention is not particularly limited.
- examples of the polycarbonate resin (B) include a polymer obtained by a reaction between a polyfunctional hydroxy compound and a carbonate ester-forming compound.
- an aromatic polycarbonate resin is preferred from the viewpoint of compatibility with the methacrylic resin (A) and good transparency of the resulting film.
- the polycarbonate resin (B) used in the present invention has an MVR value at 300 ° C. and 1.2 kg from the viewpoints of compatibility with the methacrylic resin (A), transparency of the resulting film, surface smoothness, and the like. preferably 1 ⁇ 250cm 3/10 min, more preferably 3 ⁇ 230cm 3/10 min.
- the polycarbonate resin (B) used in the present invention was measured by gel permeation chromatography (GPC) from the viewpoints of compatibility with the methacrylic resin (A), transparency of the resulting film, surface smoothness, and the like.
- the weight average molecular weight calculated by converting the chromatogram into the molecular weight of standard polystyrene is preferably 18,000 to 75,000, more preferably 20,000 to 60,000.
- the MVR value and the weight average molecular weight of the polycarbonate resin (B) can be adjusted by adjusting the amounts of the terminal terminator and the branching agent.
- the glass transition temperature of the polycarbonate resin (B) used in the present invention is preferably 130 ° C. or higher, more preferably 135 ° C. or higher, and further preferably 140 ° C. or higher.
- the upper limit of the glass transition temperature of the polycarbonate resin is usually 180 ° C.
- the glass transition temperature is an intermediate glass transition temperature measured according to JIS K7121 (temperature increase rate 20 ° C./min).
- the method for producing the polycarbonate resin (B) is not particularly limited. Examples thereof include a phosgene method (interfacial polymerization method) and a melt polymerization method (transesterification method).
- the aromatic polycarbonate resin preferably used in the present invention may be obtained by subjecting a polycarbonate resin raw material produced by a melt polymerization method to a treatment for adjusting the amount of terminal hydroxy groups.
- Examples of the polyfunctional hydroxy compound that is a raw material for producing the polycarbonate resin (B) include 4,4′-dihydroxybiphenyls which may have a substituent; bis (hydroxy) which may have a substituent Phenyl) alkanes; bis (4-hydroxyphenyl) ethers optionally having substituents; bis (4-hydroxyphenyl) sulfides optionally having substituents; Bis (4-hydroxyphenyl) sulfoxides which may be substituted; bis (4-hydroxyphenyl) sulfones which may have a substituent; bis (4-hydroxyphenyl) ketones which may have a substituent; Bis (hydroxyphenyl) fluorenes optionally having substituents; Dihydroxy-p-terphenyls optionally having substituents; Dihydroxy-p-quarterphenyls which may have a group; bis (hydroxyphenyl) pyrazines which may have a substituent; bis (hydroxyphenyl) menthanes which may have a
- carbonate ester-forming compounds include various dihalogenated carbonyls such as phosgene, haloformates such as chloroformate, and carbonate ester compounds such as bisaryl carbonate.
- the amount of the carbonate ester-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.
- the reaction for producing the polycarbonate resin (B) is usually performed in a solvent in the presence of an acid binder.
- acid binders include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, trimethylamine, triethylamine, tributylamine, Tertiary amines such as N, N-dimethylcyclohexylamine, pyridine, dimethylaniline, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide Quaternary ammonium salts, quaternary phosphonium salts such as tetrabutylphosphonium chloride, tetrabutylphosphon
- an antioxidant such as sodium sulfite or hydrosulfide may be added to this reaction system.
- the amount of the acid binder may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.
- an acid binder may be used in an amount of 1 equivalent or more, preferably 1 to 5 equivalents, per mole of hydroxyl group of the starting polyfunctional hydroxy compound.
- End terminators include pt-butyl-phenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluorohexylphenyl) Phenol, pt-perfluorobutylphenol, 1- (p-hydroxybenzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotridodecyloxy) -1,1,1,3,3,3 -Hexafluoropropyl] phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H- Per
- branching agents include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,6-dimethyl-2,4,6-tris (4- Hydroxyphenyl) -3-heptene, 2,4-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (2-hydroxyphenyl) benzene, 1,3,5- Tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) ) Cyclohexyl] propane, 2,4-bis [2-bis (4-hydroxyphenyl) -2-propyl] phenol, 2,6-bis (2-hydroxy) 5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl)
- the polycarbonate resin (B) may contain a unit having a polyester, polyurethane, polyether or polysiloxane structure in addition to the polycarbonate unit.
- the mass ratio (A) / (B) of the methacrylic resin (A) to the polycarbonate resin (B) is usually 95/5 to 99.9 / 0.1, preferably 96 / It is 4 to 99/1, more preferably 97/3 to 98/2.
- the methacrylic resin (A) and the polycarbonate resin (B) are completely compatible, it is easy to obtain a film having high transparency and good surface smoothness.
- the absolute value of the phase difference of the obtained stretched film can be made small because it exists in this range.
- the total amount of the methacrylic resin (A) and the polycarbonate resin (B) contained in the resin composition according to the present invention is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 94 to 100% by mass, most preferably 96 to 100% by mass.
- the resin composition according to the present invention may contain a filler as necessary within a range not impairing the effects of the present invention.
- the filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate.
- the amount of filler that can be contained in the resin composition of the present invention is preferably 3% by mass or less, more preferably 1.5% by mass or less.
- the resin composition according to the present invention may contain other polymers as long as the effects of the present invention are not impaired.
- Other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1 and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, Styrenic resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate polymer other than methacrylic resin (A), methyl methacrylate-styrene copolymer; polyethylene terephthalate, polybutylene terephthalate Polyester resins such as nylon 6, nylon 66, polyamide such as polyamide elastomer; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, poly Setar
- an antioxidant in the resin composition used in the present invention, an antioxidant, a thermal deterioration inhibitor, an ultraviolet absorber, a light stabilizer, a lubricant, a mold release agent, a polymer processing aid, as long as the effects of the present invention are not impaired. It may contain additives such as an antistatic agent, a flame retardant, a dye / pigment, a light diffusing agent, an organic dye, a matting agent, an impact modifier, and a phosphor.
- the antioxidant alone has an effect of preventing oxidative deterioration of the resin in the presence of oxygen.
- phosphorus antioxidants, hindered phenol antioxidants, thioether antioxidants and the like can be mentioned.
- phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable, and the combined use of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable.
- a phosphorus antioxidant and a hindered phenol antioxidant are used in combination, it is preferable to use a phosphorus antioxidant / hindered phenol antioxidant at a mass ratio of 0.2 / 1 to 2/1. It is preferable to use 0.5 / 1 to 1/1.
- Examples of phosphorus antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA; trade name: ADK STAB HP-10), tris (2,4-di-) t-Butylphenyl) phosphite (manufactured by BASF; trade name: IRUGAFOS168), 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3 , 9-diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: ADK STAB PEP-36).
- hindered phenol antioxidants include 3,5-di-tert-butyl-4-hydroxytoluene, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. ] (Made by BASF; trade name IRGANOX 1010), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (made by BASF; trade name IRGANOX 1076) and the like are preferable.
- the thermal degradation inhibitor can prevent thermal degradation of the resin by trapping polymer radicals that are generated when exposed to high heat in a substantially oxygen-free state.
- the thermal degradation inhibitor include 2-t-butyl-6- (3′-t-butyl-5′-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GM), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilyzer GS) is preferable. .
- the ultraviolet absorber is a compound having an ability to absorb ultraviolet rays, and is mainly said to have a function of converting light energy into heat energy.
- the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like.
- benzotriazoles, triazines, or ultraviolet absorbers having a maximum molar extinction coefficient ⁇ max at a wavelength of 380 to 450 nm of 100 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less are preferable.
- Benzotriazoles are preferable as ultraviolet absorbers used when the film of the present invention is applied to optical applications because it has a high effect of suppressing deterioration of optical properties such as coloring due to ultraviolet irradiation.
- benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329), 2- (2H- Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234), 2,2′-methylenebis [6- (2H-benzotriazole-2) -Yl) -4-t-octylphenol] (manufactured by ADEKA; LA-31), 2- (5-octylthio-2H-benzotriazol-2-yl) -6-tert-butyl-4
- an ultraviolet absorber having a maximum molar extinction coefficient ⁇ max at wavelengths of 380 to 450 nm of 1200 dm 3 ⁇ mol ⁇ 1 cm ⁇ 1 or less can suppress discoloration of the resulting film.
- examples of such an ultraviolet absorber include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan, trade name: Sundebore VSU).
- benzotriazoles are preferably used from the viewpoint of suppressing resin degradation due to ultraviolet irradiation.
- a triazine UV absorber is preferably used.
- examples of such an ultraviolet absorber include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; LA-F70), Hydroxyphenyl triazine-based UV absorbers (manufactured by BASF; TINUVIN477 and TINUVIN460), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine Can be mentioned.
- WO2011 / 089794A1 WO2012 / 124395A1, JP2012-012476, JP2013-023461, JP2013-112790
- Metal complexes having a heterocyclic ligand disclosed in JP2013-194037, JP2014-62228, JP2014-88542, JP2014-88543, and the like for example, A compound having a structure represented by the formula (A) is preferably used as the ultraviolet absorber.
- M is a metal atom.
- Y 1 , Y 2 , Y 3 and Y 4 are each independently a divalent group other than a carbon atom (oxygen atom, sulfur atom, NH, NR 5 etc.).
- R 5 is each independently a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, and an aralkyl group. The substituent may further have a substituent on the substituent.
- Z 1 and Z 2 are each independently a trivalent group (nitrogen atom, CH, CR 6 etc.).
- R 6 is each independently a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, and an aralkyl group.
- the substituent may further have a substituent on the substituent.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, alkyl group, hydroxyl group, carboxyl group, alkoxyl group, halogeno group, alkylsulfonyl group, monophorinosulfonyl group, piperidinosulfonyl group, thio Substituents such as a morpholinosulfonyl group and a piperazinosulfonyl group.
- the substituent may further have a substituent on the substituent.
- a, b, c and d each represent the number of R 1 , R 2 , R 3 and R 4 and are any integer of 1 to 4; ]
- Examples of the ligand of the heterocyclic structure include 2,2′-iminobisbenzothiazole, 2- (2-benzothiazolylamino) benzoxazole, 2- (2-benzothiazolylamino) benzimidazole, ( 2-benzothiazolyl) (2-benzimidazolyl) methane, bis (2-benzoxazolyl) methane, bis (2-benzothiazolyl) methane, bis [2- (N-substituted) benzimidazolyl] methane, and their derivatives .
- As the central metal of such a metal complex copper, nickel, cobalt, and zinc are preferably used.
- the metal complexes In order to use these metal complexes as ultraviolet absorbers, it is preferable to disperse the metal complexes in a medium such as a low molecular compound or a polymer.
- the addition amount of the metal complex is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the film of the present invention. Since the metal complex has a large molar extinction coefficient at a wavelength of 380 nm to 400 nm, the amount to be added is small in order to obtain a sufficient ultraviolet absorption effect. If the amount added is small, deterioration of the resin film appearance due to bleeding out or the like can be suppressed. Moreover, since the metal complex has high heat resistance, there is little deterioration and decomposition during molding. Furthermore, since the metal complex has high light resistance, the ultraviolet absorption performance can be maintained for a long time.
- the light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light.
- Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
- lubricant examples include stearic acid, behenic acid, stearamide acid, methylene bisstearamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hardened oil.
- the mold release agent is a compound having a function of facilitating separation of the molded product from the mold.
- the mold release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride.
- the mass ratio of higher alcohols / glycerin fatty acid monoester is preferably 2.5 / 1 to 3.5 / 1, and preferably 2.8. More preferably, it is used in the range of / 1 to 3.2 / 1.
- polymer particles having a particle diameter of 0.05 to 0.5 ⁇ m which can be usually produced by an emulsion polymerization method, can be used.
- the polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be.
- particles having a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl / g or more in the outer layer are preferable.
- the polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g.
- the impact resistance modifier examples include a core-shell type modifier containing acrylic rubber or diene rubber as a core layer component; a modifier containing a plurality of rubber particles.
- the organic dye a compound having a function of converting ultraviolet rays that are harmful to the resin into visible light is preferably used.
- the light diffusing agent and matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.
- the phosphor examples include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent brightener, and a fluorescent bleach.
- additives may be used alone or in combination of two or more.
- these additives may be added to the polymerization reaction liquid when producing the methacrylic resin (A) or the polycarbonate resin (B), or to the produced methacrylic resin (A) or the polycarbonate resin (B). It may be added or may be added when preparing the resin composition of the present invention.
- the total amount of additives contained in the resin composition of the present invention is preferably 7% by mass or less, more preferably 5% by mass with respect to the methacrylic resin (A) from the viewpoint of suppressing poor appearance of the molded product. Hereinafter, it is more preferably 4% by mass or less.
- the method for preparing the resin composition is not particularly limited.
- a method of polymerizing a monomer mixture containing methyl methacrylate in the presence of polycarbonate resin (B) to produce methacrylic resin (A), or melt-kneading methacrylic resin (A) and polycarbonate resin (B) can be mentioned.
- the melt-kneading method is preferable because the process is simple.
- other polymers and additives may be mixed as necessary, and after mixing methacrylic resin (A) with other polymers and additives, mixed with polycarbonate resin (B).
- the polycarbonate resin (B) may be mixed with other polymers and additives and then mixed with the methacrylic resin (A), or other methods may be used.
- the kneading can be performed using, for example, a known mixing apparatus or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer. Of these, a twin screw extruder is preferred.
- the temperature at the time of mixing and kneading can be appropriately adjusted according to the melting temperature of the methacrylic resin (A) and the polycarbonate resin (B) to be used, but is preferably 110 ° C to 300 ° C.
- the resin composition of the present invention has a glass transition temperature of preferably 120 ° C. or higher, more preferably 123 ° C. or higher, still more preferably 124 ° C. or higher, and particularly preferably 125 ° C. or higher.
- the upper limit of the glass transition temperature of the resin composition of the present invention is not particularly limited, but is preferably 135 ° C.
- the glass transition temperature is an intermediate glass transition temperature measured according to JIS K7121 (temperature increase rate 20 ° C./min).
- Mw determined by GPC measurement is preferably 70,000 to 200,000, more preferably 72,000 to 180,000, still more preferably 75,000 to 150,000.
- Mw / Mn determined by GPC measurement is preferably 1.2 to 5.0, more preferably 1.5 to 3.5.
- the resin composition of the present invention has a melt flow rate determined by measurement under the conditions of 230 ° C. and a load of 3.8 kg, preferably 0.1 to 15 g / 10 minutes, more preferably 0.5 to 5 g / 10. Min, most preferably 1.0 to 3 g / 10 min.
- the resin composition of the present invention has a 1.0 mm thick haze, preferably 1.0% or less, more preferably 0.7% or less, and still more preferably 0.5% or less.
- the resin composition of the present invention can be formed into a molded body such as a film in any form such as pellets, granules, and powders.
- the resin composition of the present invention can be molded into various molded products by a known method.
- the molding method include an extrusion molding method, an injection molding method, a calendar molding method, a blow molding method, a compression molding method, and a solution casting method.
- a known composite molded body manufacturing method such as an insert molding method or a coating molding method can be employed.
- a preferable molded body in the resin composition of the present invention is a film.
- the film which concerns on one Embodiment of this invention is not specifically limited by the manufacturing method.
- the film forming method include a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, and a blow molding method. Of these, the extrusion method is preferred. According to the extrusion method, a film having excellent transparency, improved toughness, excellent handleability, and excellent balance between toughness, surface hardness, and rigidity can be obtained.
- the temperature of the resin composition according to the present invention discharged from the extruder is preferably set to 160 to 270 ° C., more preferably 220 to 260 ° C.
- the resin composition is extruded from a T die in a molten state, and then it is applied to two or more specular rolls.
- molding is preferable.
- the mirror roll or the mirror belt is preferably made of metal.
- the linear pressure between the pair of mirror rolls or the mirror belt is preferably 10 N / mm or more, more preferably 30 N / mm or more.
- the surface temperature of the mirror roll or the mirror belt is preferably 130 ° C. or less.
- the pair of mirror rolls or mirror belts preferably have at least one surface temperature of 60 ° C. or higher. When such a surface temperature is set, the resin composition discharged from the extruder can be cooled at a speed faster than natural cooling, and the film of the present invention having excellent surface smoothness and low haze can be produced. easy.
- the film of the present invention is preferably subjected to a stretching treatment in at least one direction.
- the stretching treatment is not particularly limited, and examples thereof include uniaxial stretching, simultaneous biaxial stretching, sequential biaxial stretching, and Tubler stretching.
- the temperature during stretching is preferably from 100 to 200 ° C., more preferably from 120 to 160 ° C. from the viewpoint that uniform stretching can be performed and a high-strength film can be obtained.
- Stretching is usually performed at 100 to 5000% / min on a length basis.
- the area stretch ratio is preferably 1.5 to 8 times. After stretching, a film with less heat shrinkage can be obtained by heat-setting or relaxing the film.
- the amount of the methacrylic resin (A) contained therein is preferably 73 to 99% by mass, more preferably 80%, from the viewpoint that transparency and the absolute value of retardation in the thickness direction are small. It is -97 mass%, More preferably, it is 85-95 mass%.
- the amount of the polycarbonate resin (B) contained therein is preferably 1 to 5% by mass, more preferably 1.% by mass from the viewpoint that the absolute value of retardation in the thickness direction is small. It is 5 to 4% by mass, more preferably 2 to 3% by mass.
- the thickness of the film of the present invention is preferably 1 to 200 ⁇ m, more preferably 10 to 50 ⁇ m, and still more preferably 15 to 40 ⁇ m.
- the film of the present invention has a haze at a thickness of 40 ⁇ m, preferably 0.3% or less, more preferably 0.2% or less. Thereby, it is excellent in surface glossiness and transparency. Further, in optical applications such as a liquid crystal protective film and a light guide film, the use efficiency of the light source is preferably increased. Furthermore, it is preferable because it is excellent in shaping accuracy when performing surface shaping.
- the in-plane retardation Re at a thickness of 40 ⁇ m with respect to light having a wavelength of 590 nm is preferably 19 nm or less, more preferably 15 nm or less, still more preferably 10 nm or less, particularly preferably 5 nm or less, and most preferably 1 nm. It is as follows.
- the film of the present invention has a thickness direction retardation Rth at a thickness of 40 ⁇ m with respect to light having a wavelength of 590 nm, preferably ⁇ 12 nm to 12 nm, more preferably ⁇ 5 nm to 5 nm, still more preferably ⁇ 3 nm to 3 nm, particularly It is preferably ⁇ 2 nm or more and 2 nm or less, and most preferably ⁇ 1 nm or more and 1 nm or less.
- the in-plane direction phase difference Re and the thickness direction phase difference Rth are values defined by the following equations, respectively.
- n x is a refractive index in a slow axis direction of the film
- n y is a refractive index in a fast axis direction of the film
- n z is a refractive index in the thickness direction of the film
- d [nm ] Is the thickness of the film.
- the slow axis is an axis in the direction in which the refractive index in the film plane becomes maximum.
- the fast axis is an axis in a direction perpendicular to the slow axis in the plane.
- the film of the present invention has a photoelastic coefficient ⁇ with respect to light having a wavelength of 590 nm, preferably ⁇ 3.0 ⁇ 10 ⁇ 12 Pa ⁇ 1 or more and 3.0 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less, more preferably ⁇ 2.0.
- ⁇ 10 ⁇ 12 Pa ⁇ 1 or more and 2.0 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less more preferably ⁇ 1.0 ⁇ 10 ⁇ 12 Pa ⁇ 1 or more and 1.0 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less.
- the in-plane direction phase difference Re, the thickness direction phase difference Rth, and the photoelastic coefficient ⁇ are within such ranges, the influence on the display characteristics of the image display apparatus due to the phase difference can be remarkably suppressed. More specifically, interference unevenness and 3D image distortion when used in a liquid crystal display device for 3D display can be significantly suppressed.
- a functional layer may be provided on the surface of the film of the present invention.
- the functional layer include a hard coat layer, an antiglare layer, an antireflection layer, an anti-sticking layer, a diffusion layer, an antiglare layer, an antistatic layer, an antifouling layer, and a slippery layer such as fine particles.
- the film of the present invention has high transparency, low thermal shrinkage, small dimensional change due to water absorption, uniform thickness, and excellent surface smoothness.
- the retardation film, the polarizer protective film, the liquid crystal protective plate, the surface material of the portable information terminal, the display window of the portable information terminal It is suitable for protective films, light guide films, transparent conductive films coated with silver nanowires and carbon nanotubes on the surface, and front plate applications for various displays.
- the film of the present invention is suitable for a polarizer protective film because the absolute value of the retardation in the thickness direction can be reduced.
- the film of the present invention has high transparency and heat resistance, IR cut film, crime prevention film, anti-scattering film, decorative film, metal decorative film, solar cell back sheet, flexible solar, etc. can be used for applications other than optical applications. It can be used for a battery front sheet, a shrink film, and an in-mold label film.
- the polarizing plate of the present invention has a polarizer and the film of the present invention laminated on the polarizer.
- the film of the present invention may be laminated on both sides of the polarizer or may be laminated on one side.
- an optical film other than the film of the present invention can be laminated on another side.
- the optical film include a polarizer protective film, a viewing angle adjusting film, a retardation film, and a brightness enhancement film. Lamination can also be performed via an adhesive layer.
- the polarizing plate according to a preferred embodiment of the present invention is formed by laminating the film of the present invention, an easily adhesive layer, an adhesive layer, a polarizer, an adhesive layer, and the film of the present invention in this order, or
- stacked in order of optical films other than the film of this invention (refer FIG. 1) can be mentioned.
- the polarizer is a known optical element.
- a polarizer what consists of polyvinyl alcohol-type resin can be mentioned.
- the polyvinyl alcohol resin used for the polarizer has a polymerization degree of preferably 100 to 5000, more preferably 1400 to 4000.
- a polyvinyl alcohol-type resin film can be manufactured by the casting method, the casting method, the extrusion method etc., for example.
- the thickness of the polyvinyl alcohol-based resin film used for the polarizer can be appropriately set according to the purpose and use of the LCD in which the polarizing plate is used, but is typically 5 to 80 ⁇ m.
- the adhesive layer that can be provided on the polarizing plate of the present invention is not particularly limited as long as it is optically transparent.
- an adhesive constituting the adhesive layer for example, a water-based adhesive, a solvent-based adhesive, a hot-melt adhesive, an active energy ray-curable adhesive, or the like can be used. Of these, water-based adhesives and active energy ray-curable adhesives are suitable.
- the water-based adhesive is not particularly limited.
- the aqueous adhesive may be in the form of an aqueous solution or latex.
- the water-based adhesive include a vinyl polymer-based adhesive, a gelatin-based adhesive, a polyurethane-based adhesive, an isocyanate-based adhesive, a polyester-based adhesive, and an epoxy-based adhesive.
- an adhesive containing a vinyl polymer is preferable.
- the vinyl polymer a polyvinyl alcohol resin is preferable.
- the adhesive containing a polyvinyl alcohol-based resin can contain a water-soluble crosslinking agent such as boric acid, borax, glutaraldehyde, melamine, or oxalic acid.
- An adhesive containing a polyvinyl alcohol-based resin is suitable because it has excellent adhesiveness with a polarizer made of a polyvinyl alcohol-based resin film.
- An adhesive containing a polyvinyl alcohol-based resin having an acetoacetyl group is more preferably used because it improves the durability of the polarizing plate.
- the solid content contained in the aqueous adhesive is usually 0.5 to 60% by mass.
- the water-based adhesive may contain an additive such as a crosslinking agent, a catalyst such as an acid, and a metal compound filler. With the metal compound filler, the fluidity of the adhesive layer can be controlled, the film thickness can be stabilized, and a polarizing plate having a good appearance, uniform in-plane and no adhesive variation can be obtained.
- the active energy ray-curable adhesive a compound having a monofunctional or bifunctional (meth) acryloyl group or a compound having a vinyl group is used as a curable component, and an epoxy compound, an oxetane compound, a photoacid generator, It is also possible to use a photocationic curing component mainly composed of As the active energy ray, an electron beam or an ultraviolet ray can be used.
- the method for forming the adhesive layer is not particularly limited. For example, it can be formed by applying the adhesive to an object and then heating or drying. Application
- coating of an adhesive agent may be performed with respect to a polarizer protective film, and may be performed with respect to a polarizer. After forming the adhesive layer, both can be laminated by pressing the polarizer protective film and the polarizer together. In the lamination, a roll press machine or a flat plate press machine can be used. The heating and drying temperature and drying time are appropriately determined according to the type of adhesive.
- the thickness of the adhesive layer is preferably 0.01 to 10 ⁇ m, more preferably 0.03 to 5 ⁇ m in the dry state.
- the easy-adhesion layer that can be provided on the polarizing plate of the present invention improves the adhesion of the surface where the polarizer protective film and the polarizer are in contact.
- the easy adhesion layer can be provided by an easy adhesion treatment or the like. Examples of the easy adhesion treatment include surface treatment such as corona treatment, plasma treatment, and low-pressure UV treatment.
- the easy adhesion layer can be provided by a method of forming an anchor layer or a combination of the surface treatment and the method of forming an anchor layer. Among these, a corona treatment, a method of forming an anchor layer, and a method of using these in combination are preferable.
- the anchor layer examples include a silicone layer having a reactive functional group.
- the material of the silicone layer having a reactive functional group is not particularly limited.
- an isocyanate group-containing alkoxysilanol, an amino group-containing alkoxysilanol, a mercapto group-containing alkoxysilanol, a carboxy-containing alkoxysilanol, an epoxy group-containing Examples include alkoxysilanols, vinyl-type unsaturated group-containing alkoxysilanols, halogen group-containing alkoxysilanols, and isocyanate group-containing alkoxysilanols. Of these, amino silanols are preferred.
- the adhesive strength can be strengthened.
- other additives include tackifiers such as terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins; stabilizers such as ultraviolet absorbers, antioxidants, and heat stabilizers.
- the layer which consists of what saponified cellulose acetate butyrate resin as an anchor layer is also mentioned.
- the anchor layer is formed by coating and drying by a known technique.
- the thickness of the anchor layer is preferably 1 to 100 nm, more preferably 10 to 50 nm in a dry state.
- the anchor layer forming chemical may be diluted with a solvent.
- the dilution solvent is not particularly limited, and examples thereof include alcohols.
- the dilution concentration is not particularly limited, but is preferably 1 to 5% by mass, more preferably 1 to 3% by mass.
- the optical film other than the film of the present invention is not particularly limited by the material constituting it.
- the material for the optical film include cellulose resin, polycarbonate resin, cyclic polyolefin resin, and methacrylic resin.
- Cellulose resin is an ester of cellulose and fatty acid.
- cellulose ester resins include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Among these, cellulose triacetate is particularly preferable.
- Many products of cellulose triacetate are commercially available, which is advantageous in terms of availability and cost. Examples of commercially available cellulose triacetate products are trade names “UV-50”, “UV-80”, “SH-80”, “TD-80U”, “TD-TAC”, “UZ-” manufactured by FUJIFILM Corporation. TAC ",” KC series "manufactured by Konica Minolta, and the like.
- the cyclic polyolefin resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Can be mentioned. Specific examples include cyclic olefin ring-opening (co) polymers, cyclic olefin addition polymers, copolymers of cyclic olefins and ⁇ -olefins such as ethylene and propylene (typically random copolymers), And the graft polymer which modified these by unsaturated carboxylic acid or its derivative (s), those hydrides, etc. can be mentioned. Specific examples of the cyclic olefin include norbornene monomers.
- cyclic polyolefin resins As specific examples, trade names “ZEONEX” and “ZEONOR” manufactured by ZEON Corporation, “ARTON” manufactured by JSR, “TOPAS” manufactured by Polyplastics, and “Product Name” manufactured by Mitsui Chemicals, Inc. APEL ".
- methacrylic resin used for the optical film other than the film of the present invention any appropriate methacrylic resin can be adopted as long as the effects of the present invention are not impaired.
- methacrylic acid ester polymer such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- ( (Meth) acrylic acid copolymer, (meth) methyl acrylate-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (eg, methyl methacrylate-cyclohexyl methacrylate copolymer, etc.) Can be mentioned.
- the methacrylic resin for example, an acrylic resin obtained by copolymerizing methyl methacrylate and a maleimide monomer described in Acrypet VH or Acrypet VRL20A manufactured by Mitsubishi Rayon Co., Ltd., or JP2013-033237A or WO2013 / 005634A.
- Tg glass transition temperature
- a methacrylic resin used for an optical film other than the film of the present invention a methacrylic resin having a lactone ring structure can also be used. It is because it has high mechanical strength by high heat resistance, high transparency, and biaxial stretching.
- the methacrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, JP 2005-146084, and the like.
- a methacrylic resin having a lactone ring structure as described in 1. above.
- the polarizing plate of the present invention can be used for an image display device.
- the image display device include a self-luminous display device such as an electroluminescence (EL) display, a plasma display (PD), and a field emission display (FED), and a liquid crystal display (LCD).
- EL electroluminescence
- PD plasma display
- FED field emission display
- LCD liquid crystal display
- the liquid crystal display device includes a liquid crystal cell and the polarizing plate disposed on at least one side of the liquid crystal cell.
- the unstretched film is cut into a size of 20 mm ⁇ 40 mm, the film piece is set on an elliptical polarization measuring device with both ends in the major axis direction sandwiched, and a temperature of 23 is applied while applying a stress of 10 6 to 10 7 Pa in the major axis direction.
- the in-plane direction phase difference Rin at the center of the film piece in light having a wavelength of 590 nm was measured under the conditions of ⁇ 2 ° C. and humidity of 50 ⁇ 5%.
- the unstretched film was cut into a size of 100 mm ⁇ 50 mm, the film piece was set on a cylindrical mandrel bending tester equipped with a cylindrical mandrel having a diameter of 6 mm, and the state of the film piece when bent 180 degrees was evaluated. .
- Mw and Mw / Mn were calculated from the values obtained by measuring chromatograms under gel gel permeation chromatography (GPC) under the following conditions and converting them to the molecular weight of standard polystyrene.
- GPC device manufactured by Tosoh Corporation, HLC-8320 Detector: Differential refractive index detector
- Eluent Tetrahydrofuran
- Eluent flow rate 0.35 ml / min
- Column temperature 40 ° C
- Calibration curve Created using 10 standard polystyrene data
- Glass transition temperature Tg Glass transition temperature Tg
- DSC-50 product number manufactured by Shimadzu Corporation
- MVR Melt volume flow rate
- Total light transmittance (T t ) The total light transmittance was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) according to JIS K7361-1.
- haze (H) Based on JIS K7136, haze (H) was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150).
- Phase difference in in-plane direction (Re) A test piece of 40 mm x 40 mm is set in an automatic birefringence meter (KOBRA-WR manufactured by Oji Scientific Co., Ltd.), and the phase difference at a wavelength of 590 nm and an incident angle of 0 ° is obtained at a temperature of 23 ⁇ 2 ° C and a humidity of 50 ⁇ 5%. It was measured.
- n x is a plane slow axis direction of the refractive index
- n y is the refractive index of the direction perpendicular in the plane with respect to the slow axis
- n z is a refractive index in the thickness direction.
- the thickness d [nm] of the test piece was measured using a digimatic indicator (manufactured by Mitutoyo Corporation).
- the average refractive index n required for calculating the refractive indices n x, n y and n z were measured by a digital precision refractometer (Kalnew Optical Industry Co., Ltd. KPR-20).
- methyl methacrylate is MMA and methacrylate tricyclo [5.2.1.0 2,6 ] decan-8-yl (X in the formula (1) is tricyclo [5.2.1. 0 2,6] compound decane-8-yl group) and TCDMA, IBMA and isobornyl methacrylate compound X is isobornane 2-yl group in the (formula (1)), CHMA cyclohexyl methacrylate, and acrylic acid Methyl is abbreviated as MA.
- the oxygen gas in the production apparatus was purged with nitrogen gas.
- the raw material liquid is supplied from an autoclave to a continuous flow tank reactor controlled at a temperature of 140 ° C. at a constant flow rate so that the average residence time is 120 minutes, and bulk polymerization is performed at a polymerization conversion rate of 57% by mass. I let you.
- the liquid discharged from the tank reactor was heated to 250 ° C., supplied to a twin-screw extruder controlled at 260 ° C. at a constant flow rate, and adiabatic flushed at the inlet of the extruder. Volatiles (monomer, dimer, trimer, etc.) removed by the adiabatic flash were discharged from the open vent.
- Volatile components mainly composed of unreacted monomers were discharged from a vent reduced to 6 Torr provided downstream from the twin-screw extruder inlet, and the remaining resin component was extruded into a strand shape with a screw.
- the strand was cut with a pelletizer to obtain a pellet-shaped methacrylic resin ⁇ PMMA1>.
- the structural unit derived from MMA was 85 mass%
- the structural unit derived from TCDMA was 14 mass%
- the structural unit derived from MA was 1 mass%.
- the weight average molecular weight (Mw) was 67000
- molecular weight distribution (Mw / Mn) was 1.81
- glass transition temperature (Tg) was 125 degreeC. Table 1 shows the analysis results of the methacrylic resin.
- MMA 3 to 11 Methyl methacrylate (MMA), tricyclomethacrylate [5.2.1.0 2,6 ] deca-8-nyl (TCDMA), methyl acrylate (MA), isobornyl methacrylate (IBMA), cyclohexyl methacrylate (CHMA) ), N-octyl mercaptan (n-OM), and pentaerythritol tetrakisthiopropionate (PETP) were changed in the same manner as in Production Example 2 except that the amount of methacrylic resin ⁇ PMMA3 ⁇ 11>. Tables 1 and 2 show the analysis results of the methacrylic resin.
- t-amyl peroxyisononanoate Arkema Yoshitomi, trade name: Luperox 570
- 0.05 parts by mass of 2-ethylhexyl phosphate Phoslex A-8, manufactured by Sakai Chemical Industry Co., Ltd.
- cyclization catalyst cyclization catalyst
- the cyclization condensation reaction was allowed to proceed for 2 hours under reflux at 0 ° C., and then the polymerization solution was heated for 30 minutes in an autoclave at 240 ° C. to further proceed the cyclization condensation reaction.
- a methacrylic resin ⁇ PMMA12> having a lactone ring in the main chain was obtained.
- Table 2 shows the analysis results of the methacrylic resin ⁇ PMMA12>.
- Paraloid K125-P (manufactured by Dow Chemical Company) was prepared as a processing aid.
- Example 1> Uniaxially stretched film 96 parts by weight of methacrylic resin ⁇ PMMA1> and 4 parts by weight of polycarbonate resin ⁇ PC1> were mixed together, and a biaxial extruder (trade name: KZW20TW-45MG-NH-600, manufactured by Technobel). A resin composition [1] was produced by kneading and extruding at 250 ° C.
- the glass transition temperature Tg and the yellow index YI of the resin composition [1] were measured.
- the resin composition [1] was subjected to hot press molding to obtain a plate-like molded body having a thickness of 50 mm ⁇ 50 mm ⁇ 1.0 mm.
- the total light transmittance T t and haze H at a thickness of 1.0 mm were measured. The results are shown in Table 3.
- Resin composition [1] was dried at 80 ° C. for 12 hours. Using a 20 mm ⁇ single screw extruder (OCS), the resin composition [1] is extruded from a 150 mm wide T-die at a resin temperature of 260 ° C., and is taken up by a roll having a surface temperature of 110 ° C. An unstretched film having a thickness of 80 ⁇ m was obtained. Table 3 shows the strength of the unstretched film and the photoelastic coefficient ⁇ .
- OCS 20 mm ⁇ single screw extruder
- the unstretched film was cut into a size of 50 mm ⁇ 40 mm, and set in a tensile tester (AG-IS 5 kN, manufactured by Shimadzu Corporation) so that the distance between chucks was 20 mm.
- the film was uniaxially stretched at a stretch rate of% / min and an area stretch ratio of 2 in the machine direction, held for 10 seconds, and then rapidly cooled to obtain a uniaxially stretched film having a thickness of 40 ⁇ m.
- Table 3 shows the measurement results of the thickness d, in-plane direction retardation Re, thickness direction retardation Rth, total light transmittance T t , haze H, and wet heat shrinkage of the uniaxially stretched film.
- An unstretched film having a width of 110 mm and a thickness of 80 ⁇ m and a uniaxially stretched film of 40 ⁇ m were prepared in the same manner as in Example 1 except that the resin compositions [2] to [17] were used instead of the resin composition [1]. Obtained.
- the evaluation results of the unstretched film and the uniaxially stretched film are shown in Table 3 or 4. In Comparative Examples 1 and 5, the unstretched film could not be uniaxially stretched due to insufficient strength.
- Example 8 Biaxially stretched film Resin composition [19] was manufactured by the same method as Example 1 except having changed into the composition shown in Table 5.
- FIG. An unstretched film having a width of 110 mm was obtained in the same manner as in Example 1 except that the resin composition [19] was used instead of the resin composition [1] and the thickness of the obtained film was 160 ⁇ m. This unstretched film was cut into a size of 100 mm ⁇ 100 mm.
- the section was set in a pantograph type biaxial stretching tester (manufactured by Toyo Seiki Co., Ltd.), stretching temperature: glass transition temperature + 20 ° C., longitudinal stretching rate: 1000% / min, transverse stretching rate 1000% / min, A biaxially stretched film having a thickness of 40 ⁇ m was obtained by simultaneous biaxial stretching at a longitudinal stretching ratio of 2 times and a transverse stretching ratio of 2 times, holding for 10 seconds, and then rapidly cooling.
- Table 5 shows the evaluation results of the resin composition [19], the unstretched film, and the biaxially stretched film.
- a resin composition [18] was produced in the same manner as in Example 8 except that the composition shown in Table 5 was changed.
- An unstretched film having a width of 110 mm and a thickness of 160 ⁇ m and a biaxially stretched film having a thickness of 40 ⁇ m were obtained in the same manner as in Example 8 except that the resin composition [18] was used instead of the resin composition [19].
- Table 5 shows the evaluation results of the resin composition [18], the unstretched film, and the biaxially stretched film. Since the saturated water absorption rate of PMMA 12 was high, the wet heat shrinkage rate was large.
- Example 12 A resin composition [23] was produced in the same manner as in Example 8 except that the composition shown in Table 5 was changed.
- An unstretched film having a width of 110 mm was obtained in the same manner as in Example 8, except that the resin composition [23] was used instead of the resin composition [19] and the thickness of the obtained film was changed to 80 ⁇ m.
- the biaxially stretched film was obtained by the same method as Example 8 except the thickness of the film obtained having been 20 micrometers.
- Table 5 shows the evaluation results of the resin composition [23], the unstretched film, and the biaxially stretched film.
- Polyester urethane (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 210, solid content: 33%) 16.8 g, cross-linking agent (oxazoline-containing polymer, product of Nippon Shokubai, trade name: Epocross WS-700, solid content: 25% ) 4.2 g, 2.0 g of 1 wt% ammonia water, 0.42 g of colloidal silica (manufactured by Fuso Chemical Co., Ltd., Quartron PL-3, solid content: 20 wt%) and 76.6 g of pure water were mixed to facilitate adhesion. An agent composition was obtained.
- N-hydroxyethylacrylamide (manufactured by Kojin Co., Ltd.) 38.3 parts by mass, tripropylene glycol diacrylate (trade name: Aronix M-220, manufactured by Toagosei Co., Ltd.) 19.1 parts by mass, acryloylmorpholine (manufactured by Kojin Co., Ltd.) 38.3 parts by mass and 1.4 parts by mass of a photopolymerization initiator (trade name: KAYACURE DETX-S, diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) are mixed and stirred at 50 ° C. for 1 hour for active energy ray curing. A mold adhesive was obtained.
- the biaxially stretched film obtained in Example 11 (hereinafter referred to as film a) was subjected to corona discharge treatment.
- the easy-adhesive composition was applied to the corona discharge-treated surface of film a with a bar coater so as to have a thickness of 100 nm after drying. Then, it dried for about 5 minutes in the hot air dryer (110 degreeC), and the easily bonding layer was formed in the single side
- the said active energy ray hardening-type adhesive agent was apply
- the film a was superposed on each of both surfaces of the polarizer using a small laminator with the adhesive layer facing the polarizer. Both sides are heated to 50 ° C. using an IR heater, irradiated with ultraviolet rays with an integrated irradiation amount of 1000 / mJ / cm 2 to cure the active energy ray-curable adhesive, and film a on both sides of the polarizer To obtain a polarizing plate X.
- the polarizing plate X was left in a constant temperature and humidity chamber at 80 ° C. and 90% RH for 100 hours. Then, the polarizing plate X taken out from the constant temperature and humidity chamber was visually observed. Degradation of the polarizer was not observed.
- Comparative Example 12 A 40 ⁇ m thick triacetylcellulose film was saponified by dipping in a 10% aqueous sodium hydroxide solution (60 ° C.) for 30 seconds. Thereafter, the film was washed with water for 60 seconds to obtain a film b. 100 parts by mass of an acetoacetyl group-containing polyvinyl alcohol resin (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetyl group modification degree: 5 mol%), and 20 parts by mass of methylol melamine at 30 ° C. An adhesive composition having a solid content concentration of 0.5% was obtained by dissolving in pure water under temperature conditions. The adhesive composition was left in an environment of 30 ° C. for 30 minutes.
- the adhesive composition was applied to film b so as to have a thickness of 50 nm after drying to form an adhesive layer.
- the film b was superposed on each of both surfaces of the polarizer using a small laminator with the adhesive layer facing the polarizer. It was dried in a hot air dryer (70 ° C.) for 5 minutes to obtain a polarizing plate Y in which the film b was laminated on both sides of the polarizer.
- the polarizing plate Y was left in a constant temperature and humidity chamber at 80 ° C. and 90% RH for 100 hours. Then, the polarizing plate Y taken out from the constant temperature and humidity chamber was visually observed. Degradation of the polarizer was observed.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polarising Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
Description
ポリカーボネート樹脂(B)とを
ポリカーボネート樹脂(B)に対するメタクリル樹脂(A)の質量比(A)/(B)が95/5~99.9/0.1で含有して成る樹脂組成物。
〔2〕 メタクリル酸多環式脂肪族炭化水素エステルが、式(1)で表される化合物である、〔1〕に記載の樹脂組成物。
〔4〕 メタクリル酸多環式脂肪族炭化水素エステル以外のメタクリル酸エステルがメタクリル酸メチルである〔1〕~〔3〕のいずれかひとつに記載の樹脂組成物。
〔5〕 JIS K7121(昇温速度20℃/分)で測定される中間点ガラス転移温度が120℃以上である〔1〕~〔4〕のいずれかひとつに記載の樹脂組成物。
〔6〕 メタクリル樹脂(A)とポリカーボネート樹脂(B)との合計含有量が80~100質量%である〔1〕~〔5〕のいずれかひとつに記載の樹脂組成物。
〔7〕 前記〔1〕~〔6〕のいずれかひとつに記載の樹脂組成物からなるフィルム。
〔8〕厚さが10~50μmである、〔7〕に記載のフィルム。
〔9〕 面積比で1.5~8倍に二軸延伸された〔7〕または〔8〕に記載のフィルム。
〔10〕 少なくとも一軸延伸された〔7〕または〔8〕に記載のフィルム。
〔11〕 前記〔7〕~〔10〕のいずれかひとつに記載のフィルムからなる偏光子保護フィルム。
〔12〕 前記〔7〕~〔10〕のいずれかひとつに記載のフィルムからなる位相差フィルム。
〔13〕 偏光子と、該偏光子に積層された〔7〕~〔10〕のいずれかひとつに記載のフィルムとを有する偏光板。
アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸2-エチルへキシルなどのアクリル酸鎖状脂肪族炭化水素エステル;アクリル酸フェニルなどのアクリル酸芳香族炭化水素エステル;アクリル酸シクロへキシル、アクリル酸ノルボルネニルなどのアクリル酸脂環式炭化水素エステルなどを挙げることができる。これらの中で熱分解が抑制でき、製膜が容易であるという点から、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチルが好ましく、アクリル酸メチルが特に好ましい。
重合反応は、重合開始剤と、前述の単量体と、必要に応じて連鎖移動剤などとを用いて行われる。
重合開始剤としては、例えば、t-ヘキシルパーオキシイソプロピルモノカーボネート、t-ヘキシルパーオキシ2-エチルヘキサノエート、1,1,3,3-テトラメチルブチルパーオキシ2-エチルヘキサノエート、t-ブチルパーオキシピバレート、t-ヘキシルパーオキシピバレート、t-ブチルパーオキシネオデカノエ-ト、t-ヘキシルパーオキシネオデカノエ-ト、1,1,3,3-テトラメチルブチルパーオキシネオデカノエート、1,1-ビス(t-ヘキシルパーオキシ)シクロヘキサン、ベンゾイルパーオキシド 、3,5,5-トリメチルヘキサノイルパーオキシド、ラウロイルパーオキシド、2,2’-アゾビス(2-メチルプロピオニトリル)、2,2’-アゾビス(2-メチルブチロニトリル)、ジメチル2,2’-アゾビス(2-メチルプロピオネート)などを挙げることができる。中でも、t-ヘキシルパーオキシ2-エチルヘキサノエート、1,1-ビス(t-ヘキシルパーオキシ)シクロヘキサン、ジメチル2,2’-アゾビス(2-メチルプロピオネート)が好ましい。
また、塊状重合の場合、好ましくは100~200℃、より好ましくは110~180℃である。塊状重合反応時の温度が100℃以上であることで、重合速度の向上、重合液の低粘度化などに起因して生産性が向上する傾向となる。また塊状重合反応時の温度が200℃以下であることで、重合速度の制御が容易になり、さらに副生成物の生成が抑制されるので本発明の樹脂組成物の着色を抑制できる。
(式中、R1、R2およびR3は、それぞれ独立して置換基を有してもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有してもよいアリール基、置換基を有していてもよいアラルキル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基またはN,N-二置換アミノ基を表す。さらに、R2およびR3は、それらが結合してなる、置換基を有していてもよいアリーレンジオキシ基であってもよい。)
また、アニオン重合法においては、重合反応を制御するために、エーテルや含窒素化合物などを共存させることもできる。
本発明に係る樹脂組成物に含有されるメタクリル樹脂(A)とポリカーボネート樹脂(B)との合計量は、好ましくは80~100質量%、より好ましくは90~100質量%、さらに好ましくは94~100質量%、最も好ましくは96~100質量%である。
リン系酸化防止剤とヒンダードフェノール系酸化防止剤とを併用する場合、リン系酸化防止剤/ヒンダードフェノール系酸化防止剤を質量比で0.2/1~2/1で使用するのが好ましく、0.5/1~1/1で使用するのがより好ましい。
該熱劣化防止剤としては、2-t-ブチル-6-(3’-t-ブチル-5’-メチル-ヒドロキシベンジル)-4-メチルフェニルアクリレート(住友化学社製;商品名スミライザーGM)、2,4-ジt-アミル-6-(3’,5’-ジ-t-アミル-2’-ヒドロキシ-α-メチルベンジル)フェニルアクリレート(住友化学社製;商品名スミライザーGS)などが好ましい。
紫外線吸収剤としては、ベンゾフェノン類、ベンゾトリアゾール類、トリアジン類、ベンゾエート類、サリシレート類、シアノアクリレート類、蓚酸アニリド類、マロン酸エステル類、ホルムアミジン類などを挙げることができる。これらの中でも、ベンゾトリアゾール類、トリアジン類、または波長380~450nmにおけるモル吸光係数の最大値εmaxが100dm3・mol-1cm-1以下である紫外線吸収剤が好ましい。
これら紫外線吸収剤の中、紫外線被照による樹脂劣化が抑えられるという観点からベンゾトリアゾール類が好ましく用いられる。
ロヘキサン1Lに紫外線吸収剤10.00mgを添加し、目視による観察で未溶解物がないように溶解させる。この溶液を1cm×1cm×3cmの石英ガラスセルに注入し、日立製作所社製U-3410型分光光度計を用いて、波長380~450nm、光路長1cmでの吸光度を測定する。紫外線吸収剤の分子量(MUV)と、測定された吸光度の最大値(Amax)とから次式により計算し、モル吸光係数の最大値εmaxを算出する。
εmax=[Amax/(10×10-3)]×MUV
〔式(A)中、Mは金属原子である。
Y1、Y2、Y3およびY4はそれぞれ独立に炭素原子以外の二価基(酸素原子、硫黄原子、NH、NR5など)である。R5はそれぞれ独立にアルキル基、アリール基、ヘテロアリール基、ヘテロアラルキル基、アラルキル基などの置換基である。該置換基は、該置換基にさらに置換基を有してもよい。
Z1およびZ2はそれぞれ独立に三価基(窒素原子、CH、CR6など)である。R6はそれぞれ独立にアルキル基、アリール基、ヘテロアリール基、ヘテロアラルキル基、アラルキル基などの置換基である。該置換基は、該置換基にさらに置換基を有してもよい。
R1、R2、R3およびR4はそれぞれ独立に水素原子、アルキル基、ヒドロキシル基、カルボキシル基、アルコキシル基、ハロゲノ基、アルキルスルホニル基、モノホリノスルホニル基、ピペリジノスルホニル基、チオモルホリノスルホニル基、ピペラジノスルホニル基などの置換基である。該置換基は、該置換基にさらに置換基を有してもよい。a、b、cおよびdはそれぞれR1、R2、R3およびR4の数を示し且つ1~4のいずれかの整数である。〕
有機色素としては、樹脂に対しては有害とされている紫外線を可視光線に変換する機能を有する化合物が好ましく用いられる。
光拡散剤や艶消し剤としては、ガラス微粒子、ポリシロキサン系架橋微粒子、架橋ポリマー微粒子、タルク、炭酸カルシウム、硫酸バリウムなどを挙げることができる。
蛍光体として、蛍光顔料、蛍光染料、蛍光白色染料、蛍光増白剤、蛍光漂白剤などを挙げることができる。
本発明の一実施形態に係るフィルムは、その製法によって特に限定されない。製膜法としては、例えば、溶液キャスト法、溶融流延法、押出成形法、インフレーション成形法、ブロー成形法などを挙げることができる。これらのうち、押出成形法が好ましい。押出成形法によれば、透明性に優れ、改善された靭性を持ち、取扱い性に優れ、靭性と表面硬度および剛性とのバランスに優れたフィルムを得ることができる。押出機から吐出される本発明に係る樹脂組成物の温度は、好ましくは160~270℃、より好ましくは220~260℃に設定する。
また、本発明のフィルムは、その中に含まれるポリカーボネート樹脂(B)の量が、厚さ方向の位相差の絶対値が小さいという観点から、好ましくは1~5質量%、より好ましくは1.5~4質量%、さらに好ましくは2~3質量%である。
本発明のフィルムは、波長590nmの光に対する厚さ40μmにおける厚さ方向位相差Rthが、好ましくは-12nm以上12nm以下、より好ましくは-5nm以上5nm以下、さらに好ましくは-3nm以上3nm以下、特に好ましくは-2nm以上2nm以下、最も好ましくは-1nm以上1nm以下である。
なお、面内方向位相差Reおよび厚さ方向位相差Rthは、それぞれ、以下の式で定義される値である。
Re=(nx-ny)×d
Rth=((nx+ny)/2-nz)×d
ここで、nxはフィルムの遅相軸方向の屈折率であり、nyはフィルムの進相軸方向の屈折率であり、nzはフィルムの厚さ方向の屈折率であり、d[nm]はフィルムの厚さである。遅相軸はフィルム面内の屈折率が最大になる方向の軸である。進相軸は面内において遅相軸に対して直角となる方向の軸である。
Rin=β×σ×d
活性エネルギー線としては、電子線や紫外線を用いることができる。
ガスクロマトグラフ(島津製作所社製、GC-14A)に、カラム(GLC-G-230 Sciences Inc.製、INERT CAP 1(df=0.4μm、I.D.0.25mm、長さ60m))を繋ぎ、injection温度180℃、detector温度180℃、カラム温度を10℃/分で60℃から200℃に昇温する条件にて分析し、その結果に基づいて重合転化率を算出した。
核磁気共鳴装置(Bruker社製 ULTRA SHIELD 400 PLUS)を用い、樹脂10mgに対して重水素化クロロホルム1mL、室温、積算回数64回の条件にて、1H-NMRスペクトルを測定し、そのスペクトルから樹脂中の単量体単位の組成を算出した。
未延伸フィルムを、20mm×40mmの大きさに切り出し、フィルム片を長軸方向の両端を挟んで楕円偏光測定装置にセットし、長軸方向に応力を106~107Paかけながら、温度23±2℃、湿度50±5%の条件で、波長590nmの光におけるフィルム片中央の面内方向位相差Rinを測定した。応力と位相差との相関関係(Rin=β×σ×d、Rin:応力σ[Pa]を印加した際の面内方向位相差〔nm〕、β:光弾性係数 [10-12Pa-1]、σ:応力 [Pa]、d:フィルム厚み [nm])から光弾性係数βを算出した。
未延伸フィルムを、100mm×50mmの大きさに切り出し、フィルム片を直径6mmの円筒形マンドレルを装着した円筒形マンドレル屈曲試験器にセットし、180度屈曲させた際のフィルム片の状態を評価した。
A:フィルムに変化はなく、得られたままの状態を保持できた。
B:フィルムがもろく、割れてしまった。
MwおよびMw/Mnは、ゲルパーミエーションクロマトグラフィー(GPC)にて下記の条件でクロマトグラムを測定し、標準ポリスチレンの分子量に換算した値から算出した。
GPC装置:東ソー株式会社製、HLC-8320
検出器:示差屈折率検出器
カラム:東ソー株式会社製のTSKgel SuperMultipore HZM-Mの2本とSuperHZ4000を直列に繋いだものを用いた。
溶離剤: テトラヒドロフラン
溶離剤流量: 0.35ml/分
カラム温度: 40℃
検量線:標準ポリスチレン10点のデータを用いて作成
JIS K7121に準拠して、示差走査熱量測定装置(島津製作所製、DSC-50(品番))を用いて、250℃まで一度昇温し、次いで室温まで冷却し、次いで室温から230℃までを20℃/分で昇温させる条件にてDSC曲線を測定した。このDSC曲線から求められる中間点ガラス転移温度を本発明におけるガラス転移温度とした。
射出成形機(住友重機械工業株式会社製、SE-180DU-HP)を使用し、製造例で得られたメタクリル樹脂を、シリンダ温度280℃、金型温度75℃、成形サイクル1分で射出成形して、長さ290mm、幅100mm、厚さ2mmの試験片を得た。温度50℃、5mmHgの条件下において3日間試験片を真空乾燥させ、絶乾時の試験片の質量W0を測定した。その後、絶乾試験片を温度60℃、湿度90%の条件下で300時間放置した。その後、試験片の質量W1を測定した。下式により飽和吸水率(%)を算出した。
飽和吸水率(%)={W1-W0}/W0×100
MVRは、JIS K7210に準拠して、300℃、1.2kg荷重、10分間の条件で測定した。
全光線透過率は、JIS K7361-1に準じて、ヘイズメータ(村上色彩研究所製、HM-150)を用いて測定した。
JIS K7136に準拠して、ヘイズメータ(村上色彩研究所製、HM-150)を用いてヘイズ(H)を測定した。
40mm×40mmの試験片を、自動複屈折計(王子計測株式会社製 KOBRA-WR)にセットし、温度23±2℃、湿度50±5%において、波長590nm、入射角0°の位相差を測定した。
40mm×40mmの試験片を、自動複屈折計(王子計測株式会社製 KOBRA-WR)にセットし、温度23±2℃、湿度50±5%において、波長590nm、40°傾斜方向の位相差を測定し、その値と平均屈折率nから屈折率nx、nyおよびnzを算出し、さらに厚さ方向位相差Rth(=((nx+ny)/2-nz)×d)を算出した。nxは面内遅相軸方向の屈折率、nyは遅相軸に対して面内で直角方向の屈折率、nzは厚さ方向の屈折率である。
試験片の厚さd[nm]は、デジマティックインジケータ(株式会社ミツトヨ製)を用いて測定した。屈折率nx、nyおよびnzの算出に必要な平均屈折率nは、デジタル精密屈折計(カルニュー光学工業株式会社 KPR-20)で測定した。
一軸延伸したフィルムの場合、延伸方向を長辺として、二軸延伸したフィルムの場合は、製膜のMD(Machine Direction)方向を長辺として150mm×1mmに切り出した試験片を準備した。試験片を40℃で12時間5Torrにて真空乾燥させた後、80℃90%RHの高温高湿度下に12時間放置した。150mmから収縮した長さを計算した。
湿熱収縮率 = (150mm―試験後の長さ)/150mm × 100(%)
実施例および比較例で作製した樹脂組成物を、熱プレス成形して50mm×50mm×1.0mm厚の板状成形体を得た。これら板状成形体の1.0mm厚のイエロインデックスを、紫外可視近赤外分光光度計(株式会社島津製作所製、UV-3600)を用い、JIS Z-8722に準拠して測定した値を元にJIS K7373に準拠してイエロインデックス(YI)算出した。
攪拌機および採取管付オートクレーブに、精製されたメタクリル酸メチル(MMA)84質量部、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イル(TCDMA)15質量部、およびアクリル酸メチル(MA)1質量部を入れて単量体混合物を調製した。単量体混合物に重合開始剤(AIBN、水素引抜能:1%、1時間半減期温度:83℃)0.006質量部および連鎖移動剤(n-オクチルメルカプタン)0.38質量部を加え溶解させて原料液を得た。窒素ガスにより製造装置内の酸素ガスを追出した。
前記原料液を、オートクレーブから、温度140℃に制御された連続流通式槽型反応器に、平均滞留時間120分間となるように、一定流量で供給して、重合転化率57質量%で塊状重合させた。
槽型反応器から排出される液を250℃に加温し、260℃に制御された二軸押出機に一定流量で供給し、押出機入り口で断熱フラッシュさせた。断熱フラッシュで除去された揮発分(単量体、二量体、三量体など)をオープンベントから排出した。未反応単量体を主成分とする揮発分を二軸押出機入口よりも下流部に設けられた6Torrに減圧されたベントから排出し、残された樹脂成分をスクリュでストランド状に押し出した。該ストランドをペレタイザーでカットし、ペレット状のメタクリル樹脂〈PMMA1〉を得た。
得られたメタクリル樹脂は、MMAに由来する構造単位が85質量%、TCDMAに由来する構造単位が14質量%、MAに由来する構造単位が1質量%であった。また、重量平均分子量(Mw)が67000であり、分子量分布(Mw/Mn)が1.81であり、ガラス転移温度(Tg)が125℃であった。表1に、メタクリル樹脂の分析結果を示す。
オートクレーブに、MMA78質量部、TCDMA22質量部、AIBN0.06質量部、1,1-ビス(t-ブチルパーオキシ)シクロへキサン0.01質量部、n-オクチルメルカプタン0.22質量部、ペンタエリスリトールテトラキスチオプロピオネート0質量部、水200質量部、分散剤2.64質量部およびpH調整剤33質量部を入れた。オートクレーブ内を攪拌しながら、液温を室温から70℃に上げ、70℃で180分間保持した。その後、120℃で60分間保持して、重合反応させた。液温を室温まで下げ、重合反応液をオートクレーブから抜き出した。重合反応液から固形分を濾過で取り出し、水で洗浄し、80℃にて24時間熱風乾燥させて、ビーズ状のメタクリル樹脂[PMMA2]を得た。表1に、メタクリル樹脂の分析結果を示す。
メタクリル酸メチル(MMA)、メタクリル酸トリシクロ[5.2.1.02,6] デカ-8-ニル(TCDMA)、アクリル酸メチル(MA)、メタクリル酸イソボルニル(IBMA)、メタクリル酸シクロヘキシル(CHMA)、n-オクチルメルカプタン(n-OM)、ペンタエリスリトールテトラキスチオプロピオネート(PETP)の量を表1または表2に示すように変更した以外は製造例2と同じ方法でメタクリル樹脂〈PMMA3~11〉を得た。表1および表2に、メタクリル樹脂の分析結果を示す。
攪拌装置、温度センサー、冷却管および窒素導入管を備えた内容積30Lの反応釜に、メタクリル酸メチル(MMA)40質量部、2-(ヒドロキシメチル)アクリル酸メチル(MHMA)10質量部、トルエン50質量部、および酸化防止剤(旭電化工業製、アデカスタブ2112)0.025質量部を仕込み、これに窒素を通じつつ、105℃まで昇温させた。昇温に伴う還流が始まったところで、t-アミルパーオキシイソノナノエート(アルケマ吉富製、商品名:ルペロックス570)0.05質量部を添加するとともに、t-アミルパーオキシイソノナノエート0.10質量部を3時間かけて滴下しながら、約105~110℃の還流下で溶液重合を進行させ、さらに4時間の熟成を行った。
次に、得られた重合溶液に、環化縮合反応の触媒(環化触媒)としてリン酸2-エチルヘキシル(堺化学工業製、Phoslex A-8)0.05質量部を加え、約90~110℃の還流下において2時間、環化縮合反応を進行させた後、240℃のオートクレーブにより重合溶液を30分間加熱し、環化縮合反応をさらに進行させた。
次に、得られた重合溶液を、バレル温度240℃、回転速度100rpm、減圧度13.3~400hPa(10~300mmHg)に設定されたリアベント1つおよびフォアベント4つを有するベント付スクリュ二軸押出機(Φ=29.75mm、L/D=30)に、樹脂量換算で2.0kg/時の処理速度で導入し、脱揮を行った。主鎖にラクトン環を有するメタクリル樹脂〈PMMA12〉を得た。表2に、メタクリル樹脂〈PMMA12〉の分析結果を示す。
PC1:住化スタイロンポリカーボネート社製、SD POLYCA TR-2001(品番)〔Mw=22000、MVR(300℃、1.2Kg)=200cm3/10分〕
PC2:住化スタイロンポリカーボネート社製、カリバー 301-40(品番)、〔Mw=35000、MVR(300℃、1.2Kg)=40cm3/10分〕
PC3:住化スタイロンポリカーボネート社製、カリバー 301-4(品番)、〔Mw=58000、MVR(300℃、1.2Kg)=4cm3/10分〕
メタクリル樹脂〈PMMA1〉96質量部およびポリカーボネート樹脂〈PC1〉4質量部を混ぜ合わせ、二軸押出機(テクノベル社製、商品名:KZW20TW-45MG-NH-600)で250℃にて混練押出して樹脂組成物〔1〕を製造した。
樹脂組成物〔1〕を熱プレス成形して50mm×50mm×1.0mm厚の板状成形体を得た。厚さ1.0mmにての全光線透過率TtおよびヘイズHを測定した。結果を表3に示す。
該一軸延伸フィルムの厚みd、面内方向位相差Re、厚さ方向位相差Rth、全光線透過率Tt、ヘイズHおよび湿熱収縮率の測定結果を表3に示す。
表3または表4に示す配合組成に変更した以外は実施例1と同じ方法で樹脂組成物〔2〕~〔17〕を製造した。樹脂組成物〔2〕~〔17〕の物性を表3または4に示す。
表5に示す配合組成に変更した以外は実施例1と同じ方法で樹脂組成物〔19〕を製造した。
樹脂組成物〔1〕の代わりに樹脂組成物〔19〕を用いて、得られるフィルムの厚さを160μmとした以外は実施例1と同じ方法で幅110mmの未延伸フィルムを得た。
この未延伸フィルムを、100mm×100mmの大きさに裁断した。該切片をパンタグラフ式二軸延伸試験機(東洋精機(株)製)にセットし、延伸温度:ガラス転移温度+20℃、縦方向延伸速度:1000%/分、横方向延伸速度1000%/分、縦方向延伸倍率:2倍、横方向延伸倍率:2倍で同時二軸延伸し、10秒間保持し、次いで急冷して、厚さ40μmの二軸延伸フィルムを得た。樹脂組成物〔19〕、未延伸フィルムおよび二軸延伸フィルムの評価結果を表5に示す。
表5に示す配合組成に変更した以外は実施例8と同じ方法で樹脂組成物〔18〕を製造した。
樹脂組成物〔19〕の代わりに樹脂組成物〔18〕を用いた以外は実施例8と同じ方法で幅110mm、厚さ160μmの未延伸フィルムおよび厚さ40μmの二軸延伸フィルムを得た。樹脂組成物〔18〕、未延伸フィルムおよび二軸延伸フィルムの評価結果を表5に示す。PMMA12の飽和吸水率が高いため、湿熱収縮率が大きかった。
表5に示す配合組成に変更した以外は実施例8と同じ方法で樹脂組成物〔20〕~〔22〕を製造した。
樹脂組成物〔19〕の代わりに樹脂組成物〔20〕~〔22〕を用いた以外は実施例8と同じ方法で幅110mm、厚さ160μmの未延伸フィルムおよび厚さ40μmの二軸延伸フィルムを得た。樹脂組成物〔20〕~〔22〕、未延伸フィルムおよび二軸延伸フィルムの評価結果を表5に示す。
表5に示す配合組成に変更した以外は実施例8と同じ方法で樹脂組成物〔23〕を製造した。
樹脂組成物〔19〕の代わりに樹脂組成物〔23〕を用いて、得られるフィルムの厚さを80μmとした以外は実施例8と同じ方法で幅110mmの未延伸フィルムを得た。また、得られるフィルムの厚さを20μmとした以外は、実施例8と同じ方法で二軸延伸フィルムを得た。樹脂組成物〔23〕、未延伸フィルムおよび二軸延伸フィルムの評価結果を表5に示す。
平均重合度2400、ケン化度99.9モル%、厚さ75μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬して膨潤させた。次いで、0.3重量%(重量比:ヨウ素/ヨウ化カリウム=0.5/8)の30℃のヨウ素溶液中で1分間染色しながら、3.5倍まで延伸した。その後、65℃の4重量%のホウ酸水溶液中に0.5分間浸漬しながら総合延伸倍率が6倍まで延伸した。延伸後、70℃のオーブンで3分間乾燥を行い、厚さ22μmの偏光子を得た。
前記活性エネルギー線硬化型接着剤を、フィルムaの易接着層の上に、乾燥後厚さ500nmとなるように塗布して、接着剤層を形成させた。
偏光子の両面のそれぞれに、接着剤層を偏光子側に向けて、前記フィルムaを、小型ラミネーターを用いて重ね合わせた。両面からIRヒーターを用いて50℃に加温し、積算照射量1000/mJ/cm2の紫外線を両面に照射して、活性エネルギー線硬化型接着剤を硬化させ、偏光子の両面にフィルムaを積層してなる偏光板Xを得た。
偏光板Xを80℃、90%RHの恒温恒湿器内に100時間放置した。その後、恒温恒湿器から取り出した偏光板Xを目視観察した。偏光子の劣化は認められなかった。
厚さ40μmのトリアセチルセルロースフィルムを、10%の水酸化ナトリウム水溶液(60℃)に30秒間浸漬してケン化した。その後、60秒間水洗して、フィルムbを得た。
アセトアセチル基含有ポリビニルアルコール系樹脂(平均重合度:1200、ケン化度:98.5モル%,アセトアセチル基変性度:5モル%)100質量部、およびメチロールメラミン20質量部を、30℃の温度条件下で純水に溶解させて、固形分濃度0.5%の接着剤組成物を得た。
該接着剤組成物を30℃の環境下に30分間放置した。該接着剤組成物をフィルムbに、乾燥後厚さ50nmとなるように塗布して、接着剤層を形成させた。
偏光子の両面のそれぞれに、接着剤層を偏光子側に向けて、前記フィルムbを、小型ラミネーターを用いて重ね合わせた。それを、熱風乾燥機(70℃)内で5分間乾燥させて、偏光子の両面にフィルムbを積層してなる偏光板Yを得た。
偏光板Yを80℃、90%RHの恒温恒湿器内に100時間放置した。その後、恒温恒湿器から取り出した偏光板Yを目視観察した。偏光子の劣化が認められた。
12 接着剤層
13 易接着層
14 偏光子保護フィルム
15 接着剤層
16 光学フィルム
Claims (13)
- メタクリル酸多環式脂肪族炭化水素エステルに由来する構造単位(a1)10~50質量%、メタクリル酸多環式脂肪族炭化水素エステル以外のメタクリル酸エステルに由来する構造単位(a2)50~90質量%、およびアクリル酸エステルに由来する構造単位(a3)0~20質量%を含有してなるメタクリル樹脂(A)と、
ポリカーボネート樹脂(B)とを
ポリカーボネート樹脂(B)に対するメタクリル樹脂(A)の質量比(A)/(B)が95/5~99.9/0.1で含有して成る樹脂組成物。 - Xがイソボルナン-2-イル基またはトリシクロ[5.2.1.02,6]デカン-8-イル基である請求項2に記載の樹脂組成物。
- メタクリル酸多環式脂肪族炭化水素エステル以外のメタクリル酸エステルがメタクリル酸メチルである請求項1~3のいずれかひとつに記載の樹脂組成物。
- JIS K7121(昇温速度20℃/分)で測定される中間点ガラス転移温度が120℃以上である請求項1~4のいずれかひとつに記載の樹脂組成物。
- メタクリル樹脂(A)とポリカーボネート樹脂(B)との合計含有量が80~100質量%である請求項1~5のいずれかひとつに記載の樹脂組成物。
- 請求項1~6のいずれかひとつに記載の樹脂組成物からなるフィルム。
- 厚さが10~50μmである、請求項7に記載のフィルム。
- 面積比で1.5~8倍に二軸延伸された請求項7または8に記載のフィルム。
- 少なくとも一軸延伸された請求項7または8に記載のフィルム。
- 請求項7~10のいずれかひとつに記載のフィルムからなる偏光子保護フィルム。
- 請求項7~10のいずれかひとつに記載のフィルムからなる位相差フィルム。
- 偏光子と、
該偏光子に積層された請求項7~10のいずれかひとつに記載のフィルムと
を有する偏光板。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201580029492.XA CN106459554B (zh) | 2014-06-03 | 2015-05-29 | 甲基丙烯酸类树脂组合物 |
JP2016525143A JP6412935B2 (ja) | 2014-06-03 | 2015-05-29 | メタクリル樹脂組成物 |
KR1020167033954A KR20170013273A (ko) | 2014-06-03 | 2015-05-29 | 메타크릴 수지 조성물 |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014115241 | 2014-06-03 | ||
JP2014-115241 | 2014-06-03 | ||
JP2014115242 | 2014-06-03 | ||
JP2014-115242 | 2014-06-03 | ||
JP2014-174915 | 2014-08-29 | ||
JP2014174915 | 2014-08-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015186629A1 true WO2015186629A1 (ja) | 2015-12-10 |
Family
ID=54766702
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/065579 WO2015186629A1 (ja) | 2014-06-03 | 2015-05-29 | メタクリル樹脂組成物 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6412935B2 (ja) |
KR (1) | KR20170013273A (ja) |
CN (1) | CN106459554B (ja) |
TW (1) | TWI658085B (ja) |
WO (1) | WO2015186629A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018124007A1 (ja) * | 2016-12-26 | 2018-07-05 | 株式会社クラレ | 延伸フィルムおよび位相差フィルム |
WO2019155791A1 (ja) * | 2018-02-07 | 2019-08-15 | 日東電工株式会社 | 偏光板および画像表示装置 |
JP2019139204A (ja) * | 2018-02-07 | 2019-08-22 | 日東電工株式会社 | 偏光板および画像表示装置 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107556686A (zh) * | 2017-08-30 | 2018-01-09 | 苏州罗格特光电科技有限公司 | 一种防静电背光液晶显示薄膜材料的制备方法 |
JP7305306B2 (ja) * | 2018-03-30 | 2023-07-10 | 日東電工株式会社 | 円偏光板 |
JP7361043B2 (ja) * | 2018-11-06 | 2023-10-13 | 株式会社日本触媒 | アクリル系ポリマー |
JP7423918B2 (ja) * | 2019-06-28 | 2024-01-30 | コニカミノルタ株式会社 | 光学フィルム、光学フィルムの製造方法および偏光板 |
JPWO2021193521A1 (ja) * | 2020-03-24 | 2021-09-30 | ||
CN112500690B (zh) * | 2020-11-13 | 2022-11-08 | 万华化学(四川)有限公司 | 一种适用于3d打印的聚碳酸酯组合物、制备方法及其应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002035263A1 (fr) * | 2000-10-24 | 2002-05-02 | Fuji Photo Film Co., Ltd. | Plaque de polarisation comprenant un film polymere et membrane de polarisation |
JP2002363342A (ja) * | 2001-06-13 | 2002-12-18 | Konica Corp | 微粒子分散液、ドープの調製方法、セルロースエステルフィルム、偏光板用保護フィルム、偏光板及び画像表示装置 |
JP2012167195A (ja) * | 2011-02-15 | 2012-09-06 | Sumitomo Chemical Co Ltd | 樹脂組成物の製造方法、樹脂組成物及び成形体 |
JP2013534942A (ja) * | 2010-06-08 | 2013-09-09 | エルジー・ケム・リミテッド | 耐熱性・高強度のアクリル系共重合体及びそれを含む光学フィルム |
WO2014024949A1 (ja) * | 2012-08-06 | 2014-02-13 | 住友化学株式会社 | 樹脂組成物、樹脂組成物の製造方法および成形体 |
JP2015081295A (ja) * | 2013-10-23 | 2015-04-27 | 住友化学株式会社 | 樹脂組成物およびその製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3870670B2 (ja) | 2000-06-29 | 2007-01-24 | 日立化成工業株式会社 | 非複屈折性ピックアップレンズ用樹脂組成物及びこれを用いたピックアップレンズ |
CN106939111B (zh) | 2008-11-28 | 2019-06-18 | Lg化学株式会社 | 共混树脂、延迟膜和包括该延迟膜的液晶显示器 |
JP2013064813A (ja) * | 2011-09-16 | 2013-04-11 | Konica Minolta Advanced Layers Inc | 偏光板保護フィルム、偏光板保護フィルムの製造方法、偏光板及び液晶表示装置 |
CN103214775B (zh) * | 2012-01-20 | 2015-06-10 | Lg化学株式会社 | 用于光学膜的树脂组合物、偏光器保护膜和包括该偏光器保护膜的液晶显示器 |
JP2015147858A (ja) * | 2014-02-06 | 2015-08-20 | 住友化学株式会社 | 樹脂組成物およびその成形体 |
-
2015
- 2015-05-29 CN CN201580029492.XA patent/CN106459554B/zh not_active Expired - Fee Related
- 2015-05-29 KR KR1020167033954A patent/KR20170013273A/ko unknown
- 2015-05-29 JP JP2016525143A patent/JP6412935B2/ja not_active Expired - Fee Related
- 2015-05-29 WO PCT/JP2015/065579 patent/WO2015186629A1/ja active Application Filing
- 2015-06-03 TW TW104117888A patent/TWI658085B/zh not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002035263A1 (fr) * | 2000-10-24 | 2002-05-02 | Fuji Photo Film Co., Ltd. | Plaque de polarisation comprenant un film polymere et membrane de polarisation |
JP2002363342A (ja) * | 2001-06-13 | 2002-12-18 | Konica Corp | 微粒子分散液、ドープの調製方法、セルロースエステルフィルム、偏光板用保護フィルム、偏光板及び画像表示装置 |
JP2013534942A (ja) * | 2010-06-08 | 2013-09-09 | エルジー・ケム・リミテッド | 耐熱性・高強度のアクリル系共重合体及びそれを含む光学フィルム |
JP2012167195A (ja) * | 2011-02-15 | 2012-09-06 | Sumitomo Chemical Co Ltd | 樹脂組成物の製造方法、樹脂組成物及び成形体 |
WO2014024949A1 (ja) * | 2012-08-06 | 2014-02-13 | 住友化学株式会社 | 樹脂組成物、樹脂組成物の製造方法および成形体 |
JP2015081295A (ja) * | 2013-10-23 | 2015-04-27 | 住友化学株式会社 | 樹脂組成物およびその製造方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018124007A1 (ja) * | 2016-12-26 | 2018-07-05 | 株式会社クラレ | 延伸フィルムおよび位相差フィルム |
JPWO2018124007A1 (ja) * | 2016-12-26 | 2019-10-31 | 株式会社クラレ | 延伸フィルムおよび位相差フィルム |
WO2019155791A1 (ja) * | 2018-02-07 | 2019-08-15 | 日東電工株式会社 | 偏光板および画像表示装置 |
JP2019139204A (ja) * | 2018-02-07 | 2019-08-22 | 日東電工株式会社 | 偏光板および画像表示装置 |
Also Published As
Publication number | Publication date |
---|---|
CN106459554B (zh) | 2018-12-21 |
TW201605956A (zh) | 2016-02-16 |
JPWO2015186629A1 (ja) | 2017-04-20 |
JP6412935B2 (ja) | 2018-10-24 |
TWI658085B (zh) | 2019-05-01 |
KR20170013273A (ko) | 2017-02-06 |
CN106459554A (zh) | 2017-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6424084B2 (ja) | フィルム及びフィルムの製造方法 | |
JP6412935B2 (ja) | メタクリル樹脂組成物 | |
JP6407270B2 (ja) | メタクリル樹脂組成物 | |
JP6470265B2 (ja) | メタクリル樹脂組成物、成形体、フィルムおよび偏光板 | |
JP6559656B2 (ja) | メタクリル樹脂組成物およびその製造方法、成形体、フィルム並びに偏光板 | |
KR102221885B1 (ko) | 필름 | |
US9605121B2 (en) | Film | |
CN107109019B (zh) | 甲基丙烯酸类树脂组合物及成型体 | |
JP2016048363A (ja) | 樹脂フィルム | |
JP2017040825A (ja) | 複層フィルムおよび偏光子保護フィルム並びに偏光板 | |
WO2018124007A1 (ja) | 延伸フィルムおよび位相差フィルム |
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: 15802803 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016525143 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167033954 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: 15802803 Country of ref document: EP Kind code of ref document: A1 |