WO2017115787A1 - Composition de résine et film - Google Patents

Composition de résine et film Download PDF

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Publication number
WO2017115787A1
WO2017115787A1 PCT/JP2016/088858 JP2016088858W WO2017115787A1 WO 2017115787 A1 WO2017115787 A1 WO 2017115787A1 JP 2016088858 W JP2016088858 W JP 2016088858W WO 2017115787 A1 WO2017115787 A1 WO 2017115787A1
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Prior art keywords
resin composition
group
resin
crosslinked rubber
mass
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PCT/JP2016/088858
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English (en)
Japanese (ja)
Inventor
祐作 野本
卓郎 新村
淳裕 中原
Original Assignee
株式会社クラレ
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Priority to JP2017559199A priority Critical patent/JP6802188B2/ja
Publication of WO2017115787A1 publication Critical patent/WO2017115787A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • 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
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

Definitions

  • the present invention relates to a resin composition.
  • Methacrylic resin is excellent in transparency, light resistance and surface hardness.
  • various optical members such as a light guide plate and a lens can be obtained.
  • a methacrylic resin composition that is a raw material for optical members is strongly required to have high transparency, low moisture absorption, high heat resistance, small dimensional change, high impact strength, good moldability, and the like.
  • a resin material for optical members for example, an optical resin material obtained by polymerizing a polymerizable composition containing 5% by weight or more of tricyclodecanyl (meth) acrylate is known (see Patent Document 1). . Since this optical resin material is brittle, its application has been limited. As a method for improving brittleness, a resin composition to which a crosslinked rubber or the like is added is known. However, a resin composition containing a structure derived from tricyclodecanyl (meth) acrylate and a crosslinked rubber is usually easily thermally decomposed during molding, which causes coloring and gel foreign matter.
  • An object of the present invention is to provide a resin composition constituting a molded article having low hygroscopicity, small dimensional change, and excellent transparency and impact strength.
  • the present invention includes the following inventions.
  • X is a cyclic hydrocarbon group having 6 or more carbon atoms.
  • a cyclic hydrocarbon group having 6 or more carbon atoms representing X has an isobornan-2-yl group, a tricyclo [5.2.1.0 2,6 ] decan-8-yl group, or a substituent.
  • a film comprising the resin composition according to any one of [1] to [8]. [10] The film according to [9], having a thickness of 10 to 50 ⁇ m.
  • a polarizer protective film comprising the film of [9] or [10].
  • a retardation film comprising the film of [9] or [10].
  • the resin composition of the present invention can form a molded article having low transparency and moisture absorption, small dimensional change, and excellent transparency and impact strength.
  • the resin composition of the present invention comprises a structural unit (a1) 10 to 50% by mass derived from a methacrylic acid cyclic hydrocarbon ester and a structural unit (a2) 50 derived from a methacrylic acid ester other than the methacrylic acid cyclic hydrocarbon ester.
  • This is a resin composition having a mass ratio (A) / (B) of rubber (B) of 95/5 to 10/90 and an acid value measured by JIS K 0070: 1992 of 7 mg / g or less.
  • the structural unit (a1) is a structural unit derived from a methacrylic acid cyclic hydrocarbon ester.
  • the cyclic hydrocarbon group constituting the methacrylic acid cyclic hydrocarbon ester is not particularly limited, and examples thereof include an octahydropentalen-1-yl group, an octahydropentalen-2-yl group, and an octahydro-1-1H.
  • the alkyl group in the above “substituted with an alkyl group” is preferably an alkyl group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. Group, tert-butyl group and the like.
  • the cyclic hydrocarbon group an aliphatic cyclic hydrocarbon group is preferable.
  • the methacrylic acid cyclic hydrocarbon ester constituting the structural unit (a1) is preferably a compound represented by the formula (1).
  • X is a cyclic hydrocarbon group having 6 or more carbon atoms.
  • X in the formula (1) is a cyclic hydrocarbon group having 6 or more carbon atoms, preferably a polycyclic aliphatic hydrocarbon group having 10 or more carbon atoms, more preferably a bridged cyclic group having 10 or more carbon atoms. It is a hydrocarbon group.
  • the bridged cyclic hydrocarbon group is an alicyclic hydrocarbon group having a structure in which two adjacent carbon atoms constituting a ring are connected by a carbon chain composed of one or more carbon atoms.
  • Such a bridged cyclic hydrocarbon group may have a condensed ring structure or a spiro ring structure in addition to a structure connected by a carbon chain.
  • the number of carbon atoms constituting the bridged cyclic hydrocarbon group is more preferably 10-20.
  • Examples of the cyclic hydrocarbon group having 6 or more carbon atoms include octahydrocyclopenta [c, d] pentalen-2A-2a (2H) -yl, 3a, 6a-dimethyloctahydropentalen-2-yl, tetra Decahydroanthracen-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-trimethylnorbornane-2-yl group, isobornan-2-yl group, 2-methylisobornan-2-yl group, 2-ethylisoborn Nan-2-yl group, decahydro-2,5-methano-7,10-methananaphthalen-1-yl group, tricyclo [5.2.1.0 2,6 ] decan-8-y
  • the structural unit (a2) possessed by the methacrylic resin (A) is a structural unit derived from a methacrylic acid ester (a2) other than the methacrylic acid cyclic hydrocarbon ester.
  • the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, methacrylic acid.
  • Methacrylic acid chain aliphatic hydrocarbon esters such as amyl acid, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate: 2-hydroxyethyl methacrylate, 2-methoxy methacrylate Examples thereof include ethyl, glycidyl methacrylate, allyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate.
  • a methacrylic acid chain aliphatic hydrocarbon ester is preferable, and methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate. Is more preferred, and methyl methacrylate is most preferred.
  • the structural unit (a3) that the methacrylic resin (A) may have is a structural unit derived from an acrylate ester.
  • the acrylate esters include acrylic acid chain aliphatic hydrocarbon esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; acrylic acid aromatics such as phenyl acrylate.
  • Acrylic alicyclic hydrocarbon esters such as cyclohexyl acrylate and norbornenyl acrylate.
  • methyl acrylate, ethyl acrylate, and butyl acrylate are preferable, and methyl acrylate is particularly preferable from the viewpoint that thermal decomposition can be suppressed and moldability is improved.
  • the methacrylic resin (A) used in the present invention may contain a structural unit (a4) in addition to the structural unit (a1), the structural unit (a2) and the structural unit (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.
  • a structural unit having an acidic functional group such as a carboxylic acid group or a sulfonic acid group derived from acrylic acid, methacrylic acid, 4-vinylbenzenesulfonic acid or the like increases the acid value. Moreover, since a water absorption rate becomes high, it is preferable not to contain.
  • the methacrylic resin (A) used in the present invention has 10 to 50% by mass of the structural unit (a1) and the structural unit (a2) from the viewpoint of high glass transition temperature, low water absorption, and small shrinkage at high temperature and high humidity.
  • the structural unit (a3) is contained in an amount of 0 to 20% by mass, preferably the structural unit (a1) is 15 to 40% by mass, the structural unit (a2) is 60 to 85% by mass, and 0 to 10% by mass of structural unit (a3), more preferably 20 to 30% by mass of structural unit (a1), 70 to 80% by mass of structural unit (a2), and 0 to 10% of structural unit (a3) 5% by mass is contained.
  • 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 80000 to 160000, still more preferably 90000 to 150,000, Preferably it is 100,000-130,000.
  • Mw weight average molecular weight
  • the film made of the resin composition of the present invention has high strength, is difficult to break, and is easy to stretch, so that a thinner film can be obtained.
  • the moldability of a methacryl resin (A) improves because Mw is 200000 or less, it becomes the tendency for the thickness of the film which consists of a resin composition of this invention to be uniform, and to be excellent in surface smoothness.
  • the methacrylic resin (A) used in the present invention has a ratio of Mw to a 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 film made of the resin composition of the present invention tends to be excellent in surface smoothness. When the molecular weight distribution is 5.0 or less, a film made of the resin composition of the present invention 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, more preferably measured at 230 ° C. under a load of 3.8 kg in accordance with JIS K7210. Is 0.5 to 5 g / 10 min, more preferably 0.8 to 3 g / 10 min.
  • the acid value of the methacrylic resin (A) used in the present invention is measured according to JIS K 0070: 1992.
  • the acid value is preferably 7 mg / g or less, preferably 5 mg / g or less, more preferably 3 mg / g or less, further preferably 1.0 mg / g or less, and most preferably 0.5 mg / g or less.
  • thermal decomposition caused by the structural unit (a1) derived from the methacrylic acid cyclic hydrocarbon ester in the methacrylic resin (A) can be suppressed.
  • the glass transition temperature of the methacrylic resin (A) used in the present invention is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° 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 cyclic 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 performed in accordance with JIS K7121 in the region of room temperature or higher.
  • the first temperature increase (1 st run) is performed at a temperature increase rate of 10 ° C./min up to 230 ° C. to cool, then, a time of, 2 nd intermediate glass transition temperature of the run to increase the temperature (2 nd run) at a heating rate of 10 ° C. / min up to 230 ° C. from room temperature.
  • 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.
  • a suspension polymerization method when a radical polymerization method is used, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or an emulsion polymerization method can be selected.
  • a suspension polymerization method or a bulk 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 radical polymerization reaction is performed using a polymerization initiator, the above-described monomer, and a chain transfer agent as necessary.
  • the polymerization initiator is not particularly limited as long as it generates a reactive radical.
  • the one-hour half-life temperature is preferably 60 to 140 ° C, more preferably 80 to 120 ° C.
  • examples of such a polymerization initiator 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-tetramethyl Butyl peroxyneodecanoate, 1,1-bis (t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2′-azobis (2 -Methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl And the like 2,2'-azobis (2-methyl propionate).
  • t-hexylperoxy 2-ethylhexanoate 1,1-bis (t-hexylperoxy) cyclohexane, and dimethyl 2,2′-azobis (2-methylpropionate) are preferable.
  • polymerization initiators may 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 0 to 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 as necessary when the methacrylic resin (A) used in the present invention is produced by the radical polymerization method 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 may 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.
  • the methacrylic resin (A) and thus the resin composition of the present invention, 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 reaction temperature when producing the methacrylic resin (A) used in the present invention by radical polymerization 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, it can be washed, dehydrated and dried by a known method after completion of the polymerization to obtain a granular polymer.
  • 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. If the devolatilization temperature is too high, the acid value of the resulting methacrylic resin (A) will be high.
  • 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 anionic polymerization 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. (See Japanese Patent Publication No. 7-25859), anionic polymerization in the presence of an organoaluminum compound using an organic alkali metal compound as a polymerization initiator (see JP-A-11-335432), and polymerization of an organic rare earth metal complex Examples of the initiator include a method of anionic polymerization (see JP-A-6-93060).
  • the methacrylic resin (A) used in the present invention is produced by an anionic polymerization method
  • an alkyl lithium such as n-butyllithium, sec-butyllithium, isobutyllithium, or t-butyllithium
  • an organoaluminum compound coexist from a viewpoint of productivity.
  • the organoaluminum compound include compounds represented by the formula: AlR 1 R 2 R 3 .
  • R 1 , R 2 and R 3 each independently have an alkyl group which may have a substituent, an cycloalkyl group which may have a substituent, or a substituent.
  • R 2 and R 3 may be an aryleneoxy group which may have a substituent formed by bonding them.
  • 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 crosslinked rubber (B) used in the present invention is a polymer exhibiting rubber elasticity in which a polymer chain is crosslinked by a structural unit derived from a crosslinking monomer.
  • the crosslinkable monomer is one having two or more polymerizable functional groups in one monomer.
  • crosslinkable monomer examples include allyl acrylate, allyl methacrylate, 1-acryloxy-3-butene, 1-methacryloxy-3-butene, 1,2-diacryloxy-ethane, 1,2-dimethacryloxy-ethane, 1,2-diacryloxy-propane, 1,3-diacryloxy-propane, 1,4-diacryloxy-butane, 1,3-dimethacryloxy-propane, 1,2-dimethacryloxy-propane, 1,4-dimethacryloxy-butane, triethylene
  • crosslinked rubber (B) used in the present invention examples include acrylic crosslinked rubber and diene crosslinked rubber, and more specifically, an acrylate monomer, a crosslinking monomer, and other vinyl.
  • Copolymer rubber with conjugated monomer Copolymer rubber with conjugated diene monomer, crosslinkable monomer and other vinyl monomer, Acrylic acid ester monomer and conjugated diene monomer And a copolymer rubber of a polymer, a crosslinkable monomer, and other vinyl monomers.
  • a crosslinked rubber not containing a structure derived from a conjugated diene monomer is preferable.
  • the crosslinked rubber (B) is preferably contained in the resin composition in the form of particles.
  • the crosslinked rubber (B) in the form of particles may be a single layer particle composed only of the crosslinked rubber, or may be a multilayer particle composed of the crosslinked rubber and another polymer.
  • core-shell type particles comprising a core composed of the crosslinked rubber and a shell composed of the other polymer are preferable.
  • the crosslinked rubber (B) that can be suitably used in the present invention is acrylic multilayer polymer particles.
  • the acrylic multilayer polymer particles have a core part and a shell part.
  • the core portion includes a center core and, if necessary, one or more inner shells that cover the center core in a substantially concentric shape.
  • the shell portion has a one-layer outer shell that covers the core portion substantially concentrically.
  • the center core, the inner shell, and the outer shell are connected to each other without a gap.
  • the center core and the inner shell contains the crosslinked rubber polymer (i), and the remaining part contains the polymer (iii).
  • the crosslinked rubber polymer (i) contained in them has the same polymer properties. Alternatively, it may have different polymer properties. Further, when the remaining part of the center core and the inner shell is two or more, the polymer (iii) contained in them may have the same polymer properties or different polymer properties. It may be a thing.
  • the crosslinked rubber polymer (i) has at least a unit derived from an acrylate monomer and / or a unit derived from a conjugated diene monomer and a unit derived from a crosslinkable monomer. From the viewpoint of enhancing light resistance, a crosslinked rubber polymer (i) that does not contain a structure derived from a conjugated diene monomer is preferred.
  • the acrylate monomer is preferably an acrylate monomer having an alkyl group having 1 to 8 carbon atoms or an acrylate monomer having an aromatic group having 6 to 24 carbon atoms.
  • Acrylic acid ester monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, benzyl acrylate, paracumylphenol ethylene oxide modified acrylate, o-phenyl A phenol ethylene oxide modified acrylate etc. can be mentioned. These may be used alone or in combination of two or more.
  • Examples of the conjugated diene monomer include butadiene and isoprene. These may be used alone or in combination of two or more.
  • the amount of the unit derived from the acrylate monomer and / or the unit derived from the conjugated diene monomer in the crosslinked rubber polymer (i) is preferably relative to the total mass of the crosslinked rubber polymer (i). Is 60% by mass or more, more preferably 70 to 99% by mass, and still more preferably 80 to 98% by mass.
  • crosslinkable monomer examples include allyl acrylate, allyl methacrylate, 1-acryloxy-3-butene, 1-methacryloxy-3-butene, 1,2-diacryloxy-ethane, 1,2-dimethacryloxy-ethane, 1,2-diacryloxy-propane, 1,3-diacryloxy-propane, 1,4-diacryloxy-butane, 1,3-dimethacryloxy-propane, 1,2-dimethacryloxy-propane, 1,4-dimethacryloxy-butane, triethylene
  • the amount of the unit derived from the crosslinkable monomer in the crosslinked rubber polymer (i) is preferably 0.05 to 10% by mass, more preferably 0.8%, based on the total mass of the crosslinked rubber polymer (i). It is 5 to 7% by mass, more preferably 1 to 5% by mass.
  • the crosslinked rubber polymer (i) may have units derived from other vinyl monomers.
  • the other vinyl monomer used in the crosslinked rubber polymer (i) is not particularly limited as long as it can be copolymerized with the acrylate monomer and the crosslinkable monomer.
  • Examples of other vinyl monomers used in the crosslinked rubber polymer (i) include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, phenyl methacrylate, benzyl methacrylate, and cyclohexyl methacrylate.
  • Monomers aromatic vinyl monomers such as styrene, p-methylstyrene, o-methylstyrene; and maleimide monomers such as N-propylmaleimide, N-cyclohexylmaleimide, N-o-chlorophenylmaleimide; Can be mentioned. These may be used alone or in combination of two or more.
  • the amount of units derived from other vinyl monomers in the crosslinked rubber polymer (i) includes units derived from acrylate monomers, units derived from conjugated diene monomers, and crosslinkable monomers. It is the remainder with respect to the total amount of the unit derived from.
  • the polymer (iii) is not particularly limited as long as it is other than the crosslinked rubber polymer (i), but preferably has a unit derived from a methacrylic acid ester monomer.
  • the polymer (iii) may contain, as other units, a unit derived from a crosslinkable monomer and / or a unit derived from another vinyl monomer.
  • the methacrylic acid ester monomer used for the polymer (iii) is a methacrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms or a methacrylic acid ester monomer having an aromatic group having 6 to 24 carbon atoms.
  • methacrylic acid ester monomer examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like. These may be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.
  • the amount of the unit derived from the methacrylic acid ester monomer in the polymer (iii) is preferably 40 to 100% by mass, more preferably 50 to 99% by mass, and further preferably 60 to 98% by mass.
  • crosslinkable monomer used in the polymer (iii) examples include the same crosslinkable monomers exemplified in the above-mentioned crosslinked rubber polymer (i).
  • the amount of the unit derived from the crosslinkable monomer in the polymer (iii) is preferably 0 to 5% by mass, more preferably 0.01 to 3% by mass, and further preferably 0.02 to 2% by mass. .
  • the other vinyl monomer used for the polymer (iii) is not particularly limited as long as it is copolymerizable with the above-mentioned methacrylic acid ester monomer and crosslinkable monomer.
  • examples of other vinyl monomers used for the polymer (iii) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, Acrylic acid ester monomers such as 2-ethylhexyl acrylate, paracumylphenol ethylene oxide modified acrylate, o-phenylphenol ethylene oxide modified acrylate; vinyl acetate; styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene , ⁇ -methylstyrene, vinyl naphthalene and other aromatic vinyl monomers;
  • the acrylic multilayer polymer particle has an outer shell containing the thermoplastic polymer (ii).
  • thermoplastic polymer (ii) has a unit derived from a methacrylic acid ester monomer.
  • the thermoplastic polymer (ii) may have units derived from other vinyl monomers.
  • the methacrylic acid ester monomer used for the thermoplastic polymer (ii) is a methacrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms or a methacrylic acid ester having an aromatic group having 6 to 24 carbon atoms. It is preferable that Examples of the methacrylic acid ester monomer include methyl methacrylate and butyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like. You may use these individually by 1 type or in combination of 2 or more types. Of these, methyl methacrylate is preferred.
  • the amount of the unit derived from the methacrylic acid ester monomer in the thermoplastic polymer (ii) is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more.
  • thermoplastic polymer (ii) examples include the same vinyl monomers as those exemplified in the polymer (iii).
  • the amount of units derived from other vinyl monomers in the thermoplastic polymer (ii) is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.
  • the core part and the shell part of the acrylic multilayer polymer particles for example, Two-layer polymer particles whose center core is a crosslinked rubber polymer (i) and whose outer shell is a thermoplastic polymer (ii); Three-layer polymer particles in which the center core is a polymer (iii), the inner shell is a crosslinked rubber polymer (i), and the outer shell is a thermoplastic polymer (ii); Three-layer polymer particles with one kind of crosslinked rubber polymer (i) having a center core, one inner shell being another kind of crosslinked rubber polymer (i), and outer shell being a thermoplastic polymer (ii) , Three-layer polymer particles in which the center core is a crosslinked rubber polymer (i), the inner shell is a polymer (iii), and the outer shell is a thermoplastic polymer (ii); 4 layers, the center core is a crosslinked rubber polymer (i), the inner inner shell is a polymer (iii), the outer inner shell is a
  • Examples thereof include polymer particles.
  • the difference in refractive index (absolute value) between adjacent layers is preferably less than 0.005, more preferably less than 0.004, and even more preferably less than 0.003. It is preferable to select a polymer contained in each layer.
  • the ratio of the outer shell part in the acrylic multilayer polymer particles is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and further preferably 20 to 40% by mass.
  • the ratio of the layer containing the crosslinked rubber polymer (i) in the core is preferably 20 to 100% by mass, more preferably 30 to 70% by mass.
  • the volume-based average particle diameter of the crosslinked rubber particles (B) used in the present invention is preferably 0.02 to 1 ⁇ m, more preferably 0.05 to 0.5 ⁇ m, still more preferably 0.1 to 0.3 ⁇ m.
  • the volume reference average particle diameter in this specification is a value calculated based on particle size distribution data measured by the light scattering light method.
  • the method for producing the crosslinked rubber particles (B) is not particularly limited. From the viewpoints of particle size control, ease of production of the multilayer structure, the emulsion polymerization method or the seed emulsion polymerization method is preferred.
  • the emulsion polymerization method is a method for producing an emulsion containing polymer particles by emulsifying a predetermined monomer and polymerizing it.
  • seed particles are obtained by emulsifying and polymerizing a predetermined monomer, and by emulsifying and polymerizing another predetermined monomer in the presence of the seed particles,
  • a method for producing an emulsion comprising core-shell polymer particles having a shell polymer coated in a substantially concentric shape.
  • Examples of the emulsifier used in the emulsion polymerization method include dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate and sodium dilauryl sulfosuccinate which are anionic emulsifiers, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, and the like.
  • the average number of repeating units of the ethylene oxide unit in the exemplary compounds of the nonionic emulsifier and the nonionic anionic emulsifier is preferably 30 or less, more preferably 20 or less, in order to prevent the foaming property of the emulsifier from becoming extremely large. More preferably, it is 10 or less.
  • the polymerization initiator used for emulsion polymerization is not particularly limited. Examples thereof include persulfate initiators such as potassium persulfate and ammonium persulfate; redox initiators such as persulfoxylate / organic peroxide and persulfate / sulfite.
  • Separation and acquisition of the crosslinked rubber (B) from the emulsion obtained by emulsion polymerization can be performed by a known method such as a salting out coagulation method, a freeze coagulation method, or a spray drying method.
  • the salting out coagulation method and the freeze coagulation method are preferable, and the freeze coagulation method is more preferable from the viewpoint that impurities contained in the crosslinked rubber (B) can be easily removed by washing with water.
  • the freeze coagulation method since an aggregating agent is not used, an acrylic resin film excellent in water resistance is easily obtained.
  • the crosslinked rubber (B) is preferably taken out as an aggregate of 1000 ⁇ m or less, and 500 ⁇ m or less. It is more preferable to take out with the aggregate.
  • the form of the aggregate of the crosslinked rubber (B) is not particularly limited, and may be, for example, a pellet form fused to each other at the shell, or a powder form or a granulated form.
  • the acid value measured by JIS K 0070: 1992 of the crosslinked rubber (B) used in the present invention is preferably 10 mg / g or less, more preferably 7 mg / g or less, further preferably 5 mg / g or less, and 3 mg / g or less. Is more preferable, and 1 mg / g or less is most preferable.
  • the acid value of the crosslinked rubber can be lowered by washing, for example. In the measurement of the acid value of the crosslinked rubber, the crosslinked rubber is not completely dissolved, but the acid value is measured with stirring the crosslinked rubber in chloroform at room temperature for 12 hours or more and leaving the undissolved crosslinked rubber remaining. That's fine.
  • the refractive index (n 23 D ) of the crosslinked rubber (B) used in the present invention varies depending on the type of the matrix resin containing the methacrylic resin (A), the optimum value for ensuring transparency varies. 45 to 1.60 are preferred, 1.48 to 1.56 are more preferred, and 1.50 to 1.54 are even more preferred. The closer the refractive index (n 23 D ) of the crosslinked rubber (B) is to the refractive index (n 23 D ) of components other than the crosslinked rubber (B), the higher the transparency of the resin composition.
  • the difference (absolute value) in refractive index between the matrix resin containing the methacrylic resin (A) and the crosslinked rubber (B) is 0.05 or less, more preferably 0.02 or less, and still more preferably 0.01. In the following, it is preferable to select appropriately so that it is most preferably 0.005 or less.
  • the matrix resin containing the methacrylic resin (A) is a resin component other than the crosslinked rubber (B) in the resin composition of the present invention.
  • the matrix resin may be composed of only the methacrylic resin (A), or may be composed of a composition of the methacrylic resin (A) and another polymer such as a polycarbonate resin.
  • the refractive index values of the matrix resin and the crosslinked rubber (B) are actually measured by the method described in the examples below. If it is difficult to prepare a sample for measuring the refractive index, the refractive index of the homopolymer is conveniently determined.
  • the weight average can be obtained according to the copolymer composition or the mass ratio of the mixing ratio.
  • the mass ratio (A) / (B) of the methacrylic resin (A) and the crosslinked rubber (B) in the resin composition according to the present invention is 95/5 to 10/90 from the viewpoint of impact resistance, and 90/10 To 30/70 is more preferable, 85/15 to 40/60 is more preferable, and 80/20 to 50/50 is most preferable.
  • the total amount of the methacrylic resin (A) and the crosslinked rubber (B) contained in the resin composition according to the present invention is preferably 40 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably 70 to 100% by mass, most preferably 80 to 100% by mass.
  • the acid value measured by JIS K 0070: 1992 of the resin composition according to the present invention is 7 mg / g or less, preferably 5 mg / g or less, more preferably 3 mg / g or less, and 1.0 mg / g or less. More preferred is 0.5 mg / g or less.
  • thermal decomposition caused by the structural unit (a1) derived from the methacrylic acid cyclic hydrocarbon ester in the methacrylic resin (A) can be suppressed.
  • the structural unit (a1) derived from the methacrylic acid cyclic hydrocarbon ester in the methacrylic resin (A) is thermally decomposed to produce a methacrylic acid structural unit.
  • the thermal decomposition of the resin composition is promoted by the carboxylic acid group, and the production of coloring and foreign matters is promoted. What is necessary is just to measure similarly in the case of the film which is 1 aspect of a composition.
  • the resin composition contains the crosslinked rubber (B), it is not completely dissolved, but the resin composition is stirred and dissolved in chloroform at room temperature for 12 hours or more to leave undissolved crosslinked rubber (B). In this state, the acid value may be measured.
  • the acid value is within the above range, the yellow index of the resin composition can be lowered, coloring can be reduced, and the thermal decomposition resistance can be maintained high.
  • the resin composition according to the present invention may further contain a polycarbonate resin (C).
  • the polycarbonate resin (C) that may be added to the resin composition of the present invention is not particularly limited, and examples thereof 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 excellent transparency of the resulting film.
  • the polycarbonate resin (C) used in the present invention has a melt volume flow rate (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.
  • MVR values, preferably 1 ⁇ 250cm 3/10 min, more preferably 3 ⁇ 230cm 3/10 min.
  • the polycarbonate resin (C) 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 18000-75000, more preferably 20000-60000.
  • the MVR value and the weight average molecular weight of the polycarbonate resin (C) can be adjusted by adjusting the amounts of the terminal terminator and the branching agent.
  • the glass transition temperature of the polycarbonate resin (C) 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 performed in accordance with JIS K7121 in the region of room temperature or higher.
  • the first temperature increase (1 st run) is performed at a temperature increase rate of 10 ° C./min up to 230 ° C. to cool, then, a time of, 2 nd intermediate glass transition temperature of the run to increase the temperature (2 nd run) at a heating rate of 10 ° C. / min up to 230 ° C. from room temperature.
  • the method for producing the polycarbonate resin (C) 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 one 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.
  • the polycarbonate resin (C) commercially available products and other known products can be used.
  • the polycarbonate resin (C) may contain a unit having a polyester, polyurethane, polyether or polysiloxane structure in addition to the polycarbonate unit.
  • the mass ratio (A) / (C) of the methacrylic resin (A) to the polycarbonate resin (C) is usually 98/2 to 50/50, preferably 98/2 to 60 /. 40.
  • the compatibility of the methacrylic resin (A) and the polycarbonate resin (C) is good, it is easy to obtain a film having high transparency, high refractive index, and good surface smoothness.
  • the mass ratio (A) / (C) 98/2 to 90/10 of the methacrylic resin (A) to the polycarbonate resin (C) is selected, the absolute value of the retardation of the film can be reduced.
  • 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, Styrene 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 resin such as nylon 6, nylon 66, polyamide such as polyamide elastomer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, poly Setar,
  • the resin composition according to the present invention is an antioxidant, a thermal deterioration inhibitor, an ultraviolet absorber, a light stabilizer, a lubricant, a mold release agent, a polymer processing aid, an antistatic agent, as long as the effects of the present invention are not impaired. It may contain additives such as additives, flame retardants, dyes and pigments, light diffusing agents, organic dyes, matting agents, and phosphors.
  • additives may be used singly or in combination of two or more. Moreover, these additives may be added to the polymerization reaction liquid when producing the methacrylic resin (A) or the crosslinked rubber (B), or the produced methacrylic resin (A) or the crosslinked rubber (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 of the present invention is not particularly limited. For example, a method of polymerizing a monomer mixture containing methyl methacrylate in the presence of a crosslinked rubber (B) to produce a methacrylic resin (A), or melt-kneading a methacrylic resin (A) and a crosslinked rubber (B) The method of doing can be mentioned. In the melt-kneading, other polymers and additives may be mixed as necessary, and the methacrylic resin (A) is mixed with the other polymers and additives and then mixed with the crosslinked rubber (B).
  • the crosslinked rubber (B) may be mixed with other polymer and additive 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 crosslinked rubber (B) to be used, but is preferably 110 ° C. to 280 ° C., more preferably 200 ° C. to 270 ° C. If the melting temperature is too high, the acid value of the resulting resin composition will be high.
  • the resin composition of the present invention has a glass transition temperature of preferably 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 122 ° 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 performed in accordance with JIS K7121 in the region of room temperature or higher.
  • the first temperature increase (1 st run) is performed at a temperature increase rate of 10 ° C./min up to 230 ° C. to cool, then, a time of, 2 nd intermediate glass transition temperature of the run to increase the temperature (2 nd run) at a heating rate of 10 ° C. / min up to 230 ° C. from room temperature.
  • the Mw determined by gel permeation chromatography (GPC) measurement of the solvent-soluble content of the resin composition of the present invention is preferably 70000-200000, more preferably 72000-180000, and further preferably 75000-150,000.
  • the Mw / Mn determined by gel permeation chromatography (GPC) measurement of the solvent-soluble content of the resin composition of the present invention is preferably 1.2 to 5.0, more preferably 1.5 to 3.5. It is. When Mw and Mw / Mn are in this range, the molding processability of the resin composition becomes good, and it becomes easy to obtain a molded article excellent in impact resistance and toughness.
  • the resin composition of the present invention has a melt flow rate (MFR) determined by measurement under conditions of 230 ° C. and a load of 3.8 kg, preferably 0.1 to 15 g / 10 min, more preferably 0.5 to 5 g / 10 min, most preferably 1.0 to 3 g / 10 min.
  • MFR melt flow rate
  • 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, For example, a solution cast method, a melt casting method, an extrusion molding method, an inflation molding method, a blow molding method etc. can be mentioned. 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. If the temperature of the resin composition becomes too high, the acid value of the resulting film will be high.
  • 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 may be stretched in at least one direction.
  • 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.
  • an 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 it is 5 nm or less, Most preferably, it is 1 nm or less.
  • 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.
  • the in-plane retardation Re per 40 ⁇ m thickness is preferably 10 to 200 nm, more preferably 10 to 180 nm, and even more preferably 10 to 150 nm.
  • the thickness direction retardation is preferably ⁇ 10 to ⁇ 250 nm, more preferably ⁇ 20 to ⁇ 230 nm, and further preferably ⁇ 30 to ⁇ 200 nm.
  • 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, an anti-slip layer such as fine particles, and a gas barrier layer. it can.
  • the film of the present invention is excellent in thermal decomposition resistance and has impact resistance, a retardation film, a polarizer protective film, a liquid crystal protective plate, a surface material for a portable information terminal, a display window protective film for a portable information terminal, It is suitable for light guide films, transparent conductive films coated with silver nanowires or carbon nanotubes, optical gas barrier films, front plate applications for various displays, and the like.
  • the film of the present invention has excellent thermal decomposition resistance and impact resistance, it can be used for applications other than optical applications, such as IR cut films, crime prevention films, scattering prevention films, decorative films, metal decorative films, and solar cell backs. It can be used for sheets, front sheets for flexible solar cells, shrink films, and films for in-mold labels.
  • the polarizing plate in which the film of the present invention is used has at least 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 in which the film of the present invention is used 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), 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 film of the present invention has excellent thermal decomposition resistance and impact resistance, it is also suitable as a film used for an organic electroluminescence lighting device or an organic electroluminescence display device.
  • composition of monomer units in resin Using a nuclear magnetic resonance apparatus (ULTRA SHIELD 400 PLUS manufactured by Bruker), 1 H-NMR spectrum was measured under the conditions of 1 mL of deuterated chloroform, room temperature, and 64 times of accumulation for 10 mg of resin. The composition of monomer units in the resin was calculated.
  • Mw Weight average molecular weight (Mw) Mw was calculated from the value obtained by measuring the chromatogram under the following conditions by gel permeation chromatography (GPC) and converting it 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
  • Calibration curve Created using 10 standard polystyrene data
  • Glass transition temperature (Tg) Glass transition temperature (Tg)
  • DSC-50 product number manufactured by Shimadzu Corporation
  • Total light transmittance (T t ) The total light transmittance was measured with a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) according to JIS K7361-1, using a test piece (optical path length: 3 mm) prepared by measuring saturated water absorption. .
  • Haze (H) Haze (H) was measured using a haze meter (manufactured by Murakami Color Research Laboratory, HM-150) in accordance with JIS K7136, using a test piece (optical path length: 3 mm) prepared by measuring saturated water absorption.
  • the test piece prepared by measuring the saturated water absorption was measured for refractive index at a measurement wavelength of 587.6 nm (d line) at 23 ° C. using Kalnew Optical Co., Ltd. yKPR-20 ”.
  • the sample contained a crosslinked rubber it was not completely dissolved, but was stirred and dissolved in chloroform at room temperature for 12 hours or more, and the acid value was measured in a state where undissolved crosslinked rubber remained.
  • ⁇ YI A test piece prepared with a saturated water absorption rate is exposed for 200 hours at 80 mW / cm 2 and a temperature of 55 ° C. using a super UV tester (Iwasaki Electric Co., Ltd., SUV-F1). The difference of the index (YI) was set as ⁇ YI and evaluated as follows. A: ⁇ YI ⁇ 5 B: ⁇ YI> 5
  • ⁇ Production Example 1> In an autoclave, 63 parts by weight of methyl methacrylate (MMA), 35 parts by weight of dicyclopentanyl methacrylate (TCDMA), 2 parts by weight of methyl acrylate (MA), 0.47 parts by weight of pentaerythritol tetrakisthiopro Pionate, 0.06 parts by weight of azobisisobutyronitrile, 0.01 parts by weight of 1,1-bis (1,1-dimethylperoxy) cyclohexane, 231 parts by weight of water, 1.4 parts by weight And 17.5 parts by weight of a pH adjuster were added.
  • MMA methyl methacrylate
  • TCDMA dicyclopentanyl methacrylate
  • MA methyl acrylate
  • MA pentaerythritol tetrakisthiopro Pionate
  • azobisisobutyronitrile 0.01 parts by weight of 1,1-bis (1,1-dimethylperoxy) cyclo
  • the liquid temperature was raised from room temperature to 70 ° C., held at 70 ° C. for 120 minutes, and then held at 120 ° C. for 60 minutes to cause a polymerization reaction.
  • the liquid temperature was lowered to room temperature, and the polymerization reaction liquid was extracted from the autoclave.
  • the solid content was removed from the polymerization reaction solution by filtration, washed with water, and dried in hot air at 80 ° C. for 24 hours.
  • the obtained solid content was supplied to a hopper of a twin screw extruder and melt kneaded at a cylinder temperature of 230 ° C.
  • ⁇ Production Example 2 48 kg of ion-exchanged water is charged into a 100-liter reaction tank equipped with a condenser, a thermometer and a stirrer, and then dissolved with 416 g of sodium stearate, 128 g of sodium lauryl sarcosinate and 16 g of sodium carbonate. I let you. Next, 11.2 kg of methyl methacrylate and 110 g of allyl methacrylate were added and the temperature was raised to 70 ° C. while stirring. Thereafter, 560 g of a 2% aqueous potassium persulfate solution was added to initiate emulsion polymerization.
  • 720 g of a 2% aqueous sodium persulfate solution was added to the obtained emulsion.
  • a mixture of 12.4 kg of butyl acrylate, 1.76 kg of styrene and 280 g of allyl methacrylate was dropped over 60 minutes. After completion of the dropwise addition, stirring was continued for 60 minutes to perform the second stage seed emulsion polymerization.
  • 320 g of 2% potassium persulfate aqueous solution is added to the emulsion after the seed emulsion polymerization in the second stage, and further comprises 4.2 kg of methyl methacrylate, 2.0 kg of TCDMA, 0.2 kg of methyl acrylate and 200 g of n-octyl mercaptan.
  • the mixture was added over 30 minutes. After completion of the addition, stirring was continued for 60 minutes to perform the third stage seed emulsion polymerization.
  • the resulting emulsion was cooled to room temperature.
  • an emulsion containing 40% of the core-shell three-layer structure crosslinked rubber (B-1) having a volume-based average particle size of 0.23 ⁇ m was obtained.
  • the resulting emulsion was frozen at ⁇ 20 ° C. for 2 hours.
  • the frozen emulsion was poured into 80 times hot water of twice that amount and allowed to thaw to obtain a slurry.
  • the slurry (S1) was kept at 80 ° C. for 20 minutes, then dehydrated and dried at 70 ° C. to obtain a crosslinked rubber (B-1) having a refractive index of 1.49 as particles.
  • 320 g of 2% aqueous potassium persulfate solution is added to the emulsion after seed emulsion polymerization in the first stage, and further comprises 4.2 kg of methyl methacrylate, 2.0 kg of TCDMA, 0.2 kg of methyl acrylate, and 200 g of n-octyl mercaptan.
  • the mixture was added over 30 minutes. After completion of the addition, stirring was continued for 60 minutes to perform seed emulsion polymerization in the second stage. The resulting emulsion was cooled to room temperature.
  • B-3 three-layer structure crosslinked rubber
  • the resulting emulsion was frozen at ⁇ 20 ° C. for 2 hours.
  • the frozen emulsion was poured into 80 times hot water of twice that amount and allowed to thaw to obtain a slurry.
  • the slurry was held at 80 ° C. for 20 minutes, then dehydrated, and water was added to a solids concentration of 10%. Subsequently, it was dehydrated and dried at 70 ° C. to obtain a crosslinked rubber (B-3) having a refractive index of 1.52 as particles.
  • Example 1 100 parts by weight of methacrylic resin (A-1) and 43 parts by weight of cross-linked rubber (B-2) were dry-mixed with a tumbler and a twin screw extruder with a shaft diameter of 20 mm (trade name: KZW20TW-45MG-, manufactured by Technobel Co., Ltd.).
  • NH-600 is melt kneaded under the conditions of a cylinder temperature of 200 to 250 ° C., a die temperature of 240 ° C., and a screw rotation speed of 100 rpm, and a pellet-shaped resin composition (hereinafter referred to as “resin composition (R-1)”).
  • Resin composition (R-1) a pellet-shaped resin composition
  • ⁇ Comparative Example 4 100 parts by weight of methacrylic resin (A-1) and 43 parts by weight of cross-linked rubber (B-1) were dry-mixed with a tumbler, and a twin screw extruder with a shaft diameter of 20 mm (trade name: KZW20TW-45MG-, manufactured by Technobel Co., Ltd.) NH-600) is melt kneaded under the conditions of a cylinder temperature of 200 to 280 ° C., a die temperature of 270 ° C., and a screw rotation speed of 200 rpm, and a pellet-shaped resin composition (hereinafter referred to as “resin composition (R-6)”). ) Table 1 shows the composition and physical properties of the resin composition (R-6).

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Abstract

L'invention concerne une composition de résine servant à former un article moulé présentant une faible hygroscopicité, une faible variation dimensionnelle, une excellente transparence et une excellente résistance aux chocs. La composition de résine contient une résine méthacrylate (A) et un caoutchouc réticulé (B), la résine méthacrylate (A) comprenant de 10 à 50 % en masse d'un motif structural (a1) dérivé d'un ester d'hydrocarbure cyclique de l'acide méthacrylique, de 50 à 90 % en poids d'un motif structural (a2) dérivé d'un ester de méthacrylate différent de l'ester d'hydrocarbure cyclique de l'acide méthacrylique, et de 0 à 20 % en poids d'un motif structural (a3) dérivé d'un ester d'acrylate. La composition de résine contient la résine méthacrylate (A), par rapport au caoutchouc réticulé (B), selon un rapport massique (A)/(B) allant de 95/5 à 10/90. L'indice d'acidité de la composition de résine, mesuré conformément à la norme JIS K0070:1992, est inférieur ou égal à 7 mg/g.
PCT/JP2016/088858 2015-12-29 2016-12-27 Composition de résine et film WO2017115787A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017204243A1 (fr) * 2016-05-27 2017-11-30 株式会社クラレ Composition de résine thermoplastique, corps moulé, film, et stratifié
WO2018124007A1 (fr) * 2016-12-26 2018-07-05 株式会社クラレ Film étiré et film de retard
JP2021009178A (ja) * 2019-06-28 2021-01-28 コニカミノルタ株式会社 光学フィルムおよび偏光板

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6173705A (ja) * 1984-09-20 1986-04-15 Hitachi Chem Co Ltd 重合体からなる光学機器
JPH04356502A (ja) * 1990-07-18 1992-12-10 Kuraray Co Ltd アクリル系重合体凝固組成物、その製法およびその成形物
WO2012053190A1 (fr) * 2010-10-20 2012-04-26 株式会社カネカ Film de résine (méth)acrylique
JP2015199779A (ja) * 2014-04-04 2015-11-12 三菱化学株式会社 ポリカーボネート樹脂用強化剤、ポリカーボネート樹脂組成物及び成形品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6173705A (ja) * 1984-09-20 1986-04-15 Hitachi Chem Co Ltd 重合体からなる光学機器
JPH04356502A (ja) * 1990-07-18 1992-12-10 Kuraray Co Ltd アクリル系重合体凝固組成物、その製法およびその成形物
WO2012053190A1 (fr) * 2010-10-20 2012-04-26 株式会社カネカ Film de résine (méth)acrylique
JP2015199779A (ja) * 2014-04-04 2015-11-12 三菱化学株式会社 ポリカーボネート樹脂用強化剤、ポリカーボネート樹脂組成物及び成形品

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017204243A1 (fr) * 2016-05-27 2017-11-30 株式会社クラレ Composition de résine thermoplastique, corps moulé, film, et stratifié
JPWO2017204243A1 (ja) * 2016-05-27 2019-03-28 株式会社クラレ 熱可塑性樹脂組成物、成形体、フィルム及び積層体
US10858488B2 (en) 2016-05-27 2020-12-08 Kuraray Co., Ltd. Thermoplastic resin, molded product, film, and layered product
JP7202181B2 (ja) 2016-05-27 2023-01-11 株式会社クラレ 熱可塑性樹脂組成物、成形体、フィルム及び積層体
WO2018124007A1 (fr) * 2016-12-26 2018-07-05 株式会社クラレ Film étiré et film de retard
JP2021009178A (ja) * 2019-06-28 2021-01-28 コニカミノルタ株式会社 光学フィルムおよび偏光板
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

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