CN106471055A - Methacrylic resin composition and its manufacture method, formed body, thin film and polarization plates - Google Patents

Abstract

The present invention offer transparency is high, thickness direction phase contrast is little, the methacrylic resin composition of easy stretching.The content that the methacrylic resin composition of the present invention contains the construction unit from methyl methacrylate be more than 80 mass % and weight average molecular weight be less than 200000 methacrylic resin, have more than 1000 and less than 32000 viscosity-average molecular weight and with respect to the content of described methacrylic resin 100 mass parts be 1～4 mass parts polycarbonate resin and have 3000～40000 average degree of polymerization and be 0.3～6 mass parts with respect to the content of described methacrylic resin 100 mass parts polymer processing aid, the described methacrylic resin containing in methacrylic resin composition is more than 80 mass % with the total amount of described polycarbonate resin.

Description

Methacrylic resin composition and its manufacture method, formed body, thin film and partially Vibration plate

Technical field

The present invention relates to the methacrylic resin composition containing methacrylic resin and polycarbonate resin. In addition, being related to thin film, formed body and the polarization plates possessing above-mentioned thin film comprising above-mentioned methacrylic resin composition.

Background technology

Liquid crystal indicator uses various resin-made membranes.Wherein, mainly use triacetyl in polarizer protection film Base cellulose.The moisture permeability comprising the thin film of tri acetyl cellulose is high, therefore, carries out with filming, exists and cause polarization The tendency that the quality of piece reduces.The improvement of polarizer protection film becomes problem in the slimming of liquid crystal indicator.

Therefore, have studied methacrylic resin as the material of new polarizer protection film.Known to comprising first When the thin film of base acrylic resin carries out stretch processing, toughness improves (patent documentation 1 reference).But, to common methyl When acrylic resin thin film is stretched, phase contrast increases, such as, in IPS crystal liquid mode, cause the grade of picture to reduce.

The known resin by adding polycarbonate resin etc. in methacrylic resin, is readily obtained phase contrast little Thin film (patent documentation 2～5).But, for these methacrylic resin compositions, in order to ensure the transparency It is added with the low polycarbonate resin of molecular weight, therefore draftability is insufficient.Specifically, hold when being drawn into thin film further Easily rupturable, in addition, when being stretched at lower temperatures to improve the thin film strength after stretching, existing and be susceptible to The problem of fracture.In addition, for the thermostability improving methacrylic resin composition, the syndiotaxy in terms of triad The high general narrow molecular weight distribution of methacrylic resin of regularity (rr), and using common methacrylic resin Methacrylic resin composition is compared, and draftability is simultaneously insufficient.

Prior art literature

Patent documentation

Patent documentation 1：Japanese Patent Publication 57-32942 publication

Patent documentation 2：Japanese Unexamined Patent Publication 5-32846 publication

Patent documentation 3：Japanese Unexamined Patent Publication 2012-514759 publication

Patent documentation 4：Japanese Unexamined Patent Publication 2013-148655 publication

Patent documentation 5：Japanese Unexamined Patent Publication 2014-51649 publication

Content of the invention

Invent problem to be solved

The present invention be in view of above-mentioned background and complete, its object is to provide that the transparency is high, the phase contrast of thickness direction The methacrylic resin composition of little, easy stretching.Additionally, it is provided thickness is uniform and surface smoothness is excellent, productivity ratio The thin film comprising methacrylic resin composition high, that intensity is big.

Method for solve problem

The present inventor has been repeated research to realize above-mentioned purpose, and result completes and comprises following mode The present invention.

[1]：A kind of methacrylic resin composition, it is containing methacrylic resin, polycarbonate resin With the methacrylic resin composition of polymer processing aid, wherein,

The content of the construction unit from methyl methacrylate of above-mentioned methacrylic resin is 80 mass % Above, weight average molecular weight is less than 200000,

Above-mentioned polycarbonate resin has more than 1000 and less than 32000 viscosity-average molecular weight, with respect to above-mentioned methyl-prop The content of the above-mentioned polycarbonate resin of olefin(e) acid resinoid 100 mass parts is below more than 1 mass parts and 4 mass parts,

Above-mentioned polymer processing aid has more than 3000 and less than 40000 average degree of polymerization,

It is 0.3 matter with respect to the content of the above-mentioned polymer processing aid of above-mentioned methacrylic resin 100 mass parts More than amount part and below 6 mass parts,

The above-mentioned methacrylic resin containing in methacrylic resin composition and above-mentioned polycarbonate resin Total amount be 80 mass % more than.

[2]：Methacrylic resin composition as described in [1], wherein, above-mentioned methacrylic resin with three The degree of syndiotacticity (rr) of unit group meter is more than 50%, and the content of the construction unit from methyl methacrylate For more than 92 mass % and below 100 mass %.

[3]：Methacrylic resin composition as described in [1] or [2], wherein, above-mentioned methacrylic resin Degree of syndiotacticity (rr) be more than 58% and less than 85%.

[4]：Methacrylic resin composition as any one of [1]～[3], wherein, above-mentioned metering system The content of the construction unit from methyl methacrylate of acid resin is more than 99 mass %.

[5]：Methacrylic resin composition as any one of [1]～[4], wherein, above-mentioned Merlon Resin has more than 5000 and less than 18000 viscosity-average molecular weight.

[6]：Methacrylic resin composition as any one of [1]～[5], wherein, above-mentioned metering system The weight average molecular weight of acrylic resin composition is 70000～200000.

[7]：Methacrylic resin composition as any one of [1]～[6], wherein, above-mentioned metering system The molecular weight distribution of acrylic resin composition is 1.2～2.5.

[8]：A kind of formed body, it comprises the methacrylic resin composition any one of [1]～[7].

[9]：A kind of thin film, it comprises the methacrylic resin composition any one of [1]～[7].

[10]：Thin film as described in [9], its thickness is 10～50 μm.

[11]：Thin film as described in [9] or [10], it is biaxially stretched to 1.5～8 times in terms of area ratio.

[12]：Thin film as any one of [9]～[11], it uses as polarizer protection film.

[13]：A kind of polarization plates, it is laminated with the thin film described at least [12].

[14]：A kind of manufacture method of methacrylic resin composition, wherein, methacrylic resin composition By following at least three kinds compositions are obtained by mixing：

From the content of the construction unit of methyl methacrylate be more than 80 mass % and weight average molecular weight is Less than 200000 methacrylic resin 100 mass parts,

More than polycarbonate resin 1 mass parts of the viscosity-average molecular weight with more than 1000 and less than 32000 and 4 mass parts Below and

More than polymer processing aid 0.3 mass parts of the average degree of polymerization with more than 3000 and less than 40000 and 6 matter Below amount part.

Invention effect

In accordance with the invention it is possible to providing, the transparency is high, thickness direction phase contrast is little, the methacrylic of easy stretching Resin combination.In addition, playing following excellent results：Thickness can be provided uniform and surface smoothness is excellent, productivity ratio is high, What intensity was big comprises the thin film of methacrylic resin composition.

Brief description

Fig. 1 is the sectional view of of the polarization plates representing embodiments of the present invention.

Specific embodiment

The methacrylic resin composition of the present invention contains methacrylic resin, polycarbonate resin and high score Sub- processing aid.In addition, the thin film of the present invention is the thin film comprising above-mentioned methacrylic resin composition.

In methacrylic resin used in the present invention, from the viewpoint of the thermostability of obtained thin film, come Come from methyl methacrylate construction unit content on the basis of the quality of methacrylic resin be 80 mass % with On, more than preferably 92 mass %, more than more preferably 95 mass %, more than more preferably 97 mass %, particularly preferably More than 99 mass %, most preferably 100 mass %.

Used in the present invention, methacrylic resin can contain the construction unit from methyl methacrylate Construction unit in addition, can enumerate for example：Ethyl methacrylate, cyclohexyl methacrylate, Tert-butyl Methacrylate, Methacrylic acid 2- isobornyl thiocyanoacetate, methacrylic acid 8- tri- ring [5.2.1.0^2,6] last of the ten Heavenly stems ester, methacrylic acid 4- t-butyl cyclohexyl methacrylate Deng the alkyl methacrylate beyond methyl methacrylate；Acrylic acid methyl ester., ethyl acrylate, propyl acrylate, propylene The alkyl acrylates such as acid butyl ester, 2-EHA；The benzyl acrylate such as phenyl acrylate；Cyclohexyl acrylate, The acrylate base esters such as acrylic acid norborneol ester；Acrylamide；Methacrylamide；Acrylonitrile；Methacrylonitrile；Deng one Only there is in molecule the construction unit of the vinyl monomer of a polymerism carbon-to-carbon double bond.From methyl methacrylate Construction unit beyond construction unit is preferably below 8 mass %, below more preferably 5 mass %, more preferably 3 matter Amount below %, below particularly preferably 1 mass %, most preferably 0 mass %.

In methacrylic resin used in the present invention, from the viewpoint of thermostability, in terms of triad between The lower limit of same steric regularity (rr) is preferably 50%, more preferably 55%, more preferably 58%, even more preferably for 59%, most preferably 60%.From the viewpoint of film property, this methacrylic resin in terms of triad between with vertical The upper limit of structure regularity (rr) is preferably 99%, more preferably 85%, more preferably 77%, even more preferably for 70%, even more preferably for 65%, most preferably 64%.There is the methacrylic tree of such degree of syndiotacticity Fat makes draftability insufficient because of narrow molecular weight distribution, and therefore, the interpolation of polymer processing aid plays effect further.

Degree of syndiotacticity (rr) (below, sometimes referred to simply as " degree of syndiotacticity (rr) ") in terms of triad It is that two chains (diad, diad) of having of chain (triad, triad) of continuous 3 construction units are outer disappearing The ratio of rotation (being expressed as rr).It should be noted that by the chain (diad, diad) of the construction unit in polymer molecule The identical person of spatial configuration is referred to as meso (meso), spatial configuration opposite is referred to as raceme (racemo), is expressed as m、r.

The degree of syndiotacticity (rr) (%) of methacrylic resin can calculate as follows：30 in deuterochloroform Measure at DEG C¹H-NMR composes, by this spectrum measure the area (X) in the region making 0.6～0.95ppm that TMS is during 0ppm and 0.6～ The area (Y) in the region of 1.35ppm, using formula：(X/Y) × 100 calculate above-mentioned degree of syndiotacticity.

Used in the present invention, the weight average molecular weight (below, sometimes referred to as " Mw ") of methacrylic resin is 200000 Hereinafter, preferably 80000～200000, more preferably 85000～160000, more preferably 90000～120000.Pass through Make that this Mw is more than 80000 and degree of syndiotacticity (rr) is more than 50%, obtained thin film strength is high, not fragile Split, easily stretch.Therefore, it is possible to make thin film thinner.In addition, by making Mw be less than 200000, methacrylic resin Shaping processability improves, therefore, the tendency that thickness is uniform and surface smoothness is excellent of the thin film obtained by having.

Used in the present invention Mw of methacrylic resin with number mean molecule quantities (below, sometimes referred to as " Mn ") it Than (Mw/Mn：Hereinafter, sometimes this value is referred to as " molecular weight distribution ") it is preferably 1.2～2.0, more preferably 1.3～1.7.Pass through Molecular weight distribution is made to be more than 1.2, the mobility of methacrylic resin improves, and obtained thin film has surface smoothness Excellent tendency.By making molecular weight distribution be less than 2.0, obtained thin film has inclining of resistance to impact and good-toughness To.It should be noted that Mw and Mn is will to be scaled standard polyphenyl second using the chromatogram that gel permeation chromatography (GPC) measures It is worth obtained from the molecular weight of alkene.

Used in the present invention methacrylic resin, according to JIS K7210 230 DEG C, 3.8kg load condition The melt flow rate (MFR) of lower mensure preferably 0.1～5g/10 minute, more preferably 0.5～4g/10 minute, most preferably 1.0～3g/10 minute.

Used in the present invention, the glass transition temperature of methacrylic resin is preferably more than 110 DEG C, more preferably For more than 118 DEG C, more preferably more than 120 DEG C, even more preferably for more than 123 DEG C, most preferably more than 124 DEG C. The upper limit of the glass transition temperature of this methacrylic resin is usually 140 DEG C, preferably 130 DEG C.Glass transition temperature Degree can be controlled by Molecular regulator amount, degree of syndiotacticity (rr).Glass transition temperature within the range when, be difficult The deformation such as thermal contraction of thin film obtained by occurring.It should be noted that glass transition temperature is to be recorded using embodiment The intermediate point glass transition temperature that method measures.

The manufacture method of methacrylic resin is not particularly limited.For example, in radical polymerization, anionic polymerisation In the known polymerization such as method, to polymerization temperature, polymerization time, the species of chain-transferring agent and amount, the species of polymerization initiator and Amount etc. is adjusted, thus, it is possible to manufacture the methacrylic acid that the characteristics such as Mw, degree of syndiotacticity (rr) meet expected range Resinoid.

For example, in the case of radical polymerization, preferably make polymerization temperature be less than 80 DEG C, more preferably 70 DEG C with Under, more preferably less than 60 DEG C.So, when temperature being adjusted, easily improve degree of syndiotacticity (rr).

In the case of anionic polymerization, as polymerization initiator, preferably use n-BuLi, s-butyl lithium, isobutyl The lithium alkylides such as base lithium, tert-butyl lithium.In addition, from the viewpoint of productivity ratio, organo-aluminum compound has preferably coexisted.As organic Aluminum, can enumerate the compound represented by following formula.

AlR¹R²R³

(in formula, R¹、R²And R³Represent independently of one another and can have the alkyl of substituent group, can have the cycloalkanes of substituent group Base, can have the aryl of substituent group, can have the aralkyl of substituent group, can have the alkoxyl of substituent group, can have The aryloxy group of substituted base or N, N- disubstituted amido.R²And R³Can being formed for respective bonding, can have substituent group Arlydene two epoxide)

Specifically, double (2, the 6- di-t-butyl -4- methylphenoxy) aluminum of isobutyl group, isobutyl group double (2,6- can be enumerated Di-t-butyl phenoxy group) aluminum, isobutyl group [2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert butyl phenoxy)] aluminum etc..

In addition, in anionic polymerization, in order to control polyreaction it is also possible to ether, nitrogen-containing compound etc. have coexisted.

In addition, in the case that methacrylic resin is manufactured by anionic polymerization, in the midway of polyreaction Than add polymerization initiator the few amount of amount, specifically with respect to the amount of polymerization initiator be preferably 1 mole of %～50 mole %, The short-stopper of more preferably 2 moles %～20 mole %, more preferably 5 moles of %～10 mole %, or poly- The midway closing reaction adds to add and is preferably 1 mole of %～50 mole %, more with respect to the amount of the initial polymerization initiator adding It is preferably the polymerization initiator of 2 moles of %～20 mole %, more preferably 5 moles of %～10 mole %, thus, it is possible to adjust Section weight average molecular weight.

As the methacrylic tree obtaining weight average molecular weight, degree of syndiotacticity (rr) etc. and having desired characteristic The second method of fat, can be listed below method：The methacrylic resin being unsatisfactory for desired characteristic of a mixing part Or will be unsatisfactory between the methacrylic resin of desired characteristic suitably mixing, thus obtain that there is desired characteristic The methacrylic resin of (characteristic such as weight average molecular weight, degree of syndiotacticity (rr)).The process management of the method is easy. The mixing of multiple methacrylic resins can use known method, such as kneading extruder, extruder, mixing mill, class In uncle, the melting mixing device such as mixer is carrying out.Temperature during mixing can be according to the methacrylic resin being used Melt temperature suitably to be adjusted, usually 150～300 DEG C.

As the 3rd manufacture method obtaining the methacrylic resin with desired characteristic, have desired in deviation In the presence of the methacrylic resin of characteristic range, monomer is polymerized to manufacture desired weight average molecular weight, syndiotaxy rule The method that the characteristics such as whole degree (rr) meet the methacrylic resin of desired scope.This polymerization can be with above-mentioned free radical Polymerization, anionic polymerization are similarly carried out.According to the 3rd manufacture method, compared with the second manufacture method, put on methyl The thermal history of acrylic resin shortens, therefore, methacrylic resin thermally decompose to yield suppression, be readily obtained coloring, The thin film of few foreign.

In the manufacture method of methacrylic resin as above, from the high methyl of the transparency can be easily manufactured The methacrylic acid of desired scope from the viewpoint of acrylic resin, is preferably met by anionic polymerization manufacturing characteristics Resinoid method；By the methacrylic resin that will be manufactured using anionic polymerization with using radical polymerization manufacture Methacrylic resin mixing come manufacturing characteristics meet prescribed limit methacrylic resin method；With by will Using the anionic polymerization methacrylic resin manufacturing and the metering system being manufactured using other anionic polymerization Acid resin mixing carrys out the method that manufacturing characteristics meet the methacrylic resin of desired scope, more preferably passes through to utilize The methacrylic resin that anionic polymerization manufactures is mixed with using the methacrylic resin that radical polymerization manufactures Carry out the method that manufacturing characteristics meet the methacrylic resin of desired scope.

Used in the present invention, polycarbonate resin is by multifunctional hydroxy compounds and carbonic ester formative compound The polymer that obtains of reaction.From the good sight of the transparency of the compatibility with methacrylic resin, obtained thin film Point considers, this polycarbonate resin optimization aromatic polycarbonate resin.

From the viewpoint of Merlon is difficult to ooze out from obtained methacrylic resin composition, the present invention Used in polycarbonate resin viscosity-average molecular weight (below, sometimes referred to as " Mv ") be more than 1000, preferably more than 3000, More preferably more than 5000, more preferably more than 10000.In addition, from the sight with the compatibility of methacrylic resin Point considers, viscosity-average molecular weight is less than 32000, preferably less than 22000, more preferably less than 18000, more preferably Less than 17000.The degree of syndiotacticity (rr) of the methacrylic resin being used is higher, then with polycarbonate resin The compatibility is higher, can be using the bigger polycarbonate resin of viscosity-average molecular weight.Adding, such viscosity-average molecular weight is less In the case of Merlon, draftability reduces, and therefore, the interpolation of polymer processing aid shows effect further.

Viscosity-average molecular weight (Mv) with regard to polycarbonate resin, using Cannon-Fenske viscometer or Ubbelohde viscometer, Specific viscosity η that polycarbonate resin 0.5g is dissolved in solution obtained from dichloromethane 100mL is measured at 20 DEG C_sp, as Meet the value of following Schnell formula, the viscous of polycarbonate resin is calculated by the limiting viscosity [η] of 20 DEG C of dichloromethane solutions Average molecular weight.

η_sp/ c=[η]+0.45 × [η]²c

(wherein, [η] is limiting viscosity, c=0.5 under these conditions)

[η]=1.23 × 10^-4Mv^0.83

In addition, from the viewpoint of the compatibility with methacrylic resin, polycarbonate resin used in the present invention 300 DEG C of fat, MVR (melt volume-flow rate) value under 1.2kg be preferably 1.0cm³More than/10 minutes, more preferably 10cm³More than/10 minutes, more preferably 25cm³More than/10 minutes, particularly preferably 33cm³More than/10 minutes.In addition, From the viewpoint of Merlon is difficult to ooze out from obtained methacrylic resin composition, preferably 2 × 10⁷cm³Less than/10 minutes, more preferably 1 × 10⁵cm³Less than/10 minutes, more preferably 10000cm³Less than/10 minutes, Particularly preferably 390cm³Less than/10 minutes.

In addition, with regard to being measured using gel permeation chromatography (GPC) of polycarbonate resin used in the present invention Chromatogram is scaled weight average molecular weight obtained from the molecular weight of polystyrene standard (Mw), is difficult from obtained from Merlon Methacrylic resin composition in ooze out from the viewpoint of, Mw be preferably more than 1300g/ mole, more preferably More than 4700g/ mole, more preferably more than 8500g/ mole, particularly preferably more than 19200g/ mole.In addition, from From the viewpoint of the compatibility of methacrylic resin, preferably less than 75000g/ mole, more preferably 48300g/ mole Hereinafter, more preferably less than 38200g/ mole, particularly preferably less than 35700g/ mole.

It should be noted that the viscosity-average molecular weight of polycarbonate resin, MVR value, weight average molecular weight can be by adjusting chain Terminator, the amount of branching agent are carrying out.

Used in the present invention, the glass transition temperature of polycarbonate resin is preferably more than 110 DEG C, and more preferably 125 More than DEG C, more preferably more than 140 DEG C.The upper limit of the glass transition temperature of this polycarbonate resin is usually 180 DEG C.

The manufacture method of polycarbonate resin is not particularly limited.For example, it is possible to enumerating phosgenation (interfacial polymerization), melting Melt polymerization (ester-interchange method) etc..In addition, the aromatic polycarbonate resin preferably using in the present invention can be to using molten The polycarbonate resin fat raw material melting polymerization manufacture implements the fragrant adoption carbon obtained from process for adjusting terminal hydroxyl amount Acid ester resin.

It is multifunctional hydroxy compounds as the raw material for manufacturing polycarbonate resin, can enumerate：Can have and take The 4,4 ' of Dai Ji-dihydroxybiphenyl class；Can have double (hydroxy phenyl) alkanes of substituent group；Can have the double of substituent group (4- hydroxy phenyl) ethers；Can have double (4- hydroxy phenyl) thioether classes of substituent group；Can have double (4- hydroxyls of substituent group Base phenyl) sulfoxide type；Can have double (4- hydroxy phenyl) sulfone classes of substituent group；Can have double (4- hydroxy benzeness of substituent group Base) ketone；Can have double (hydroxy phenyl) fluorenes classes of substituent group；Can have the dihydroxy para-terpheny class of substituent group；Can There is the dihydroxy of substituent group to quaterphenyl class；Can have double (hydroxy phenyl) Pyrazine of substituent group；Can have and take Double (hydroxy phenyl) Meng's alkanes of Dai Ji；Can have double [2- (4- hydroxy phenyl) -2- propyl group] benzene classes of substituent group；Can have The dihydroxy naphthalenes of substituted base；Can have the dihydroxy benzenes class of substituent group；Can have the polysiloxane-based of substituent group；Can To have dihydro perfluoro alkane class of substituent group etc..

In these multifunctional hydroxy compounds, double (4- hydroxy phenyl) propane of preferably 2,2-, 1,1- are double (4- hydroxy phenyl) Double (4- the hydroxy phenyl) -1- diphenylphosphino ethane of hexamethylene, double (4- hydroxy phenyl) diphenyl methane, 1,1-, 2,2- double (4- hydroxyl - 3- aminomethyl phenyl) propane, 2,2- double (4- hydroxyl -3- phenyl) propane, 4,4 '-dihydroxybiphenyl, double (4- hydroxy phenyls) Double (the bromo- 4- hydroxy phenyl of the 3,5- bis-) propane of sulfone, 2,2-, double (4- hydroxy phenyl) pentane of 3,3-, the double (4- hydroxyl -3- first of 9,9- Base phenyl) fluorenes, double (4- hydroxy phenyl) ether, 4,4 '-dihydroxy benaophenonel, double (the 4- hydroxy 3-methoxybenzene base) 1 of 2,2-, 1,1,3,3,3- HFC-236fa, α, ω-bis- [3- (2- hydroxy phenyl) propyl group] polydimethylsiloxane, resorcinol, 2,7- bis- Hydroxyl naphthalene, double (4- hydroxy phenyl) propane of particularly preferred 2,2-.

As carbonic ester formative compound, the various dihalo carbonyl compound such as phosgene, chloro-formate etc. can be enumerated The carbonate products such as haloformate, double aryl carbonates.The amount of this carbonic ester formative compound considers and multifunctional hydroxyl The stoichiometric proportion (equivalent) of the reaction of based compound suitably to be adjusted.

Reaction is carried out generally in the presence of acid binding agent in a solvent.As acid binding agent, can enumerate：Hydroxide The alkali metal hydroxides such as sodium, potassium hydroxide, Lithium hydrate, Cesium hydrate.；The alkali carbonates such as sodium carbonate, potassium carbonate；Three Methylamine, triethylamine, tri-n-butylamine, N, the tertiary amine such as N- dimethyl cyclohexyl amine, pyridine, dimethylaniline；Trimethyl benzyl ammonia chloride, three Ethylbenzylammonium chloride, tributyl benzyl ammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium chloride, tetrabutyl ammonium bromide etc. Quaternary ammonium salt；Season sulfonium salt such as tetrabutyl chlorination sulfonium, tetrabutyl phosphonium bromide sulfonium etc..Furthermore, it is possible to it is few in this reaction system according to expectation Amount adds the antioxidants such as sodium sulfite, sulfhydrate.The amount of acid binding agent considers the stoichiometric proportion (equivalent) reacted to fit When adjusting.Specifically, every with respect to the hydroxyl of the multifunctional hydroxy compounds of raw material 1 mole, using 1 equivalent or be more than The acid binding agent of the amount of 1 equivalent, preferably 1～5 equivalent.

In addition, known chain terminating agent, branching agent can be used in reaction.As chain terminating agent, can enumerate to tertiary fourth Base phenol, 4-hydroxydiphenyl, p -cumylphenol, to perfluor nonyl phenol, to (perfluor nonyl phenyl) phenol, to (perfluoro hexyl Phenyl) phenol, to perfluoro-t-butyl phenol, 1- (to hydroxybenzyl) perfluoro decane, to [2- (1H, 1H- perfluor tridecyl oxygen Base) -1,1,1,3,3,3- hexafluoro propyl group] phenol, 3,5- double (perfluoro hexyl Epoxide carbonyl) phenol, P-hydroxybenzoic acid perfluor ten Dialkyl, to (1H, 1H- perfluoro capryl epoxide) phenol, 2H, 2H, 9H- perfluoro-pelargonic acid, the fluoro- 2- propanol of 1,1,1,3,3,3- tetra- Deng.

As branching agent, phloroglucinol, 1,2,3,-thrihydroxy-benzene, 4,6- dimethyl -2 can be enumerated, 4,6- tri- (4- hydroxy phenyls) - 2- heptene, 2,6- dimethyl -2,4,6- three (4- hydroxy phenyl) -3- heptene, 2,4- dimethyl -2,4,6- three (4- hydroxy phenyl) Heptane, 1,3,5- tri- (2- hydroxy phenyl) benzene, 1,3,5- tri- (4- hydroxy phenyl) benzene, 1,1,1- tri- (4- hydroxy phenyl) ethane, Three (4- hydroxy phenyl) phenylmethane, 2,2- double [double (4- hydroxy phenyl) cyclohexyl of 4,4-] propane, double [double (the 4- hydroxyl of 2- of 2,4- Base phenyl) -2- propyl group] phenol, double (2- hydroxy-5-methyl base the benzyl) -4- methylphenol of 2,6-, 2- (4- hydroxy phenyl) -2- (2, 4- dihydroxy phenyl) propane, four (4- hydroxy phenyl) methane, four [4- (4- hydroxy phenyl isopropyl) phenoxy group] methane, 2,4- Double (3- methyl -4- the hydroxy phenyl) -2- oxo -2,3- indoline of resorcylic acid, trimesic acid, cyanuric acid, 3,3-, 3,3- double (4- hydroxyaryl) epoxide indole, 5- chlorisatide, 5,7- bis- chlorisatide, 5-bromoisatin etc..

Polycarbonate resin in addition to containing polycarbonate unit, can also contain have polyester, polyurethane, polyethers or The unit of polysiloxane structure etc..

Polymer processing aid is the material containing a large amount of high molecular weight components.In polymer processing aid and resin material Between there is macromolecule winding (network) each other, this winding point plays a role as doubtful crosslinking points.Therefore, it is being added with height In the case of molecule processing aid, can be to make the moment identical mode of rubber deformation by this resin combination Uniform Tension. In the case of being not added with the resin material of polymer processing aid, there are not this doubtful crosslinking points, thus, for example, in stretching Exist in front thin film thinner thickness part when, stress concentration in this part, produces sometimes and is partially stretched and ruptures this The unfavorable condition of sample.

Used in the present invention, polymer processing aid is the macromolecular compound that average degree of polymerization is 3000～40000, Preferably by more than methyl methacrylate units 60 mass % and can with vinyl monomer unit 40 mass % of its copolymerization below The compound constituting.Average degree of polymerization is preferably 6000～30000, more preferably 10000～25000.As can be with methyl-prop The example of the vinyl monomer of e pioic acid methyl ester copolymerization, can enumerate ethyl methacrylate, butyl methacrylate, metering system The acrylic acid such as the methacrylates such as sour cyclohexyl, ethyl acrylate, acrylic acid methyl ester., butyl acrylate, cyclohexyl acrylate The aromatic ethenyl compounds such as ester, styrene, p- methyl styrene, o- methyl styrene, N- propylmaleimide, N- ring The maleimide amine compounds such as hexyl maleimide, N-o- chlorophenylmaleimide, ethylene glycol dimethacrylate, Dimethacrylate, TEGDMA, hexanediol dimethacrylate, ethylene glycol bisthioglycolate propylene Acid esters, propylene glycol diacrylate, triethylene glycol diacrylate, allkyl methacrylate, triallyl isocyanuric acid The multi-functional monomer such as ester.As such polymer processing aid, the メ タ Block レ of Rhizoma Sparganii Li Yang company manufacture can be enumerated Application series, パ ラ ロ イ De series that the Dow Chemical Company manufactures or Wu Yu company manufactures etc..It should be noted that with regard to macromolecule plus The average degree of polymerization of work auxiliary agent, using automatic dilution capillary viscosimeter (Ubbelohde type), using chloroform as solvent, at 20 DEG C It is measured, obtained with the PMMA conversion degree of polymerization.

With regard to manufacturing the polymerization of polymer processing aid, it is not particularly limited, preferably by the method for emulsion polymerization.Make For emulsifying agent used in emulsion polymerization, it is possible to use for example as the dioctyl sodium sulfosuccinates of anion system emulsifying agent The alkylbenzenesulfonate such as dialkyl sulfosuccinates, dodecylbenzene sodium sulfonate such as sour sodium, dilauryl sodium sulfosuccinate, The alkyl sulfates such as sodium lauryl sulphate, the polyoxyethylene alkyl ether as nonionic system emulsifying agent, ethylene nonyl benzene Base ether etc., the ethylene nonyl phenyl such as ethylene nonyl phenyl ether sodium sulfate as non-ionic anion system emulsifying agent The polyoxyethylene alkyl ether sulfate salts such as ether sulfate, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene tridecyl ether sodium acetate Deng alkyl ether carboxy acid salt etc..

In addition, when being made the pH of polymerization system reach alkali side according to the species of the emulsifying agent being used, in order to prevent methyl Alkyl acrylate, the hydrolysis of alkyl acrylate, it is possible to use suitable pH adjusting agent.As the pH adjusting agent being used, Can using boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid- Hydrogen citrate potassium, potassium dihydrogen phosphate-boric acid, disodium hydrogen phosphate-citric acid etc..

In addition, as polymerization initiator, can be the independent system of water soluble starter or oil-soluble initiator or oxygen Change reduction system, as the example of water soluble starter, the inorganic initiator such as common persulfate can be used alone, or Person uses by the use of with combining of sulphite, bisulfites, thiosulfate etc. as redox system initiator.

As the example of oil-soluble initiator, can be by tertiary hexyl peroxide, cumyl peroxide, benzoyl peroxide first The organic peroxides such as acyl, lauroyl peroxide, azo-compound etc. are used alone, or utilize and sodium formaldehyde sulphoxylate Deng combination to use as redox system initiator, but be not limited to this concrete example.

In addition, the average degree of polymerization of polymer processing aid can utilize the chain such as n octylmercaptan, tert-dodecylmercaotan Transfer agent, polymerizing condition etc. are arbitrarily adjusted.

The average degree of polymerization of the polymer processing aid of the present invention is set as more than 3000 and less than 40000 scope.High When the average degree of polymerization of molecule processing aid is less than 3000, form thin film in the methacrylic resin composition by the present invention Shi Keneng does not observe the raising of film property or does not observe the sufficient improvement improving draftability in stretching.Separately On the one hand, when the average degree of polymerization of polymer processing aid is more than 40000, the transparency reduces or melting tension force is too high sometimes And the both ends of melt curtain are easily torn up in film forming.The use level of polymer processing aid is with respect to methacrylic tree Fat 100 mass parts are 0.3～6 mass parts, preferably 0.5～3 mass parts.The use level of polymer processing aid is less than 0.3 matter During amount part, do not exhibit the forming thin film of methacrylic resin composition and the sufficient improvement of draftability.Separately On the one hand, when the use level of polymer processing aid is more than 6 mass parts, the glass transition of methacrylic resin composition Temperature reduces, and the transparency reduces, and then, melting tension force is too high and both ends of the melt curtain in film forming are easily torn up.

The content of the polycarbonate resin containing in the methacrylic resin composition of the present invention is with respect to above-mentioned first Base acrylic resin 100 mass parts are below more than 1 mass parts and 4 mass parts, more than more preferably 2 mass parts and 3 mass Below part.

The methacrylic resin containing in the methacrylic resin composition of the present invention and polycarbonate resin Total amount be 80 mass % more than, more than preferably 90 mass %, more than more preferably 94 mass %, more preferably 96 More than quality %.It should be noted that with regard to the upper limit of this amount, as long as can obtain in the range of the effect of the present invention at this Then it is not particularly limited containing polymer processing aid in the methacrylic resin composition of invention.

In the methacrylic resin composition of the present invention, can in the range of the effect not damaging the present invention basis Need containing filler.As filler, Calcium Carbonate, Talcum, white carbon black, titanium oxide, silicon dioxide, clay, barium sulfate, carbon can be enumerated Sour magnesium etc..Below the amount of the filler that can contain in the methacrylic resin composition of the present invention preferably 3 mass %, more It is preferably below 1.5 mass %.

In the methacrylic resin composition of the present invention, can contain in the range of the effect not damaging the present invention Other polymers.As other polymers, can enumerate：Polyethylene, polypropylene, poly 1-butene, poly- 4-methyl-1-pentene, poly- The vistanexes such as norborene；Vinyl ionomer；Polystyrene, styrene-maleic anhydride copolymer, high-impact polyphenyl second The styrene resins such as alkene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin；Methyl methacrylate Ester-styrol copolymer；The polyester resin such as polyethylene terephthalate, polybutylene terephthalate (PBT)；Nylon 6, Buddhist nun The polyamide such as dragon 66, polyamide elastomer；Polrvinyl chloride, Vingon, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, bunching Aldehyde, Kynoar, polyurethane, Noryl, polyphenylene sulfide, phenoxy resin, organic-silicon-modified resin；Acrylic compounds rubber Glue, acrylic thermoplastic's elastomer, silicone rubber；The styrene analog thermoplastic elastomers such as SEPS, SEBS, SIS；IR、EPR、 Olefin rubbers such as EPDM etc..The other polymers that can contain in methacrylic resin composition used in the present invention Amount be preferably below 10 mass %, below more preferably 5 mass %, most preferably 0 mass %.

In the methacrylic resin composition of the present invention, can contain in the range of the effect not damaging the present invention Antioxidant, anti-thermal degradation agent, UV absorbent, light stabilizer, lubricant, releasing agent, antistatic additive, fire retardant, dyestuff With additives such as pigment, light diffusing agent, organic pigment, delustering agent, resistance to impact modifying agent, fluorophor.

Antioxidant individually can have the effect of the oxidative degradation preventing resin in the presence of oxygen.Such as phosphorus can be enumerated Class antioxidant, hindered phenol anti-oxidants, thioether antioxidants etc..In these antioxidants, from preventing from being caused by coloring The effect of the deterioration of optical characteristics from the viewpoint of, preferably phosphorus antioxidants, hindered phenol anti-oxidants, more preferably Phosphorus Antioxidant is applied in combination with hindered phenol anti-oxidants.

In the case of being applied in combination phosphorus antioxidants and hindered phenol anti-oxidants, phosphorus antioxidants/hindered phenol Class antioxidant preferably with 0.2/1～2/1 use, more preferably uses with 0.5/1～1/1 by quality ratio.

As phosphorus antioxidants, preferably 2,2- di-2-ethylhexylphosphine oxide (4,6- di-tert-butyl-phenyl) octyl group phosphite ester (ADEKA Company manufactures；Trade name：ア デ カ ス タ Block HP-10), three (2,4- di-tert-butyl-phenyl) phosphite ester (BASF AG manufacture； Trade name：IRGAFOS168), double (2,6- di-t-butyl -4- methylphenoxy) -2,4,8,10- four oxa- -3,9- two phosphorus of 3,9- (ADEKA company manufactures miscellaneous spiral shell [5.5] hendecane；Trade name：ア デ カ ス タ Block PEP-36) etc..

As hindered phenol anti-oxidants, preferably tetramethylolmethane four [3- (3,5- di-tert-butyl-hydroxy phenyl) propanoic acid Ester] (BASF AG manufactures；Trade name IRGANOX1010), octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propanoic acid (BASF AG manufactures ester；Trade name IRGANOX1076) etc..

Anti-thermal degradation agent can be exposed to the polymer producing during hyperpyrexia certainly by the state of capture substantially anaerobic Prevent the heat deterioration of resin by base.

As this anti-thermal degradation agent, and the preferably 2- tert-butyl group -6- (3 '-tert-butyl group -5 '-methylhydroxy benzyl) -4- methylbenzene (the sumitomo chemical company manufacture of base acrylate；Trade name ス ミ ラ イ ザ GM), 2,4- bis- tertiary pentyl -6- (3 ', 5 '-two uncles penta Base -2 '-hydroxy-alpha-methyl benzyl) phenyl acrylate (sumitomo chemical company manufacture；Trade name ス ミ ラ イ ザ GS) etc..

UV absorbent is that have the compound of the ability absorbing ultraviolet, is considered as mainly having and changes luminous energy Compound for the function of heat energy.

As UV absorbent, benzophenone, benzotriazole, triazines, benzoates, bigcatkin willow can be enumerated Esters of gallic acid, cyanoacrylate, oxanilide class, malonic acid esters, formamidine etc..Wherein, preferably benzotriazole, triazine The maximum ε of class or the molar absorption coefficient at wavelength 380～450nm_maxFor 100dm³·mol^-1cm^-1Following ultraviolet Absorbent.

Benzotriazole suppression irradiates, by ultraviolet, the effect height that the optical characteristics such as the coloring causing reduce, it is therefore preferable that As the UV absorbent being applied to use during optical applications by the thin film of the present invention.As benzotriazole, preferably 2- (BASF AG manufactures (2H- benzotriazole -2- base) -4- (1,1,3,3- tetramethyl butyl) phenol；Trade name TINUVIN329), (BASF AG manufactures double (1- methyl isophthalic acid-phenylethyl) phenol of 2- (2H- benzotriazole -2- base) -4,6-；Trade name TINUVIN234), (ADEKA company manufactures 2,2 '-di-2-ethylhexylphosphine oxide [6- (2H- benzotriazole -2- base) -4- tert-octyl phenol]； LA-31), 2- (5- pungent sulfenyl -2H- benzotriazole -2- base) -6- tert-butyl-4-methyl-Phenol etc..

In addition, the maximum ε of the molar absorption coefficient at wavelength 380～450nm_maxFor 1200dm³·mol^-1cm^-1With Under UV absorbent can suppress obtained by thin film variable color.As such UV absorbent, 2- can be enumerated Ethyl -2 ' (Clariant Japanese firm manufactures-ethyoxyl oxanilide；Trade name サ Application デ ユ ボ ア VSU) etc..

In these UV absorbent, from the viewpoint of can suppressing to be irradiated the resin deterioration causing by ultraviolet, excellent Choosing uses benzotriazole.

In addition, in the case of wanting to effectively absorb the wavelength near wavelength 380nm, preferably using the ultraviolet of triazines Light absorbers.As such UV absorbent, 2,4,6- tri- (2- hydroxyl -4- hexyl epoxide -3- methylbenzene can be enumerated Base) (ADEKA company manufactures -1,3,5- triazine；LA-F70), as the hydroxyphenyltriazinuv class UV absorbent of its analog (BASF AG manufactures；TINUVIN477, TINUVIN460), 2,4- diphenyl -6- (2- hydroxyl -4- hexyl phenyl) -1, 3,5- triazine etc..

It should be noted that the maximum ε of the molar absorption coefficient of UV absorbent_maxFollowing mensure.In hexamethylene 1L Middle interpolation UV absorbent 10.00mg, makes it to dissolve in the way of there is not undissolved thing when being observed by visual observation.Will This solution is injected in the quartz glass pond of 1cm × 1cm × 3cm, the U-3410 type light splitting being manufactured using company of Hitachi Photometer, measures the absorbance under wavelength 380～450nm, optical path length 1cm.Molecular weight (M by UV absorbent_UV) and Maximum (the A of the absorbance being measured_max) calculated using following formula, calculate the maximum ε of molar absorption coefficient_max.

ε_max=[A_max/(10×10^-3)]×M_UV

Light stabilizer is considered as the change mainly with the function of free radical that capture generates in the oxidation causing because of light Compound.As preferred light stabilizer, the hindered amines such as the compound with 2,2,6,6- tetraalkyl piperidine skeletons can be enumerated.

As lubricant, such as stearic acid, behenic acid, stearoyl amino acid, methylene bis stearamide, hydroxyl can be enumerated Glycerol stearate three ester, paraffin, ketone wax, capryl alcohol, hydrogenated oil and fat etc..

Releasing agent is that have to make formed products become the compound of easy function from the disengaging of mould.As releasing agent, can To enumerate：The higher alcohols such as spermol, stearyl alcohol；The glycerol higher fatty acids such as glycerol stearate monoesters, glycerol stearate diester Ester etc..In the present invention, preferred compositions are used as releasing agent using higher alcohols and glycerol fatty acid monoester.Senior being applied in combination In the case of alcohols and glycerol fatty acid monoester, the mass ratio of higher alcohols/glycerol fatty acid monoester is preferably with 2.5/1～3.5/ 1 scope is used, and is more preferably used with 2.8/1～3.2/1 scope.

As resistance to impact modifying agent, can enumerate：Containing acrylic rubber or polydiene as stratum nucleare composition Hud typed modifying agent；Comprise modifying agent of multiple rubber particles etc..

As organic pigment, preferably use and there is the function that the ultraviolet that will be considered to that resin is harmful to is converted to visible ray Compound.

As light diffusing agent, delustering agent, glass granules, polysiloxane-based crosslinked fine particles, cross linked polymer can be enumerated micro- Grain, Talcum, Calcium Carbonate, barium sulfate etc..

As fluorophor, fluorescent pigment, fluorescent dye, fluorescent white dyestuff, fluorescent whitening agent, fluorescent bleach can be enumerated Agent etc..

These additives can be used alone one kind or are applied in combination two or more.In addition, these additives can add It is added in polymerization liquid when manufacturing methacrylic resin or polycarbonate resin it is also possible to be added to manufactured first In base acrylic resin or polycarbonate resin, can also be added when preparing methacrylic resin composition. From the viewpoint of the bad order of suppression thin film, contain in methacrylic resin composition used in the present invention adds Plus the total amount of agent is preferably below 7 mass % with respect to methacrylic resin, below more preferably 5 mass %, enter one Step is preferably below 4 mass %.

The preparation method of above-mentioned methacrylic resin composition is not particularly limited.For example, it is possible to enumerate：In poly- carbon Contain the monomer mixture polymerization of methyl methacrylate when in the presence of acid ester resin and generate methacrylic resin Method, by method of methacrylic resin and polycarbonate resin melting mixing etc..Wherein, the operation letter of melting mixing method Single, therefore preferably.In melting mixing, other polymers, additive can be mixed as needed it is also possible to by metering system Acid resin is mixed with polycarbonate resin after being mixed with other polymers and additive, can also by polycarbonate resin with Mix with methacrylic resin after other polymers and additive mixing.Mixing for example can use kneading extruder, squeeze Go out the known mixing arrangement such as machine, mixing mill, banbury mixers or kneading device to carry out.Wherein, preferred biaxial extruder. Temperature when mixing, mixing can according to using methacrylic resin and the melt temperature etc. of polycarbonate resin come Suitably adjust, preferably 110 DEG C～300 DEG C.The methacrylic resin composition prepared by method as above can To form the arbitrary form such as granule, powder, powder and to be configured to thin film.

The glass transition temperature of the methacrylic resin composition of the present invention is preferably more than 120 DEG C, more preferably For more than 123 DEG C, more preferably more than 124 DEG C.The glass transition temperature of methacrylic resin composition upper Limit is not particularly limited, preferably 140 DEG C, more preferably 130 DEG C.

It is preferably 70000 using the Mw that GPC is measured and determines to the methacrylic resin composition of the present invention ～200000, more preferably 72000～160000, more preferably 75000～120000.Made in the present invention using GPC The molecular weight distribution that methacrylic resin composition is measured and determines is preferably 1.2～2.5, more preferably 1.3～2.0.Mw, molecular weight distribution within the range when, the shaping processability of methacrylic resin composition is good, holds Be easy to get the formed body of resistance to impact, good-toughness.

Under conditions of 230 DEG C and 3.8kg load, the methacrylic resin composition of the present invention is measured and The melt flow rate (MFR) determining preferably 0.1～6g/10 minute, more preferably 0.5～5g/10 minute, most preferably 1.0 ～3g/10 minute.

The mist degree of the 1.0mm thickness of the methacrylic resin composition of the present invention is preferably less than 1.0%, more preferably For less than 0.7%, more preferably less than 0.5%.

The thin film of the present invention is not particularly limited to by its preparation method.The thin film of the present invention for example can pass through above-mentioned methyl-prop Olefin(e) acid based resin composition utilizes solution-casting method, melting the tape casting, extrusion molding method, inflation forming process, blow-moulding process etc. Known method carries out film forming to obtain.Wherein, preferred extrusion molding method.According to extrusion molding method, the transparency can be obtained excellent Good, have that improved toughness, treatability be excellent, thin film that the balance of toughness and case hardness and rigidity is excellent.From extrusion The temperature of the methacrylic resin composition that machine spues is preferably set to 160～270 DEG C, is more preferably set as 220～260 ℃.

In extrusion molding method, from the viewpoint obtaining good surface smoothness, good bright luster, the thin film of low haze Consider, the method preferably including following operation：By above-mentioned methacrylic resin composition in the molten state from T-shaped mould head It then is clamped to form by middle extrusion with plural mirror roller or minute surface band.Mirror roller or minute surface band are preferably Metal system.Line pressure between a pair of mirror roller or minute surface band is preferably more than 10N/mm, more preferably more than 30N/mm.

In addition, the surface temperature of mirror roller or minute surface band is preferably all less than 130 DEG C.In addition, a pair of mirror roller or minute surface The surface temperature of at least one of band is preferably more than 60 DEG C.When being set as such surface temperature, can make from extruder The above-mentioned methacrylic resin composition spuing is cooled down with letting cool fast speed than naturally, and easy to manufacture surface smooths Property is excellent and the thin film of the low present invention of mist degree.

The thin film of the present invention can be the thin film after implementing stretch processing.By stretch processing, mechanical strength can be obtained Improve, be not likely to produce the thin film in crack.Drawing process is not particularly limited, can enumerate uniaxial tension, simultaneously biaxial drawing method, Gradually biaxial stretching process, tubular pull method etc..From the viewpoint of the thin film that can be evenly stretched, obtain high intensity, stretching When temperature be preferably 100～200 DEG C, more preferably 120～160 DEG C.In addition, in the case of particularly desirable increase intensity, More preferably low temperature, for example, it is preferable to be 110～150 DEG C, more preferably 125～140 DEG C.Preferably in methacrylic More than the glass transition temperature of resin combination stretched.Stretching is generally in terms of length standard with 100～5000%/minute Carry out.Implement heat fixation after the stretch or make lax, less thereby, it is possible to the make thermal contraction thin film of thin film.Stretching ratio Do not limit, in terms of area ratio, be generally set as about 1.5 times～about 8 times.

For the thin film of the present invention, from the viewpoint of the phase contrast of the transparency, thickness direction is little, the methyl that wherein contains The amount of acrylic resin is preferably 78～98.7 mass %, more preferably 85～97 mass %.

In addition, for the thin film of the present invention, from the viewpoint of the phase contrast of thickness direction is little, the poly- carbonic acid that wherein contains The amount of ester resin is preferably 1～3.8 mass %, more preferably 2～2.9 mass %.

In addition, for the thin film of the present invention, from the viewpoint of draftability, the amount of the polymer processing aid wherein containing It is preferably 0.3～5.6 mass %, more preferably 0.5～2.9 mass %.

The thickness of the thin film of the present invention is not particularly limited, and in the case of using as optical thin film, its thickness is preferred For 1～300 μm, more preferably 10～50 μm, more preferably 15～40 μm.

The mist degree in 50 μm of thickness for the thin film of the present invention is preferably less than 0.2%, more preferably less than 0.1%.Thus, Lustrous surface, excellent transparency.In addition, in the optical applications such as liquid crystal protective film, light directing film, the utilization ratio of light source increases Height, thus preferably.Additionally, the figuration precision carrying out during the figuration of surface is excellent, therefore preferably.

With regard to direction phase contrast Re in the face of the light to wavelength 590nm for the thin film of the present invention, it is 40 μm in the thickness of thin film When, preferably below 5nm, more preferably below 4nm, more preferably below 3nm, particularly preferably below 2nm, most preferably For below 1nm.

With regard to the thickness direction phase contrast Rth of the light to wavelength 590nm for the thin film of the present invention, it is 40 μm in the thickness of thin film When, preferably more than -10nm and below 10nm, more preferably more than -5nm and below 5nm, more preferably more than -4nm and Below 4nm, more preferably more than -3nm and below 3nm, particularly preferably more than -2nm and below 2nm, most preferably - More than 1nm and below 1nm.

When in face, direction phase contrast and thickness direction phase contrast are this scope, because phase contrast cause to image display device The impact of display characteristic can significantly be inhibited.More specifically, interfere uneven, 3D display liquid crystal indicator The deformation of 3D rendering during middle use can significantly be inhibited.

It should be noted that direction phase contrast Re and thickness direction phase contrast Rth is defined by following formula respectively in face Value.

Re=(nx-ny) × d

Rth=((nx+ny)/2-nz) × d

Here, nx is the slow mutually axial refractive index of thin film, ny is the refractive index in the leading phase shaft direction of thin film, and nz is thin The refractive index of the thickness direction of film, d (nm) is the thickness of thin film.Phase axle refers to that the refractive index in pellicular front reaches the side of maximum late To leading phase shaft refers to vertical with slow phase axle direction in face.

The transparency of the thin film of the present invention is high, thermostability is high, phase contrast is little and thin, is thus suitable for polarizer protection film With various thin film described later etc..

The polarization plates of the present invention are laminated with the polarizer protection film of an at least thin film comprising the present invention.Preferably will be by The polaroid that polyvinyl alcohol resin is formed is formed across adhesive layer stackup with the polarizer protection film of the present invention.

The polarization plates of a preferred embodiment of the present invention as shown in figure 1, on a face of polaroid 11 layer successively The polarizer protection film 14 of folded gluing oxidant layer 12, easy adhesive layer 13 and the present invention and on another face of polaroid 11 successively Laminated stickiness oxidant layer 15 and optical thin film 16 and formed.

The above-mentioned polaroid being formed by polyvinyl alcohol resin is for example by by polyvinyl alcohol resin thin film dichromatic Material (being iodine, dichroic dye with representing) dyes and carries out uniaxial tension to obtain.Polyvinyl alcohol resin thin film can lead to Cross and (for example, resin will be made to be dissolved in water or organic solvent to obtain using arbitrarily suitable method by polyvinyl alcohol resin Solution carry out the tape casting of casting film-forming, casting, extrusion molding) carry out film forming to obtain.This polyvinyl alcohol resin poly- Right preferably 100～5000, more preferably 1400～4000.In addition, polyvinyl alcohol resin used in polaroid The thickness of thin film suitably can set according to the purpose of the LCD using polarization plates and purposes, is 5～80 μm with representing.

As long as the gluing oxidant layer that can arrange in the polarization plates of the present invention is optically transparent, it is not particularly limited.Make For constituting the adhesive of gluing oxidant layer, it is possible to use such as water system adhesive, solvent system adhesive, hot melt system adhesive, activity Energy ray-curable adhesive etc..Wherein, preferably water system adhesive and active energy ray curable adhesive.

The form of water system adhesive can be aqueous solution or latex.As water system adhesive, especially do not limit Fixed, can illustrate for example vinyl polymerization species, gelatin class, vinyl latex class, polyurethaness, isocyanates, polyesters, Epoxiess etc..In such water system adhesive, the catalyst such as cross-linking agent and other additives, acid can also be coordinated as needed. As above-mentioned water system adhesive, preferably use adhesive containing polyvinyl etc., as polyvinyl, preferably poly- Vinyl alcohol resin.In addition, the water such as boric acid, Borax, glutaraldehyde, tripolycyanamide, oxalic acid can be contained in polyvinyl alcohol resin Dissolubility cross-linking agent.Particularly in the case of use the thin polymer film of polyvinyl alcohol as polaroid, from adhesivity Viewpoint considers, preferably uses the adhesive containing polyvinyl alcohol resin.Additionally, from the viewpoint of improving durability, more excellent The adhesive containing the polyvinyl alcohol resin with acetoacetyl for the choosing.Above-mentioned water system adhesive is generally to be formed by aqueous solution Adhesive form use, usually contain the solid constituent of 0.5～60 mass %.

As active energy ray curable adhesive, except using more than simple function and two senses there is (methyl) third The compound of enoyl-, have the compound of vinyl as curability composition beyond, can also use with epoxide, oxygen Oxetane compounds and photoacid generator are as the cationic curing composition of light of main body.As active energy beam, can make With electron ray, ultraviolet.

In addition, in above-mentioned adhesive, metallic compound filler can be contained.Using metallic compound filler, can control The mobility of gluing oxidant layer, makes thickness stable, can obtain having good outward appearance, in face uniformly and there is no the fluctuation of adhesivity Polarization plates.

The forming method of gluing oxidant layer is not particularly limited.For example, it is possible to by above-mentioned adhesive is applied to object Go up, then heated or be dried to be formed.The coating of adhesive can be to the polarizer protection film of the present invention or optically thin Film is carried out it is also possible to carry out to polaroid.After forming gluing oxidant layer, polarizer protection film or optical thin film are squeezed with polaroid Pressure, thereby, it is possible to be laminated both.In stacking, it is possible to use roll squeezer, platen-press etc..Heat drying temperature, drying time Species according to adhesive is suitably determining.

The thickness of gluing oxidant layer is preferably 0.01～10 μm in the dry state, more preferably 0.03～5 μm.

The easy adhesive layer that can arrange in the polarization plates of the present invention is to improve polarizer protection film to contact with polaroid The layer of the adhesivity in face.Easily adhesive layer can be configured by easily gluing process etc..As easily gluing process, electricity can be enumerated The surface treatments such as dizzy process, corona treatment, the process of low pressure UV.In addition, easy adhesive layer can be by forming the side of anchor layer Method is configured or by the Combination of Methods of above-mentioned surface treatment and formation anchor layer using being configured.Wherein, excellent Select sided corona treatment, the method forming anchor layer and the method that they are applied in combination.

As above-mentioned anchor layer, the silicone layer for example with reactive functional groups can be enumerated.There is reactive functional The material of the silicone layer of group is not particularly limited, and can enumerate and for example contains the alkoxyl silicone alcohols of NCO, contains amino Alkoxyl silicone alcohols, containing the alkoxyl silicone alcohols of sulfydryl, carboxylic alkoxyl silicone alcohols, the alkoxyl silanol containing epoxy radicals Class, the alkoxyl silicone alcohols containing vinyl-type unsaturated group, the alkoxyl silicone alcohols of Halogen group elements, the alkane containing NCO Epoxide silanol class.Wherein, preferred amino system silanol.By adding in above-mentioned silanol for making the titanium system of silanol highly effective reaction urge Agent, stannum series catalysts, can make adhesive tension become firm.Furthermore it is possible in the above-mentioned organosilicon with reactive functional groups Middle other additives of interpolation.As other additives, can enumerate：The dilute resin of terpene, phenolic resin, terpene be dilute-phenolic resin, Colophonium The viscosifier such as resin, xylene resin；Stabilizers such as UV absorbent, antioxidant, heat-resisting stabilizing agent etc..In addition, conduct Anchor layer, can enumerate by the layer making the resin after cellulose acetate butyrate resin saponification constitute.

Above-mentioned anchor layer is coated by using known technology, is dried to be formed.The thickness of anchor layer is being dried shape It is preferably 1～100nm, more preferably 10～50nm under state.During coating, anchor layer formation medicinal liquid solvent can be entered Row dilution.Retarder thinner is not particularly limited, and can enumerate alcohols.Diluted concentration is not particularly limited, preferably 1～5 matter Amount %, more preferably 1～3 mass %.

Optical thin film 16 can be the polarizer protection film of the present invention or arbitrarily suitable optically thin of others Film.The optical thin film being used is not particularly limited, and can enumerate and for example comprise celluosic resin, polycarbonate resin, ring-type The thin film of vistanex, methacrylic resin etc..

Celluosic resin is the ester of cellulose and fatty acid.As the concrete example of such cellulose esters system resin, permissible Enumerate cellulosic triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate etc..Wherein, especially excellent Select cellulosic triacetate.Cellulosic triacetate is commercially available substantial amounts of product, from the viewpoint of easy acquisition, cost is also Favourable.As the example of the commercially available product of cellulosic triacetate, the trade name " UV- of Fuji Photo Film Co., Ltd.'s manufacture can be enumerated 50 ", " the KC series " that " UV-80 ", " SH-80 ", " TD-80U ", " TD-TAC ", " UZ-TAC ", Konica Minolta company manufacture Deng.

Cyclic polyolefin resin is the general name of the resin being polymerized as polymerized unit using cyclic olefin, can enumerate example As Japanese Unexamined Patent Publication 1-240517 publication, Japanese Unexamined Patent Publication 3-14882 publication, Japanese Unexamined Patent Publication 3-122137 publication etc. The resin recorded.As concrete example, the open loop (co) polymer of cyclic olefin, the addition polymers of cyclic olefin, ring-type can be enumerated The copolymer (representing ground for random copolymer) of alkene and the alpha-olefin such as ethylene, propylene and by they with unsaturated carboxylic acid or its Graft polymers obtained from derivative modified and their hydride etc..As the concrete example of cyclic olefin, can enumerate Norborneol alkene monomer.

As cyclic polyolefin resin, commercially available have various products.As concrete example, Japanese auspicious father-in-law can be enumerated public The trade name " ゼ オ ネ ッ Network ス " of department's manufacture, " ゼ オ ノ ア ", the trade name " ア ト Application " of JSR company manufacture, Port リ プ ラ ス The trade name " APEL " that the trade name " ト パ ス " of チ ッ Network ス company manufacture, Mitsui Chemicals, Inc.'s system are made.

As methacrylic resin used in optical thin film 16 grade optical thin film, in the effect not damaging the present invention In the range of, can be using arbitrarily suitable methacrylic resin.For example, it is possible to enumerate polymethyl methacrylate etc. Polymethacrylates, methyl methacrylate-(methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylic acid Ester copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, (methyl) acrylate-styrene are common Polymers (MS resin etc.), (for example, methyl methacrylate-cyclohexyl methacrylate is common to have the polymer of alicyclic alkyl Polymers, methyl methacrylate-(methyl) acrylic acid norborneol ester copolymer etc.).

As the concrete example of methacrylic resin used in optical thin film 16 grade optical thin film, can enumerate for example ア Network リ ペ ッ ト VH, ア Network リ ペ ッ ト VRL20A, Japanese Unexamined Patent Publication 2013-033237 and WO2013/ that Rhizoma Sparganii Li Yang company manufactures No. 005634 publication record by acrylic resin obtained from methyl methacrylate maleimide amine system monomer copolymerization, Acrylic resin, the Japanese Unexamined Patent Publication 2009-197151 in intramolecular with ring structure that WO2005/108438 publication is recorded What number publication was recorded has the methacrylic resin of ring structure, anti-by intramolecular crosslinking or intramolecular cyclization in intramolecular High glass-transition temperature (Tg) methacrylic resin that should obtain.

As methacrylic resin, it is possible to use have the methacrylic resin of lactone ring structure.This is Because there is high-fire resistance, high transparent, by carrying out biaxial stretch-formed, there are high mechanical properties.

As the above-mentioned methacrylic resin with lactone ring structure, Japanese Unexamined Patent Publication 2000-230016 can be enumerated Number publication, Japanese Unexamined Patent Publication 2001-151814 publication, Japanese Unexamined Patent Publication 2002-120326 publication, Japanese Unexamined Patent Publication 2002- The methacrylic with lactone ring structure described in No. 254544 publications, Japanese Unexamined Patent Publication 2005-146084 publications etc. Resin.

The polarization plates of the present invention can be used for image display device.As the concrete example of image display device, can enumerate Electroluminescent (EL) display, plasma scope (PD), Field Emission Display (FED：Field Emission Display) such self-luminous display device, liquid crystal indicator.Liquid crystal indicator has liquid crystal cell and configuration at this At least unilateral above-mentioned polarization plates of liquid crystal cell.

In the methacrylic resin composition of the present invention, methacrylic resin is with polycarbonate resin equably Compatible, therefore, the transparency is high, even and if be stretched, the phase contrast of thickness direction is also little.In addition, the drawing of obtained thin film Stretching property is high.Therefore, the methacrylic resin composition according to the present invention, can obtain that thin, inner evenness is excellent, surface The high thin film of flatness.In addition, stretching at low temperatures is possibly realized, the big thin film of intensity can be obtained.Additionally, passing through The degree of syndiotacticity (rr) of methacrylic resin is set as particular value, it is possible to increase thermostability is such that it is able to carry For the little thin film of percent thermal shrinkage.

Embodiment

Hereinafter, by embodiment and comparative example, specifically the present invention will be described, but the present invention is not limited to following realities Apply example.It should be noted that the mensure of physics value etc. is implemented by following method.

(polymerisation conversion)

The gas chromatograph GC-14A that company of Shimadzu Seisakusho Ltd. manufactures connects what GL Sciences company manufactured Inert CAP 1 (df=0.4 μm, 0.25mmI.D. × 60m), as chromatographic column, is set as following condition：The injection temperature is made to be 180 DEG C, make detector temperature be 180 DEG C, column temperature was warming up to 10 DEG C/min of programming rate from 60 DEG C (keeping 5 minutes) 200 DEG C, and keep 10 minutes, it is measured, polymerisation conversion is calculated based on this result.

(weight average molecular weight (Mw), molecular weight distribution (Mw/Mn))

With regard to the methacrylic resin that obtains in each Production Example, embodiment and comparative example and methacrylic resin The Mw of compositionss and molecular weight distribution, measure chromatogram under the following conditions by gel permeation chromatography (GPC), calculate conversion Value for the molecular weight of polystyrene standard.Baseline is set as the slope at the peak of the high molecular side of GPC figure from retention time Early unilateral observation from zero be changed on the occasion of point low-molecular-weight side peak slope from the unilateral observation of retention time morning from negative value The line obtained from point connection of vanishing.

GPC device：TOSOH Co., Ltd manufactures, HLC-8320

Detector：Differential refraction rate detector

Chromatographic column：Using the TSKgel SuperMultipore HZM-M that TOSOH Co., Ltd is manufactured two with The chromatographic column that Superhz4000 is connected in series.

Eluant：Oxolane

Eluant flow：0.35mL/ minute

Column temperature：40℃

Standard curve：Data using 10 points of polystyrene standard is made

(viscosity-average molecular weight (Mv))

With regard to the viscosity-average molecular weight of polycarbonate resin, using Ubbelohde viscometer, measure polycarbonate resin at 20 DEG C Fat 0.5g is dissolved in specific viscosity η of solution obtained from dichloromethane 100mL_sp, as meeting following Schnell formula Value, is calculated the viscosity-average molecular weight of polycarbonate resin by the limiting viscosity [η] of 20 DEG C of dichloromethane solutions.

η_sp/ c=[η]+0.45 × [η]²c

(wherein, [η] is limiting viscosity, c=0.5 under these conditions)

[η]=1.23 × 10^-4Mv^0.83

(degree of syndiotacticity (rr) in terms of triad)

Using nuclear magnetic resonance device (the ULTRA SHIELD 400PLUS that Bruker company manufactures), made using deuterochloroform For solvent, measure methacrylic resin in the condition that room temperature, cumulative number are 64 times¹H-NMR composes.Being measured by this spectrum makes TMS is the area (Y) of the area (X) in the region of 0.6～0.95ppm during 0ppm and the region of 0.6～1.35ppm, then, profit Use formula：(X/Y) × 100 calculate the degree of syndiotacticity (rr) in terms of triad.

(glass transition temperature Tg)

For methacrylic resin, polycarbonate resin and methacrylic resin composition, according to JIS K7121, measures device (Shimadzu Seisakusho Ltd. manufacture, DSC-50 (model)) using means of differential scanning calorimetry, be formerly warming up to 230 DEG C, It is then cooled to room temperature and then measure DSC curve under conditions of 230 DEG C from room temperature with 10 DEG C/min.Will be by second The intermediate point glass transition temperature that the DSC curve measuring during intensification is obtained is as the glass transition temperature in the present invention.

(melt mass flow rate (MFR))

According to JIS K7210,230 DEG C, 3.8kg load, under conditions of 10 minutes, make in each embodiment and comparative example Used in manufacture for thin film, the methacrylic resin of the raw material of methacrylic resin composition is measured.

(melt volume-flow rate (MVR))

According to JIS K7210,300 DEG C, 1.2kg load, under conditions of 10 minutes, make in each embodiment and comparative example Used in manufacture for thin film, the polycarbonate resin of the raw material of methacrylic resin composition is measured.

(surface smoothness)

By visual observation the surface of the biaxially oriented film obtaining in each embodiment and comparative example is observed, according to following Benchmark is evaluated to surface smoothness.

A：Surface smooths.

B：Surface has concavo-convex.

(average degree of polymerization of polymer processing aid)

Using automatic dilution type capillary viscosimeter (Ubbelohde type, capillary inner diameter=0.5mm), using chloroform as solvent, It is measured at 20 DEG C, obtained with the PMMA conversion degree of polymerization.

(heat shrink rate)

The biaxially oriented film obtaining from each embodiment and comparative example cuts the test film of 100mm × 30mm, in its table Drawing lower length on face is the straight line of 70mm, heats 30 in the circulating constant temperature oven of pressure warm air of the temperature being held in 110 DEG C Minute, then, using ruler read drawn by under straight line length (L (mm)), obtain heat shrink rate using following formula.

Heat shrink rate (%)=(70-L)/70 × 100

(total light transmittance)

The biaxially oriented film obtaining from each embodiment and comparative example cuts the test film of 50mm × 50mm, according to JIS K7361-1, measures the total light transmittance of this test film using haze meter (in village, color institute manufactures, HM-150).In addition, In the evaluation of methacrylic resin composition, shape the thick formed body of 1.0mm by hot pressing, measure total light transmission Rate.

(mist degree)

The biaxially oriented film obtaining from each embodiment and comparative example cuts the test film of 50mm × 50mm, according to JIS K7136, measures the mist degree of this test film using haze meter (in village, color institute manufactures, HM-150).In addition, methacrylic acid In the evaluation of based resin composition, shape the thick formed body of 1.0mm by hot pressing, measure mist degree.

(direction phase contrast Re in thickness direction phase contrast Rth dough-making powder)

The biaxially oriented film obtaining from each embodiment and comparative example cuts the test film of 40mm × 40mm.For this examination Test piece, using automatic birefringence meter (prince measures Co., Ltd. and manufactures, KOBRA-WR), 23 ± 2 DEG C of temperature, humidity 50 ± Under conditions of 5%, three-dimensional refractive index nx, ny, nz are obtained by the phase difference value of wavelength 590nm, 40 ° of incline directions, by aforementioned Formula calculate direction phase contrast Re in thickness direction phase contrast Rth dough-making powder.The thickness d (nm) of test film uses thousand points of digital display Table (デ ジ マ テ ィ ッ Network イ Application ジ ケ タ) (Mitutoyo Corp's manufacture) is measured, and refractive index n is rolled over using digital precision Penetrate meter (カ Le ニ ュ optics industry Co., Ltd., KPR-20) to be measured.

(draftability)

When biaxial stretch-formed is carried out to the non-stretched film obtaining in each embodiment and comparative example, according to following benchmark evaluation Draftability.In stretching, non-stretched film is cut into 100mm × 100mm, using scaling type biaxial tension-compression strength machine (Toyo Seiki Company manufactures), under the draft temperature of+10 DEG C of glass transition temperature, with one direction be 120%/minute draw speed, with One direction is that 2 times of stretching ratio carries out gradually biaxial stretch-formed rear (being calculated as 4 times with area ratio), keeps 10 seconds, then carries out cold But.

A：It is obtained in that the thin film not having rupture or crackle of more than 5 samples in 10 samples.

B：It is only capable of obtaining the thin film not having rupture or crackle of below 4 samples in 10 samples.

<Production Example 1>

Enter line replacement by being provided with the glass system reaction vessel of the 5L of stirring vane and three-way cock with nitrogen.In room temperature Under put into toluene 1600g, 1,1,4,7,10,10- hexamethyl three second tetramine 2.49g (10.8mmol), concentration 0.45M thereto The toluene solution 53.5g (30.9mmol) of double (2,6- di-t-butyl -4- methylphenoxy) aluminum of isobutyl group and concentration 1.3M secondary Solution (the solvent of butyl lithium：Hexamethylene 95 mass %, n- hexane 5 mass %) 6.17g (10.3mmol).While stirring, With the methyl methacrylate 550g of 30 minutes Deca distillation purifyings thereto at -20 DEG C.After completion of dropwise addition, at -20 DEG C Stirring 180 minutes.The color of solution becomes colorless from yellow.The polymerisation conversion of the methyl methacrylate in this moment is 100%.

Toluene 1500g is added to be diluted in obtained solution.Then, this diluent is injected into methanol 100kg In, it is precipitated thing.Obtained precipitate is dried 24 hours under 80 DEG C, 140Pa, obtaining Mw is that 96100, molecular weight divides Cloth is 1.07, degree of syndiotacticity (rr) is that 83%, glass transition temperature is 133 DEG C and derives from methyl methacrylate Construction unit ratio be 100 mass % methacrylic resin [PMMA1].

<Production Example 2>

Enter line replacement by being provided with the glass system reaction vessel of the 5L of stirring vane and three-way cock with nitrogen.In room temperature Under put into 1600g, 1,1,4,7,10,10- hexamethyl three second tetramine 2.49g (10.8mmol), the isobutyl of concentration 0.45M thereto Double (2,6- di-t-butyl -4- methylphenoxy) the toluene solution 53.5g (30.9mmol) of aluminum of base and the sec-butyl of concentration 1.3M Solution (the solvent of lithium：Hexamethylene 95%, n- hexane 5%) 6.17g (10.3mmol).While stirring, at 20 DEG C, use 30 The methyl methacrylate 550g of minute Deca distillation purifying thereto.After completion of dropwise addition, stir 90 minutes at 20 DEG C.Solution Color become colorless from yellow.The polymerisation conversion of the methyl methacrylate in this moment is 100%.

Toluene 1500g is added to be diluted in obtained solution.Then, this diluent is injected into methanol 100kg In, it is precipitated thing.Obtained precipitate is dried 24 hours under 80 DEG C, 140Pa, obtaining Mw is that 81400, molecular weight divides Cloth is 1.08, degree of syndiotacticity (rr) is that 73%, glass transition temperature is 131 DEG C and derives from methyl methacrylate Construction unit content be 100 mass % methacrylic resin [PMMA2].

<Production Example 3>

Enter line replacement by being provided with the autoclave of blender and collection tube with nitrogen.Load the methyl-prop of purification wherein Double (2- methyl the propionitrile) (ability of dehydrogenation of e pioic acid methyl ester 100 mass parts, 2,2 '-azo：1%th, 1 hour half life temperature：83℃) 0.0052 mass parts and n octylmercaptan 0.28 mass parts, stirring, obtain material liquid.Send into nitrogen in this material liquid, will be former Dissolved oxygen in feed liquid removes.

In the tank reactor being connected with autoclave by pipe arrangement, charging feedstock liquid is to the 2/3 of capacity.By temperature It is maintained at 140 DEG C, first polyreaction is started with intermittent mode.When polymerisation conversion reaches 55 mass %, during with average stop Between for the flow of 150 minutes by material liquid from autoclave supplies to tank reactor, and with the supply flow rate phase with material liquid When flow reactant liquor is extracted out from tank reactor, temperature is maintained at 140 DEG C, is converted to the polymerization of continuous flow mode Reaction.After conversion, the polymerisation conversion under stable state is 55 mass %.

The flow supply that the reactant liquor extracted out from the tank reactor reach stable state is 2 minutes with mean residence time Heated in the multi tube heat exchanger being 230 DEG C to interior temperature.Then, the reactant liquor after heating is imported to adiabatic flash vessel In, the volatile ingredient using unreacted monomer as main component is removed, obtains molten resin.Molten after volatile ingredient by removing In the double screw extruder that it is 260 DEG C to interior temperature that melt resin supplies, spued with strands shape, cut with comminutor, obtain Granular, Mw be 82000, molecular weight distribution be 1.85, degree of syndiotacticity (rr) be that 52%, glass transition temperature is 120 DEG C and from methyl methacrylate construction unit content be 100 mass % methacrylic resin [PMMA3].

<Production Example 4>

In addition to by the quantitative change of n octylmercaptan more 0.225 mass parts, carry out operating with Production Example 3 identical, obtain To Mw be 103600, molecular weight distribution be 1.81, degree of syndiotacticity (rr) be 52%, glass transition temperature be 120 DEG C, And derive from the methacrylic resin [PMMA4] that the ratio of the construction unit of methyl methacrylate is 100 mass %.

<Production Example 5>

In addition to by the quantitative change of n octylmercaptan more 0.30 mass parts, carry out operating with Production Example 3 identical, obtain Mw is 76400, molecular weight distribution is 1.81, degree of syndiotacticity (rr) is that 53%, glass transition temperature is 119 DEG C and comes The content coming from the construction unit of methyl methacrylate is the methacrylic resin [PMMA5] of 100 mass %.

<Production Example 6>

Methacrylic resin [PMMA2] 57 mass parts and methacrylic resin [PMMA4] 43 mass parts are mixed Close, using biaxial extruder, (テ クノベル company manufactures, trade name：KZW20TW-45MG-NH-600) knead at 250 DEG C Extrusion, manufactures methacrylic resin [PMMA6].

Using ス ミ ペ ッ Network ス MHF (sumitomo chemical company manufacture) as methacrylic resin [PMMA7].

The physical property of above-mentioned [PMMA1]～[PMMA7] is shown in Table 1.

[table 1]

Used in embodiment, polycarbonate resin is as described below, and physical property is as described in Table 2.

PC1：Chu Guangxingchan company manufactures, タ Off ロ Application LC1700 (model)；MVR (300 DEG C, 1.2Kg)=40cm³/10 Minute, Mv=16200

PC2：Mitsubishi Engineering-Plastics company manufactures, ユ ピ ロ Application HL-4000 (model)；MVR (300 DEG C, 1.2Kg)= 60cm³/ 10 minutes, Mv=15100

PC3：Live to change the manufacture of Si Tailong Merlon company, SD POLYCA SD-2201W (model)；MVR(300℃、 1.2Kg)=115cm³/ 10 minutes, Mv=13000

PC4：Live to change the manufacture of Si Tailong Merlon company, SD POLYCA TR-2001 (model)；MVR(300℃、 1.2Kg)=200cm³/ 10 minutes, Mv=11400

PC5：Mitsubishi Engineering-Plastics company manufactures, AL071；MVR (300 DEG C, 1.2Kg)=1000cm³More than/10 minutes (mobility high and be difficult to Accurate Determining), Mv=5500

PC6：50 mass parts of PC4 and the mixture of 50 mass parts of PC5；MVR (300 DEG C, 1.2kg)=1000cm³/10 Minute above (mobility is high and be difficult to Accurate Determining), Mv=8500

[table 2]

Used in embodiment, polymer processing aid is as described below.It should be noted that here, MMA means to originate In the construction unit of methyl methacrylate, BA means the construction unit from butyl acrylate.

B1：The メ タ Block レ Application P570A (average degree of polymerization that Rhizoma Sparganii Li Yang company manufactures：2384th, MMA53 mass %/BA47 Quality %)

B2：The メ タ Block レ Application P550A (average degree of polymerization that Rhizoma Sparganii Li Yang company manufactures：7734th, MMA88 mass %/BA12 Quality %)

B3：The パ ラ ロ イ De K125P (average degree of polymerization that Wu Yu company manufactures：19874th, MMA79 mass %/BA21 matter Amount %)

B4：The メ タ Block レ Application P530A (average degree of polymerization that Rhizoma Sparganii Li Yang company manufactures：24455th, MMA80 mass %/ BA20 mass %)

B5：The メ タ Block レ Application P531A (average degree of polymerization that Rhizoma Sparganii Li Yang company manufactures：37162nd, MMA80 mass %/ BA20 mass %)

As UV absorbent, using 2,4,6- tri- (2- hydroxyl -4- hexyl epoxide -3- aminomethyl phenyls) -1,3,5- tri- (ADEKA company manufactures piperazine；LA-F70).

<Embodiment 1>

Methacrylic resin [PMMA1] 100 mass parts, polycarbonate resin [PC1] 2.5 mass parts and processing are helped Agent [B2] 2 mass parts mix, and using biaxial extruder, (テ クノベル company manufactures, trade name：KZW20TW-45MG-NH- 600) mixing extrusion at 250 DEG C, manufactures methacrylic resin composition [1].To obtained methacrylic tree Oil/fat composition [1] carries out hot forming, forms the tabular formed body of 50mm × 50mm × 1.0mm, measures total light transmittance, mist Degree and glass transition temperature.The physical property of methacrylic resin composition [1] is shown in Table 3.

Methacrylic resin composition [1] is dried 12 hours at 80 DEG C.UseSingle axle extruding machine (manufacture of OCS company), will be T-shaped for 150mm from width for methacrylic resin composition [1] at 260 DEG C of resin temperature Extrude in die head, it carried out tractive using the roller of 85 DEG C of surface temperature, obtain width 110mm, 160 μm of thickness non-stretched thin Film.

The non-stretched film obtaining by said method is cut into 100mm × 100mm, using scaling type biaxial tension-compression strength Machine (manufacture of Toyo Seiki company), under the draft temperature of+10 DEG C of glass transition temperature, is 500%/minute with one direction Draw speed, it is that 2 times of stretching ratio carries out gradually biaxial stretch-formed (being calculated as 4 times with area ratio) with one direction, cooled down with 2 minutes To less than 100 DEG C and take out, obtain the biaxially oriented film of 40 μm of thickness.By the surface with regard to obtained biaxially oriented film Flatness, heat shrink rate, total light transmittance, mist degree, direction phase contrast Re, thickness direction phase contrast Rth and by not in face The measurement result that oriented film makes draftability during oriented film is shown in Table 3.

<Embodiment 2～11, comparative example 1～7>

In addition to being set as the cooperation shown in table 3 and table 4, metering system is manufactured by method same as Example 1 Acrylic resin composition [2]～[18].Obtained methacrylic resin composition [2]～[18] are hot pressed into Shape, forms the tabular formed body of 50mm × 50mm × 1.0mm, measures total light transmittance, mist degree and glass transition temperature.Will The physical property of methacrylic resin composition [2]～[18] is shown in table 3 and table 4.

Except replacing methacrylic resin composition using methacrylic resin composition [2]～[18] [1], beyond, biaxially oriented film is obtained by method same as Example 1.Evaluation result is shown in table 3 and table 4.

[table 3]

* 1 draft temperature：Tg+10℃

[table 4]

* 1 draft temperature：Tg+10℃

(polaroid)

By average degree of polymerization 2400,99.9 moles of % of saponification degree, 75 μm of thickness polyvinyl alcohol film in 30 DEG C of warm water Middle dipping 60 seconds and make swelling.Then, in 0.3 mass % (weight ratio：Iodine/potassium iodide=0.5/8) 30 DEG C of iodine solution in While dyeing 1 minute, it is stretched to 3.5 times.Then, 0.5 minute same of dipping in the boric acid aqueous solution of 65 DEG C of 4 mass % When, stretched in the way of making total stretching ratio reach 6 times.After stretching, 70 DEG C of baking oven carries out drying in 3 minutes, obtains To 22 μm of polaroid of thickness.

<The making of polarization plates X>

The biaxially oriented film that embodiment 8 is used is as polarizer protection film A.By polyester urethane (the first work Industry drugmaker manufactures, trade name：ス パ Off レ ッ Network ス 210, solid constituent：33%) 16.8g, cross-linking agent (containAzoles The polymer of quinoline, Japanese catalyst Co. manufacture, trade name：エ Port Network ロ ス WS-700, solid constituent：25%) 4.2g, 1 matter The ammonia 2.0g of amount %, colloidal silica (manufacture of chemical industrial company of Hibiscus rosa-sinensis, Network ォ ト ロ Application PL-3, solid constituent：20 Quality %) 0.42g and pure water 76.6g mixing, obtain easy adhesive compound.

By obtained easy adhesive compound to make the mode as 100nm for the dried thickness be applied to using bar coater Implement on the Corona discharge Treatment face of the biaxially oriented film of embodiment 8 after Corona discharge Treatment.Then, thin film is put into In air drier (110 DEG C), so that easy adhesive compound is dried about 5 minutes, the biaxially oriented film of embodiment 8 is formed Easily adhesive layer.

Then, N- hydroxyacrylamide (manufacture of Xing Ren company) 38.3 mass parts, tripropylene glycol diacrylate (commodity Name：ア ロ ニ ッ Network ス M-220, East Asia Synesis Company manufacture) 19.1 mass parts, acryloyl morpholine (manufacture of Xing Ren company) 38.3 parts and Photoepolymerizationinitiater initiater (trade name：KAYACURE DETX-S, diethyl thioxanthone, Japanese chemical medicine company system is made) 1.4 Mass parts mix, and stir 1 hour, reach active energy ray curable adhesive at 50 DEG C.

By above-mentioned active energy ray curable adhesive to make the mode as 500nm for the dried thickness be applied to polarization The easy adhesive layer side of piece protective film A.Then, using small-sized laminating machine, across active energy ray curable adhesive, front The both sides of the polaroid stated are laminated each polarizer protection film A.The both sides of the polarizer protection film A after laminating, make It is heated to 50 DEG C with IR heater, two sides is irradiated with accumulative irradiation dose is 1000mJ/cm²Ultraviolet, make active energy beam Curing type adhesive solidifies, and obtains polarization plates X on the two sides of polaroid with transparent polarizer protection film A.To make Polarization plates X made are put in the constant temperature and humidity machine of 80 DEG C of 90%RH, the journey of the deterioration of polaroid after visually observing 100 hours Degree is as a result, be not observed deterioration.

<The making of polarization plates Y>

40 μm of triacetyl cellulose film of thickness is impregnated 30 seconds in 10% sodium hydrate aqueous solution (60 DEG C) And make its saponification, then, wash 60 seconds, obtain polarizer protection film B.

With respect to the polyvinyl alcohol resin (average degree of polymerization containing acetoacetyl：1200th, saponification degree：98.5 moles of %, Acetoacetyl modified degree：5 moles of %) 100 mass parts, make melamine methylol 20 mass parts under 30 DEG C of temperature conditionss It is dissolved in pure water, obtain the aqueous solution of solid component concentration 0.5%.Using obtained aqueous solution as adhesive compound, Use under 30 DEG C of temperature conditionss.

By the above-mentioned adhesive compound after 30 minutes from preparation to make the mode as 50nm for the dried thickness be coated with To on polarizer protection film B.Then, using small-sized laminating machine, across adhesive compound in the both sides of aforesaid polaroid Laminated polarizing piece protective film B respectively, puts in air drier (70 DEG C) so as to be dried 5 minutes, obtains polarization plates Y.Will Polarization plates Y making are put in the constant temperature and humidity machine of 80 DEG C of 90%RH, the deterioration of polaroid after visually observing 100 hours Degree is as a result, observe deterioration in entire surface.

This application claims the priority based on Japanese publication Patent 2014-88810 that on April 23rd, 2014 proposes, Its entire disclosure is incorporated in this specification.

Industrial applicability

The transparency of the methacrylic resin composition of the present invention is high, thickness direction phase contrast is little and heat-resisting Property high, can thinly stretch, be thus suitable for polarizer protection film, phase-contrast film, liquid crystal protection board, portable information The surfacing of terminal, the display window protective film of portable data assistance, light directing film, it is coated with silver nanoparticle from the teeth outwards Silk, front panel purposes of the transparent conductive film of CNT, various display etc..Particularly, the phase place of the thin film of the present invention Difference is little, is thus suitable for polarizer protection film.

The transparency of the thin film of the present invention, thermostability are high, accordingly, as the purposes beyond optical applications, can be used for IR Cut-off thin film, prevention of criminality thin film, anti-disperse thin film, decorating film, metal finishing thin film, the notacoria of solaode, flexibility Cephacoria used for solar batteries, shrinkable film, in-mold labels thin film.

Symbol description

11 polaroids

12 gluing oxidant layer

13 easy adhesive layers

14 polarizer protection films

15 gluing oxidant layer

16 optical thin films

Claims (14)

1. a kind of methacrylic resin composition, it is containing methacrylic resin, polycarbonate resin and high score The methacrylic resin composition of sub- processing aid, wherein,

The content of the construction unit from methyl methacrylate of described methacrylic resin be 80 mass % more than, Weight average molecular weight is less than 200000,

Described polycarbonate resin has more than 1000 and less than 32000 viscosity-average molecular weight, with respect to described methacrylic acid The content of the described polycarbonate resin of resinoid 100 mass parts is below more than 1 mass parts and 4 mass parts,

Described polymer processing aid has more than 3000 and less than 40000 average degree of polymerization,

It is 0.3 mass parts with respect to the content of the described polymer processing aid of described methacrylic resin 100 mass parts Above and below 6 mass parts,

The described methacrylic resin containing in methacrylic resin composition and the conjunction of described polycarbonate resin Measure more than for 80 mass %.

2. methacrylic resin composition as claimed in claim 1, wherein, described methacrylic resin with three The degree of syndiotacticity (rr) of unit group meter is more than 50%, and the content of the construction unit from methyl methacrylate For more than 92 mass % and below 100 mass %.

3. methacrylic resin composition as claimed in claim 1 or 2, wherein, described methacrylic resin Degree of syndiotacticity (rr) is more than 58% and less than 85%.

4. the methacrylic resin composition as any one of claims 1 to 3, wherein, described methacrylic acid The content of the resinoid construction unit from methyl methacrylate is more than 99 mass %.

5. the methacrylic resin composition as any one of Claims 1 to 4, wherein, described polycarbonate resin Fat has more than 5000 and less than 18000 viscosity-average molecular weight.

6. the methacrylic resin composition as any one of Claims 1 to 5, wherein, described methacrylic acid The weight average molecular weight of based resin composition is 70000～200000.

7. the methacrylic resin composition as any one of claim 1～6, wherein, described methacrylic acid The molecular weight distribution of based resin composition is 1.2～2.5.

8. a kind of formed body, it comprises the methacrylic resin composition any one of claim 1～7.

9. a kind of thin film, it comprises the methacrylic resin composition any one of claim 1～7.

10. thin film as claimed in claim 9, its thickness is 10～50 μm.

11. thin film as described in claim 9 or 10, it is biaxially stretched to 1.5～8 times in terms of area ratio.

12. thin film as any one of claim 9～11, it uses as polarizer protection film.

A kind of 13. polarization plates, it is laminated with the thin film described at least one claim 12.

A kind of 14. manufacture methods of methacrylic resin composition, wherein, described methacrylic resin composition leads to Cross and following at least three kinds compositions are obtained by mixing：

From methyl methacrylate construction unit content be 80 mass % more than and weight average molecular weight be 200000 with Under methacrylic resin 100 mass parts,

More than polycarbonate resin 1 mass parts of the viscosity-average molecular weight with more than 1000 and less than 32000 and 4 mass parts with Under and

More than polymer processing aid 0.3 mass parts of the average degree of polymerization with more than 3000 and less than 40000 and 6 mass parts Below.