KR20170013273A - Methacrylic resin composition - Google Patents

Abstract

From 10 to 50 mass% of a structural unit (a1) derived from a methacrylic acid polycyclic aliphatic hydrocarbon ester, from 50 to 90 mass% of a structural unit (a2) derived from a methacrylic acid ester other than a methacrylic acid polycyclic aliphatic hydrocarbon ester, (A) containing a structural unit (a3) derived from an acrylate ester and 0 to 20 mass% of a structural unit derived from an acrylate ester, and a polycarbonate resin (B) containing a methacrylic resin (A) relative to the polycarbonate resin The resin composition is obtained by melt kneading or the like at a mass ratio (A) / (B) of 95/5 to 99.9 / 0.1. The resin composition is molded by a known method to obtain a film.

Description

[0001] METHACRYLIC RESIN COMPOSITION [0002]

The present invention relates to a methacrylic resin composition. More specifically, the present invention relates to a film comprising a methacrylic resin and a polycarbonate resin which are excellent in heat resistance and transparency, have a small absolute value of the retardation in the thickness direction, are uniform in thickness and can easily obtain a film having excellent surface smoothness To a resin composition.

(Hereinafter may be referred to as MMA-CHMA resin) and a polycarbonate resin (hereinafter sometimes referred to as PC resin) copolymerized with methyl methacrylate (MMA) and cyclohexyl methacrylate (CHMA) Since the resin composition made by blending is excellent in transparency, it has been proposed to produce an optical film using the resin composition (Patent Documents 1, 2 and 3).

Japanese Unexamined Patent Application Publication No. 2012-167195 Japanese Laid-Open Patent Publication No. 2014-031459 Japanese Published Patent Application No. 2012-507040 Japanese Patent Application Laid-Open No. 2002-12728 (Japanese Patent No. 3870670)

However, the resin composition comprising the MMA-CHMA resin and the PC resin has a low glass transition temperature and a large shrinkage under high temperature and high humidity. Even if the resin composition is molded by a known method, it is difficult to obtain a film having good balance of various characteristics.

Disclosure of the Invention Problems to be Solved by the Invention It is an object of the present invention to provide a methacrylic resin which is excellent in heat resistance and transparency, has a small absolute value of retardation in the thickness direction, has a small shrinkage under high temperature and high humidity, has a uniform thickness, And a resin composition containing the polycarbonate resin.

As a result of repeated studies to attain the above object, the present invention has been completed including the following aspects.

(A2) 50 to 90% by weight of a structural unit derived from a methacrylic acid ester other than a methacrylic acid polycyclic aliphatic hydrocarbon ester, A methacrylic resin (A) containing 0 to 20% by mass of a structural unit (a3) derived from an acrylate ester,

The polycarbonate resin (B)

Wherein the mass ratio (A) / (B) of the methacrylic resin (A) to the polycarbonate resin (B) is 95/5 to 99.9 / 0.1.

[2] The resin composition according to [1], wherein the methacrylic acid polycyclic aliphatic hydrocarbon ester is a compound represented by formula (1).

[Chemical Formula 1]

(In the formula (1), X is a polycyclic aliphatic hydrocarbon group having at least 10 carbon atoms)

[3] The resin composition according to [2], wherein X is an isobornan-2-yl group or a tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group.

[4] The resin composition according to any one of [1] to [3], wherein the methacrylic acid ester other than the methacrylic acid polycyclic aliphatic hydrocarbon ester is methyl methacrylate.

[5] The resin composition according to any one of [1] to [4], wherein the midpoint glass transition temperature measured by JIS K7121 (heating rate: 20 ° C / min) is 120 ° C or higher.

[6] The resin composition according to any one of [1] to [5], wherein the total content of the methacrylic resin (A) and the polycarbonate resin (B) is 80 to 100 mass%.

[7] A film comprising the resin composition according to any one of [1] to [6].

[8] A film according to [7], wherein the film has a thickness of 10 to 50 μm.

[9] A film according to [7] or [8], wherein the film is biaxially stretched at an area ratio of 1.5 to 8 times.

[10] A film according to [7] or [8] which is at least monoaxially stretched.

[11] A polarizer protective film comprising the film according to any one of [7] to [10].

[12] A retardation film comprising the film according to any one of [7] to [10].

[13] A polarizer having a polarizer and a film described in any one of [7] to [10] laminated on the polarizer.

The resin composition of the present invention has a high glass transition temperature, a high light transmittance and a low haze. By molding the resin composition of the present invention by a known method, a film having excellent heat resistance and transparency, having an absolute value of retardation in the thickness direction, having a small shrinkage under high temperature and high humidity, having a uniform thickness, Can be obtained. By laminating the film related to the present invention with a polarizer, it is possible to provide a polarizing plate for producing a liquid crystal display device having functions such as high coloring, wide viewing angle and low color distortion.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a configuration of a polarizing plate according to an embodiment of the present invention. Fig.

A resin composition according to one embodiment of the present invention comprises a methacrylic resin (A) and a polycarbonate resin (B).

The methacrylic resin (A) comprises a structural unit (a1), a structural unit (a2) and a structural unit (a3).

The structural unit (a1) is one derived from a methacrylic polycyclic aliphatic hydrocarbon ester, preferably a methacryloyl group in a methacrylic polycyclic aliphatic hydrocarbon ester. The structural unit (a1) is preferably a unit represented by the formula (2).

(2)

Cy in the formula (2) is a polycyclic aliphatic hydrocarbon group.

Examples of the polycyclic aliphatic hydrocarbon group include, but are not limited to, an octahydrophthalene-1-yl group, an octahydrophthalene-2-yl group, an octahydro-1-1H- A decahydronaphthalene-1-yl group, a decahydronaphthalene-2-yl group, an octahydrocyclopenta [c, d] pentalene-2A-2a (2H) -yl group, 3a, 6a-dimethyloctahydropentalene-2-yl group, tetradecahydroanthracene- , A condensed polycyclic aliphatic hydrocarbon group such as a cholestan-5-yl group; Methyl norbornan-2-yl group, a 2-ethylnorbornan-2-yl group, a 1,3,3-trimethylnorbornan-2-yl group, , A 3-tetramethylnorbornane-2-yl group, a 1,3-trimethylnorbornane-2-yl group, an isobornyl- An isobornyl-2-yl group, a decahydro-2,5-methano-7,10-methanonaphthalen-1-yl group, a tricyclo [5.2.1.0 ^2,6 ] decan- Cyclohexyl [5.2.1.0 ^2,6 ] decan-8-yl group, 8-ethyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, adamantan-1-yl group, adamantan- Bridging such as a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group or a decahydro-3,6-methano-2,2,7,7-tetramethylnaphthalen- A cyclic aliphatic hydrocarbon group; Alicyclic hydrocarbon group having a spiro structure such as spirobicyclo-pentane-2-yl group, spirobicyclopentan-3-yl group, spirobicyclohexan-2-yl group, have.

The methacrylic polycyclic aliphatic hydrocarbon ester is preferably a compound represented by the formula (1).

(3)

X in the formula (1) is a polycyclic aliphatic hydrocarbon group having 10 or more carbon atoms, preferably a crosslinked cyclic aliphatic hydrocarbon group having 10 or more carbon atoms. The crosslinked cyclic aliphatic hydrocarbon is an alicyclic hydrocarbon having a structure in which two non-neighboring carbon atoms constituting a ring are linked by a carbon chain comprising at least one carbon atom. Such a crosslinked cyclic aliphatic hydrocarbon may have a condensed ring structure or a spiro ring structure in addition to a structure connected by a carbon chain. The number of carbon atoms constituting the polycyclic aliphatic hydrocarbon group is more preferably from 10 to 20.

Examples of the polycyclic aliphatic hydrocarbon group having 10 or more carbon atoms include octahydrocyclopenta [c, d] pentalene-2A-2a (2H) -yl group, 3a, 6a- Yl group, a cholestan-5-yl group, a 1,3,3-trimethylnorbornane-2-yl group, a 1,2,3,3-tetramethyl 2-yl group, 2-methylisobornan-2-yl group, 2-ethylisoboron-2-yl group, Dihydroxy-2,5-methano-7,10-methanonaphthalen-1-yl group, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 8-methyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 8-ethyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, adamantan-1-yl group, adamantan- Yl group, 2-ethyladamantan-2-yl group, decahydro-3,6-methano-2,2,7,7-tetramethylnaphthalen-1-yl group, spirobicyclohexane- Diary, Spiro Cyclohexane may be mentioned 3-yl group and the like. Among them, a 1,3,3-trimethylnorbornane-2-yl group, a 1,2,3,3-tetramethylnorbornane-2-yl group, a 1,3,3-trimethylnorbornane- Methyl isobornyl-2-yl group, a 2-ethylisobornan-2-yl group, a decahydro-2,5-methano-7,10-methanonaphthalene- -Thiocyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 8-methyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 8-ethyltricyclo [5.2.1.0 ^2,6 Adamantan-2-yl group, 2-methyladamantan-2-yl group and 2-ethyladamantan-2-yl group are preferable, and isobor I-2-yl group, tricyclo [5.2.1.0 ^2,6] decane-8-diary, and more preferably, tricyclo [5.2.1.0 ^2,6] decane-8-group (trivial name: dicyclopentanyl group) is Particularly preferred.

The structural unit (a2) is one derived from a methacrylate ester (a2), preferably one formed by an addition reaction of a methacryloyl group in the methacrylate ester (a2). The methacrylic acid ester (a2) is a methacrylic acid ester other than the methacrylic acid polycyclic aliphatic hydrocarbon ester.

Examples of the methacrylic acid ester (a2) include methacrylic monocyclic aliphatic hydrocarbon esters such as cyclohexyl methacrylate, cyclopentyl methacrylate, and cycloheptyl methacrylate; Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, Methacrylic acid chain-like aliphatic hydrocarbon esters such as amyl methacrylate, methacrylic acid iodine, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, 2-hydroxyethyl, 2-methoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and phenyl methacrylate. Of these, methacrylic acid chain type aliphatic hydrocarbon esters or methacrylic monocyclic aliphatic hydrocarbon esters are preferable from the viewpoint of improving transparency and heat resistance, and methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methacryl N-butyl acrylate, t-butyl methacrylate and cyclohexyl methacrylate are preferable, and methyl methacrylate is most preferable.

The structural unit (a3) is one derived from an acrylate ester, preferably an addition reaction of an acryloyl group in an acrylate ester.

Examples of the acrylic esters include acrylic acid chain type aliphatic hydrocarbon esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; Acrylic acid aromatic hydrocarbon esters such as phenyl acrylate; And acrylic acid alicyclic hydrocarbon esters such as cyclohexyl acrylate and norbornenyl acrylate. Of these, methyl acrylate, ethyl acrylate and butyl acrylate are preferable, and methyl acrylate is particularly preferable in view of the fact that thermal decomposition can be suppressed and film production is easy.

The methacrylic resin (A) used in the present invention may contain the structural unit (a4) in addition to the structural units (a1), (a2) and (a3). The structural unit (a4) is derived from a monomer other than a methacrylate ester and an acrylate ester. Such monomers include, for example, acrylamide; Methacrylamide; Acrylonitrile; Monomers having only one polymerizable carbon-carbon double bond in one molecule such as methacrylonitrile and styrene.

The methacrylic resin (A) used in the present invention usually contains 10 to 50% by mass of the structural unit (a1) and the structural unit (a2) in view of the high glass transition temperature and low shrinkage at high temperature and high humidity. (A1) in an amount of from 15 to 40 mass%, the structural unit (a2) in an amount of from 60 to 85 mass%, and the structural unit (a3) in an amount of from 50 to 90 mass% (A3) in an amount of 0 to 10 mass%, more preferably 20 to 30 mass% of the structural unit (a1), 70 to 80 mass% of the structural unit (a2) 5% by mass. The content of the structural unit (a4) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and still more preferably 0 to 2% by mass.

The methacrylic resin (A) used in the present invention preferably has a weight average molecular weight (hereinafter sometimes referred to as " Mw ") of preferably 60,000 to 200,000, more preferably 80,000 to 160,000 Preferably from 90,000 to 150,000, and particularly preferably from 100,000 to 130,000. When such Mw is 60,000 or more, the resulting film has high strength, is not easily cracked, and is easily stretched. Therefore, the film can be made thinner. Further, when the Mw is 200,000 or less, the methacrylic resin (A) has a high molding processability, so that the thickness of the resulting film tends to be uniform and the surface smoothness tends to be excellent.

The methacrylic resin (A) used in the present invention has a ratio of Mw to a number average molecular weight (hereinafter sometimes referred to as "Mn") (Mw / Mn: hereinafter referred to as "molecular weight distribution" ) Is preferably 1.2 to 5.0, more preferably 1.5 to 3.5. When the molecular weight distribution is 1.2 or more, the flowability of the methacrylic resin (A) is improved, and the obtained film tends to have excellent surface smoothness. A film obtained by a molecular weight distribution of 5.0 or less tends to have excellent impact resistance and toughness. Mw and Mn are values obtained by converting the chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene.

The methacrylic resin (A) to be used in the present invention preferably has a melt flow rate measured at 230 占 폚 under a load of 3.8 kg in accordance with JIS K7210 of preferably 0.1 to 15 g / 10 min, Is 0.5 to 5 g / 10 min, and more preferably 0.8 to 3 g / 10 min.

The glass transition temperature of the methacrylic resin (A) used in the present invention is preferably 120 占 폚 or higher, more preferably 123 占 폚 or higher, even more preferably 124 占 폚 or higher, particularly preferably 125 占 폚 or higher. The upper limit of the glass transition temperature of the methacrylic resin (A) is usually 140 占 폚. The glass transition temperature can be controlled by controlling the proportion of the structural units derived from the methacrylic acid polycyclic aliphatic hydrocarbon ester. When the glass transition temperature is within this range, the heat resistance of the resulting film is improved and deformation such as heat shrinkage does not occur. Here, the glass transition temperature is the mid-point glass transition temperature measured in accordance with JIS K7121 (rate of temperature increase of 20 占 폚 / min).

The method for producing the methacrylic resin (A) used in the present invention is not particularly limited. For example, by a known polymerization method such as a radical polymerization method or an anion polymerization method. The adjustment of the methacrylic resin (A) to the above-mentioned characteristic values can be carried out by adjusting the polymerization conditions, specifically by adjusting the polymerization temperature, the polymerization time, the kind and amount of the chain transfer agent, and the kind and amount of the polymerization initiator can do. Adjustment of the resin properties by adjusting the polymerization conditions is a well known technique to those skilled in the art.

In the case of using the radical polymerization method in the production of the methacrylic resin (A) for use in the present invention, it is possible to select the suspension polymerization method, the bulk polymerization method, the solution polymerization method and the emulsion polymerization method. In such a polymerization method, the suspension polymerization method or the bulk polymerization method is preferably used from the viewpoints of productivity and thermal decomposition resistance. The bulk polymerization is preferably carried out in a continuous flow system.

The polymerization reaction is carried out using a polymerization initiator, the above-mentioned monomer, and optionally a chain transfer agent.

The polymerization initiator used in the radical polymerization method for producing the methacrylic resin (A) used in the present invention is not particularly limited as long as it generates a reactive radical. The polymerization initiator used in the present invention has a half-life temperature of 1 hour, preferably 60 to 140 占 폚, more preferably 80 to 120 占 폚.

Examples of the polymerization initiator include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate , t-butyl peroxy pivalate, t-hexyl peroxy pivalate, t-butyl peroxy neodecanoate, t-hexyl peroxyneodecanoate, 1,1,3,3-tetramethyl butyl peroxy (T-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2'-azobis (2 -Methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), and dimethyl 2,2'-azobis (2-methylpropionate). Among them, t-hexylperoxy 2-ethylhexanoate, 1,1-bis (t-hexylperoxy) cyclohexane and dimethyl 2,2'-azobis (2-methylpropionate) are preferable.

These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator to be added, the method of addition, and the like can be suitably set according to the purpose and are not particularly limited. For example, the amount of the polymerization initiator used in the suspension polymerization method is preferably 0.0001 to 0.1 part by mass, more preferably 0.001 to 0.07 part by mass based on 100 parts by mass of the total amount of the monomers to be provided for the polymerization reaction.

The chain transfer agent used in the radical polymerization method for producing the methacrylic resin (A) used in the present invention is not particularly limited. For example, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 1,4-butane dithiol, 1,6-hexanedithiol, ethylene glycol bistyropiophonate, Hexanediol bis-thiopropionate, trimethylolpropane tris- (beta -thiopropionate), pentaerythritol tetrakisthiopropionate, etc. may be used. Alkyl mercaptans; ? -methylstyrene dimer; And terpinolene. Of these, alkyl mercaptans such as n-octyl mercaptan, pentaerythritol tetrakisthiopropionate and the like are preferable. These chain transfer agents may be used singly or in combination of two or more kinds.

The amount of such a chain transfer agent to be used is preferably 0.1 to 1 part by mass, more preferably 0.15 to 0.8 part by mass, further preferably 0.2 to 0.6 part by mass, more preferably 0.2 to 0.6 part by mass based on 100 parts by mass of the total amount of the monomers to be polymerized, Most preferably 0.2 to 0.5 parts by mass. The amount of the chain transfer agent to be used is preferably 2,500 to 10,000 parts by mass, more preferably 3,000 to 9,000 parts by mass, and still more preferably 3,500 to 6,000 parts by mass based on 100 parts by mass of the polymerization initiator. When the amount of the chain transfer agent used is within the above range, the resin composition can have good molding processability and high mechanical strength.

The monomers, the polymerization initiator and the chain transfer agent used in the production of the methacrylic resin (A) used in the present invention may be mixed with each other and the mixture may be supplied to the reaction vessel, or they may be separately supplied to the reaction vessel. In the present invention, it is preferable to mix all the components and supply the mixture to the reaction tank.

In the case of using a solvent in the radical polymerization method for producing the methacrylic resin (A) used in the present invention, the solvent is not limited as long as it can dissolve the monomer and the methacrylic resin (A), but the solvent is not limited to benzene, toluene, And aromatic hydrocarbons such as ethylbenzene are preferable. These solvents may be used singly or in combination of two or more. The amount of the solvent to be used can be appropriately set in view of the viscosity and productivity of the reaction solution. The amount of the solvent to be used is, for example, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the total amount of polymerization reaction raw materials.

The temperature for the radical polymerization for the production of the methacrylic resin (A) used in the present invention is preferably from 50 to 180 캜, more preferably from 60 to 140 캜, in the case of suspension polymerization.

In the case of bulk polymerization, it is preferably 100 to 200 占 폚, more preferably 110 to 180 占 폚. When the temperature at the bulk polymerization reaction is 100 占 폚 or higher, the productivity tends to be improved due to the improvement of the polymerization rate and the lowering of the viscosity of the polymerization liquid. When the temperature during the bulk polymerization is 200 占 폚 or less, the control of the polymerization rate is facilitated and the production of by-products is suppressed, so that the coloring of the resin composition of the present invention can be suppressed.

When the production of the methacrylic resin (A) for use in the present invention is carried out by suspension polymerization, the granular polymer can be obtained by washing, dehydrating and drying by a known method after completion of the polymerization.

The radical polymerization may be carried out using a batch reactor or a continuous flow reactor. In the continuous flow type reaction, for example, a polymerization reaction raw material (a mixed solution containing a monomer, a polymerization initiator, a chain transfer agent, etc.) is prepared in a nitrogen atmosphere or the like and fed to the reactor at a constant flow rate, The liquid in the reactor is extracted. As the reactor, it is possible to use a tubular reactor which can be close to the current (plug flow) and / or a molding reactor which can be brought into a state close to complete mixing. In addition, continuous flow type polymerization may be carried out in one reactor, or continuous flow type polymerization may be carried out by connecting two or more types of reactors. In the present invention, it is preferable to use at least one type of continuous flow type molding reactor. The amount of the liquid in the molding reactor in the polymerization reaction is preferably 1/4 to 3/4, and more preferably 1/3 to 2/3 of the volume of the molding reactor. The reactor is usually equipped with a stirrer. Examples of the stirring apparatus include a static stirring apparatus and a dynamic stirring apparatus. Examples of the dynamic stirring apparatus include a max blend type stirring apparatus, a stirring apparatus having a lattice-like blade rotating around a vertical rotating shaft disposed at the center, a propeller type stirring apparatus, and a screw type stirring apparatus. Of these, the Max Blend type stirring device is preferably used in terms of uniform mixing.

After completion of the polymerization, volatile components such as unreacted monomers are removed, if necessary. The removing method is not particularly limited, but heating deaeration is preferable. Examples of the skimming method include a balanced flash method and an adiabatic flash method. The devolatilization temperature by the adiabatic flash method is preferably 200 to 280 ° C, more preferably 220 to 260 ° C. The time for heating the resin by the adiabatic flash method is preferably 0.3 to 5 minutes, more preferably 0.4 to 3 minutes, and still more preferably 0.5 to 2 minutes. By devolatilization in such a temperature range and heating time, it is easy to obtain a methacrylic resin (A) which is less colored. The unreacted monomers thus removed can be recovered and used again in the polymerization reaction. The yellow index of the recovered monomers may be increased by the heat applied to the recovery operation or the like. The recovered monomers are preferably purified by an appropriate method to reduce the yellow index.

As a method for producing the methacrylic resin (A) used in the present invention by anionic polymerization, for example, an organic alkali metal compound may be used as a polymerization initiator and an anion such as an alkali metal or an alkaline earth metal salt, (See JP-A-7-25859), an anionic polymerization method in which an organic alkali metal compound is used as a polymerization initiator in the presence of an organoaluminum compound (see JP-A No. 11-335432) And a method of performing anionic polymerization using a metal complex as a polymerization initiator (see JP-A-6-93060).

In the anion polymerization method for producing the methacrylic resin (A) used in the present invention, alkyllithium such as n-butyllithium, sec-butyllithium, isobutyllithium, t-butyllithium, etc. is used as the polymerization initiator . From the viewpoint of productivity, it is preferable to coexist the organoaluminum compound. Examples of the organoaluminum compound include compounds represented by AlR ¹ R ² R ³ .

(Wherein R ¹ , R ² and R ³ each independently represent an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, , An aryloxy group which may have a substituent or an N, N-2-substituted amino group, and R ² and R ³ may be an arylenedioxy group which may have a substituent formed by bonding thereof.

Specific examples of the organoaluminum compound include isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6- Butyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum and the like.

In the anion polymerization method, an ether or a nitrogen-containing compound may be coexisted to control the polymerization reaction.

The polycarbonate resin (B) used in the present invention is not particularly limited. Examples of the polycarbonate resin (B) include polymers obtained by a reaction between a polyfunctional hydroxy compound and a carbonic acid ester-forming compound. In the present invention, an aromatic polycarbonate resin is preferable from the viewpoint of compatibility with the methacrylic resin (A) and transparency of the obtained film.

The polycarbonate resin (B) to be used in the present invention preferably has an MVR value at 300 DEG C and 1.2 Kg, preferably at least 300 DEG C, in view of compatibility with the methacrylic resin (A), transparency of the obtained film, 1 to 250 cm 3/10 min, and more preferably 3 to 230 cm 3/10 min.

The polycarbonate resin (B) to be used in the present invention is preferably at least one selected from the group consisting of a mixture of a methacrylic resin (A) and a polymer (B), which is measured by gel permeation chromatography (GPC) The weight average molecular weight calculated by converting the grams into the molecular weight of standard polystyrene is preferably from 18,000 to 75,000, and more preferably from 20,000 to 60,000. The adjustment of the MVR value or the weight average molecular weight of the polycarbonate resin (B) can be carried out by adjusting the amount of the terminal terminator and the branching agent.

The glass transition temperature of the polycarbonate resin (B) used in the present invention is preferably 130 占 폚 or higher, more preferably 135 占 폚 or higher, even more preferably 140 占 폚 or higher. The upper limit of the glass transition temperature of the polycarbonate resin is usually 180 占 폚. Here, the glass transition temperature is the mid-point glass transition temperature measured in accordance with JIS K7121 (rate of temperature increase of 20 占 폚 / min).

The production method of the polycarbonate resin (B) is not particularly limited. Examples thereof include a phosgene method (interfacial polymerization method) and a melt polymerization method (ester exchange method). The aromatic polycarbonate resin preferably used in the present invention may be one obtained by subjecting a polycarbonate resin raw material produced by the melt polymerization method to a treatment for adjusting the terminal hydroxy group amount.

Examples of the polyfunctional hydroxy compound as a raw material for producing the polycarbonate resin (B) include 4,4'-dihydroxybiphenyls which may have a substituent; Bis (hydroxyphenyl) alkanes which may have a substituent; Bis (4-hydroxyphenyl) ethers which may have a substituent; Bis (4-hydroxyphenyl) sulfide which may have a substituent; Bis (4-hydroxyphenyl) sulfoxide which may have a substituent; Bis (4-hydroxyphenyl) sulfone which may have a substituent; Bis (4-hydroxyphenyl) ketones which may have a substituent; Bis (hydroxyphenyl) fluorenes which may have a substituent; Dihydroxy-p-terphenyl which may have a substituent; Dihydroxy-p-quaterphenyl which may have a substituent; Bis (hydroxyphenyl) pyrazine which may have a substituent; Bis (hydroxyphenyl) mannant which may have a substituent; Bis [2- (4-hydroxyphenyl) -2-propyl] benzenes which may have a substituent; Dihydroxynaphthalenes which may have a substituent; Dihydroxybenzenes which may have a substituent; Polysiloxanes which may have a substituent; Dihydro perfluoroalkane which may have a substituent, and the like.

Among these multifunctional hydroxy compounds, preferred are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis Bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2- Propane, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, 2,2-bis (3,5-dibromo- (4-hydroxyphenyl) pentane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis Bis [3- (2-hydroxyphenyl) propyl] poly (2-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoropropane, Dimethylsiloxane, resorcin, and 2,7-dihydroxynaphthalene are preferable, and 2,2-bis (4-hydroxyphenyl) propane is more preferable.

Examples of the carbonate ester-forming compound include various dihalogenated carbonyls such as phosgene, haloformates such as chloroformate, and carbonate ester compounds such as bisaryl carbonate. The amount of the carbonic ester-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalence) of the reaction.

The reaction for preparing the polycarbonate resin (B) is usually carried out in a solvent in the presence of an acid binding agent. Examples of the acid coupling agent include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and organic bases such as trimethylamine, triethylamine, tributylamine, N, Tertiary amines such as trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide, and the like, such as trimethylbenzylammonium chloride, cyclohexylamine, pyridine and dimethyl aniline; Quaternary phosphonium salts such as ammonium salts, tetrabutylphosphonium chloride and tetrabutylphosphonium bromide. In addition, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added to the reaction system as desired. The amount of the acid binder may be appropriately adjusted in consideration of the stoichiometric ratio (equivalence) of the reaction. For example, an acid binding agent may be used in an amount of 1 equivalent or more, preferably 1 to 5 equivalents, per 1 mole of the hydroxyl group of the starting polyfunctional hydroxy compound.

As the reaction for producing the polycarbonate resin (B), known terminal terminators and branching agents can be used. Examples of the terminal terminator include pt-butyl-phenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluorohexylphenyl) , pt-perfluorobutylphenol, 1- (p-hydroxybenzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotridodecyloxy) -1,1,1,3,3 , 3-hexafluoropropyl] phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, p-hydroxybenzoic acid perfluorododecyl, p- (1H, 1H-perfluorooctyloxy ) Phenol, 2H, 2H, 9H-perfluorononanic acid, and 1,1,1,3,3,3-tetrafluoro-2-propanol.

Branching agents include, but are not limited to, fluoroglycine, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,6- Tris (4-hydroxyphenyl) heptane, 1,3,5-tris (2-hydroxyphenyl) benzene, 1 Tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2- Bis (4-hydroxyphenyl) -2-propyl] phenol, 2,6-bis (2-hydroxy- 2- (2,4-dihydroxyphenyl) propane, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- (4-hydroxyphenyl isopropyl) phenoxy] methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis Oxo-2,3-dihydroindole, 3,3-bis (4-hydro Cyano reel), and the oxy-indole, 5-chloroisatin satin, satin dikeulroroyi 5,7, 5-bromo feeders such as satin.

The polycarbonate resin (B) may contain a unit having a polyester, polyurethane, polyether or polysiloxane structure in addition to the polycarbonate unit.

In the resin composition according to the present invention, the mass ratio (A) / (B) of the methacrylic resin (A) to the polycarbonate resin (B) is usually 95/5 to 99.9 / 0.1, To 99/1, and more preferably from 97/3 to 98/2. Within this range, the methacrylic resin (A) and the polycarbonate resin (B) are completely compatible with each other, so that a film having high transparency and good surface smoothness can be easily obtained. In this range, the absolute value of the retardation of the resulting stretched film can be reduced.

The total amount of the methacrylic resin (A) and the polycarbonate resin (B) contained in the resin composition according to the present invention is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, further preferably 94 To 100% by mass, and most preferably 96% to 100% by mass.

The resin composition according to the present invention may contain a filler if necessary insofar as the effect of the present invention is not impaired. Examples of the filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate and the like. The amount of the filler that can be contained in the resin composition of the present invention is preferably 3 mass% or less, and more preferably 1.5 mass% or less.

The resin composition according to the present invention may contain other polymers insofar as the effect of the present invention is not impaired. Other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1 and polynorbornene; Ethylenic ionomers; Styrene resins such as polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin and MBS resin; Methyl methacrylate polymer other than the methacrylic resin (A), methyl methacrylate-styrene copolymer; Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Nylon 6, nylon 66, and polyamide elastomers; Polyvinylidene chloride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethane, phenoxy resin, modified polyphenylene ether, polyphenylene sulfide, silicone modified resin; Acrylic rubber, acrylic elastomer, silicone rubber; Styrene-based thermoplastic elastomers such as SEPS, SEBS and SIS; And olefin rubbers such as IR, EPR and EPDM. The amount of other polymer that can be contained in the resin composition of the present invention is preferably 10 mass% or less, more preferably 5 mass% or less, and most preferably 0 mass%.

The resin composition for use in the present invention may contain additives such as antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, release agents, polymer processing aids, antistatic agents, flame retardants, An additive such as a dispersing agent, an organic dye, a gloss remover, an impact resistance modifier, and a phosphor may be contained.

The antioxidant is effective in preventing oxidative deterioration of the resin in the presence of oxygen. Examples thereof include phosphorus antioxidants, hindered phenol antioxidants, thioether antioxidants and the like. Among them, a phosphorus-based antioxidant and a hindered phenol-based antioxidant are preferable from the viewpoint of an effect of preventing deterioration of optical characteristics due to coloring, and a phosphorus-based antioxidant and a hindered phenol-based antioxidant are more preferably used in combination.

When the phosphorus-based antioxidant and the hindered phenol-based antioxidant are used in combination, the phosphorus-based antioxidant / hindered phenol-based antioxidant is preferably used in a mass ratio of 0.2: 1 to 2: 1, more preferably 0.5: 1 to 1/1 It is more preferable to use it.

Examples of the phosphorus antioxidant include 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite (trade name: Adekastab HP-10 manufactured by ADEKA), tris (2,4- (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxane (trade name: IRUGAFOS168) -3,9-diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: Adecastab PEP-36).

Examples of the hindered phenol antioxidant include 3,5-di-tert-butyl-4-hydroxytoluene, pentaerythrityl-tetrakis [3- (3,5- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name IRGANOX1076, manufactured by BASF Corporation) and octadecyl-3- desirable.

As the thermal deterioration preventing agent, thermal degradation of the resin can be prevented by capturing polymer radicals generated when exposed to high temperature under substantially anaerobic conditions.

Examples of the thermal deterioration preventing agent include 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenylacrylate (Sumitomo Chemical Co., (3 ', 5'-di-t-amyl-2'-hydroxy- alpha -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GS) Do.

The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays and is said to have a function of mainly converting light energy into heat energy.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, anilides oxalic acid, malonic acid esters and formamidines. Among them, an ultraviolet absorber having benzotriazoles, triazines, or a maximum value (ε _max ) of the molar extinction coefficient at a wavelength of 380 to 450 nm of 100 dm 3 · mol ^-1 cm ^-1 or less is preferable.

Since benzotriazoles have a high effect of suppressing deterioration of optical properties such as coloration caused by ultraviolet ray irradiation (illumination), they are preferable as ultraviolet absorbers for use in application of the film of the present invention to optical use. Examples of benzotriazoles include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name: TINUVIN329, Methyl-1-phenylethyl) phenol (trade name: TINUVIN234, manufactured by BASF), 2,2'-methylenebis [6- (2H-benzotriazole (5-octylthio-2H-benzotriazol-2-yl) -6-tert-butyl-4- Methylphenol and the like are preferable.

The ultraviolet absorber having a maximum value (? _Max ) of the molar extinction coefficient at a wavelength of 380 to 450 nm of 1,200 dm 3 mol ^-1 cm ^-1 or less can suppress discoloration of the resulting film. Examples of such an ultraviolet absorber include 2-ethyl-2'-ethoxy-oxanilide (manufactured by Clariant Japan Co., Ltd .; trade name: SANDAYU BOA VSU).

Of these ultraviolet absorbers, benzotriazoles are preferably used from the viewpoint that the resin deterioration due to ultraviolet radiation is inhibited.

In order to efficiently absorb a short wavelength of 380 nm or shorter, a triazine-based ultraviolet absorber is preferably used. Examples of such ultraviolet absorbers include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (LA- Hydroxyphenyltriazine type ultraviolet absorber (TINUVIN477 or TINUVIN460, manufactured by BASF), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) 3,5-triazine, and the like.

The maximum value (? _Max ) of the molar absorptivity of the ultraviolet absorber is measured as follows.

10.00 mg of an ultraviolet absorber is added to 1 liter of cyclohexane, and the solution is dissolved with no visual effect by observation with the naked eye. This solution is poured into a quartz glass cell of 1 cm x 1 cm x 3 cm and the absorbance at a wavelength of 380 to 450 nm and an optical path length of 1 cm is measured using a U-3410 type spectrophotometer manufactured by Hitachi, Ltd. The maximum value? _Max of the molar extinction coefficient is calculated from the molecular weight (M _UV ) of the ultraviolet absorber and the maximum value (A _max ) of the measured absorbance by the following formula.

ε_max = [A_max/ (10 x 10^-3)] × M_UV

Further, in the case of particularly effectively absorbing light having a wavelength of 380 nm to 400 nm, it is possible to effectively absorb light having a wavelength of 380 nm to 400 nm in WO2011 / 089794A1, WO2012 / 124395A1, JP-A-2012-012476, JP- A ligand of a heterocyclic structure disclosed in Japanese Patent Application Laid-Open Nos. 2013-112790, 2013-194037, 2014-62228, 2014-88542, 2014-88543, (For example, a compound having a structure represented by the formula (A)) is preferably used as an ultraviolet absorber.

[Chemical Formula 4]

[In the formula (A), M is a metal atom.

Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent group other than a carbon atom (oxygen atom, sulfur atom, NH, NR ^5, etc.). Each R ⁵ is independently a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, or an aralkyl group. The substituent may have a substituent in addition to the substituent.

Z ¹ and Z ² are each independently a triple bond (nitrogen atom, CH, CR ^6, etc.). Each R ⁶ is independently a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroaralkyl group, or an aralkyl group. The substituent may have a substituent in addition to the substituent.

R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, a hydroxyl group, a carboxyl group, an alkoxyl group, a halogeno group, an alkylsulfonyl group, a monopolinosulfonyl group, a piperidinosulfonyl group, A sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, The substituent may have a substituent in addition to the substituent. a, b, c and d represent the numbers of R ¹ , R ² , R ³ and R ⁴ , respectively, and are any integers from 1 to 4.]

Examples of the ligand of the heterocyclic structure include 2,2'-iminobisbenzothiazole, 2- (2-benzothiazolylamino) benzoxazole, 2- (2-benzothiazolylamino) benzoimidazole, (2-benzoimidazolyl) methane, bis (2-benzoxazolyl) methane, bis (2-benzothiazolyl) Etc., and derivatives thereof. As the central metal of such a metal complex, copper, nickel, cobalt and zinc are preferably used. In order to use these metal complexes as ultraviolet absorbers, it is preferable to disperse the metal complexes in a medium such as a low molecular weight compound or a polymer. The amount of the metal complex to be added is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass based on 100 parts by mass of the film of the present invention. Since the metal complex has a large molar extinction coefficient at a wavelength of 380 nm to 400 nm, the added amount is small in order to obtain a sufficient ultraviolet absorption effect. When the addition amount is decreased, deterioration of the appearance of the resin film due to bleed-out or the like can be suppressed. In addition, since the metal complex has high heat resistance, deterioration and decomposition during molding are small. Further, since the metal complex has high light resistance, the ultraviolet absorption performance can be maintained for a long time.

The light stabilizer is a compound which is said to have a function of capturing a radical mainly generated by light oxidation. Preferable examples of the light stabilizer include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.

Examples of the lubricant include stearic acid, behenic acid, stearoamidic acid, methylenebisstearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hardened oil.

The release agent is a compound having a function of facilitating the separation of the molded article from the mold. Examples of the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; Stearic acid monoglyceride, stearic acid monoglyceride, and stearic acid diglyceride. In the present invention, it is preferable to use a combination of a higher alcohol and a glycerin fatty acid monoester as a release agent. When the higher alcohols and the glycerin fatty acid monoester are used in combination, the mass ratio of the higher alcohol / glycerin fatty acid monoester is preferably in the range of 2.5 / 1 to 3.5 / 1, more preferably in the range of 2.8 / 1 to 3.2 / It is more preferable to use it.

As the polymer processing aid, polymer particles having a particle diameter of 0.05 to 0.5 mu m, which can be usually produced by emulsion polymerization, can be used. The polymer particles may be single-layered particles composed of a polymer having a single composition ratio and a single intrinsic viscosity, or may be multilayer particles composed of two or more polymers having different composition ratios or intrinsic viscosities. Of these, particles of a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl / g or more in the outer layer are preferable. The polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g.

Examples of the impact resistance modifier include a core-shell modifier containing an acrylic rubber or a diene rubber as a core layer component; A modifier containing a plurality of rubber particles, and the like.

As the organic coloring matter, a compound having a function of converting ultraviolet rays harmful to the resin into visible light is preferably used.

Examples of the light diffusing agent and the gloss removing agent include glass fine particles, polysiloxane crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, barium sulfate and the like.

Examples of the fluorescent substance include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent whitening agent, and a fluorescent whitening agent.

These additives may be used singly or in combination of two or more. These additives may be added to the polymerization reaction liquid when the methacrylic resin (A) or the polycarbonate resin (B) is produced, or may be added to the produced methacrylic resin (A) or polycarbonate resin (B) And may be added when preparing the resin composition of the present invention. The total amount of the additives contained in the resin composition of the present invention is preferably 7% by mass or less, more preferably 5% by mass or less, further preferably 5% by mass or less based on the methacrylic resin (A) And preferably not more than 4% by mass.

The method for preparing the resin composition is not particularly limited. For example, a method of polymerizing a monomer mixture containing methyl methacrylate in the presence of a polycarbonate resin (B) to produce a methacrylic resin (A), or a method in which a methacrylic resin (A) and a polycarbonate resin (B) And a method of melt kneading. Of these, the melt-kneading method is preferable since the process is simple. (A) may be mixed with another polymer and an additive and then mixed with the polycarbonate resin (B), and the polycarbonate resin (B) may be mixed with the other polymer or additive It may be mixed with the methacrylic resin (A) after mixing with other polymers and additives, or may be other methods. The kneading can be carried out by using a known mixing device or a kneading device such as a kneader rudder, an extruder, a mixing roll, a Banbury mixer or the like. Of these, a twin-screw extruder is preferred. The temperature at the time of mixing and kneading can be suitably adjusted in accordance with the melting temperature of the methacrylic resin (A) and the polycarbonate resin (B) to be used, and is preferably 110 ° C to 300 ° C.

The resin composition of the present invention has a glass transition temperature of preferably 120 占 폚 or higher, more preferably 123 占 폚 or higher, further preferably 124 占 폚 or higher, particularly preferably 125 占 폚 or higher. The upper limit of the glass transition temperature of the resin composition of the present invention is not particularly limited, but is preferably 135 占 폚. Here, the glass transition temperature is the mid-point glass transition temperature measured in accordance with JIS K7121 (rate of temperature increase of 20 占 폚 / min).

In the resin composition of the present invention, the Mw determined by GPC measurement is preferably 70,000 to 200,000, more preferably 72,000 to 180,000, and still more preferably 75,000 to 150,000. The resin composition of the present invention preferably has Mw / Mn determined by GPC measurement of 1.2 to 5.0, more preferably 1.5 to 3.5. When the Mw or Mw / Mn is in this range, the molding processability of the methacrylic resin composition becomes favorable, and a molded article having excellent impact resistance and toughness is easily obtained.

The resin composition of the present invention preferably has a melt flow rate determined by measurement under the conditions of a load of 230 캜 and a load of 3.8 ㎏, preferably 0.1 to 15 g / 10 min, more preferably 0.5 to 5 g / 10 min, Is from 1.0 to 3 g / 10 min.

The resin composition of the present invention has a haze of 1.0 mm in thickness, preferably 1.0% or less, more preferably 0.7% or less, further preferably 0.5% or less.

The resin composition of the present invention can be formed into a molded product such as a film by any desired form such as pellet, granule, powder and the like.

The resin composition of the present invention can be molded into various molded articles by a known method. Examples of the molding method include an extrusion molding method, an injection molding method, a calendar molding method, a blow molding method, a compression molding method, and a solution casting method. In addition, in order to obtain a composite molded body with other materials, it is possible to adopt a known method of producing an integrated molded body such as an insert molding method and a coating molding method.

A preferred molded article in the resin composition of the present invention is a film.

The film relating to one embodiment of the present invention is not particularly limited by the production method. Examples of the film production method include solution casting, melt casting, extrusion molding, inflation molding, and blow molding. Of these, extrusion molding is preferable. According to the extrusion molding method, it is possible to obtain a film excellent in transparency, having improved toughness, excellent handling properties, and excellent balance between toughness, surface hardness and rigidity. The temperature of the resin composition discharged from the extruder according to the present invention is preferably set at 160 to 270 캜, more preferably at 220 to 260 캜.

From the viewpoint of obtaining a film of good surface smoothness, good mirror gloss and low haze in the extrusion molding method, the resin composition is extruded from a T-die in a molten state and then molded by sandwiching it with two or more mirror- Is preferable. The mirror-surface roll or mirror-surface belt is preferably made of metal. The linear pressure between the pair of mirror rolls or the mirror-surface belt is preferably 10 N / mm or more, and more preferably 30 N / mm or more.

The surface temperature of the mirror-surface roll or mirror-surface belt is preferably 130 ° C or lower. It is preferable that at least one surface temperature of the pair of mirror-surface rolls or mirror-surface belts is 60 占 폚 or higher. By setting the surface temperature to such a value, the resin composition discharged from the extruder can be cooled at a faster rate than the natural freezing, and the film of the present invention having an excellent surface smoothness and a low haze can be easily produced.

It is preferable that the film of the present invention is subjected to stretching treatment in at least one direction. By the stretching treatment, the mechanical strength is increased, and a film which is not cracked well can be obtained. The stretching method is not particularly limited, and examples thereof include uniaxial stretching, simultaneous biaxial stretching, sequential biaxial stretching, and tubular stretching. The temperature at the time of stretching is preferably from 100 to 200 占 폚, more preferably from 120 占 폚 to 160 占 폚, from the viewpoint that stretching can be performed uniformly and a film of high strength can be obtained. The stretching is usually carried out at 100 to 5000% / min on a length basis. The area elongation magnification is preferably 1.5 to 8 times. After the stretching, heat fixing is performed, or the film is relaxed, whereby a film with less heat shrinkage can be obtained.

The amount of the methacrylic resin (A) contained in the film of the present invention is preferably 73 to 99% by mass, more preferably 80 to 80% by mass from the viewpoint of transparency and small absolute value of retardation in the thickness direction, 97% by mass, and more preferably 85% to 95% by mass.

The amount of the polycarbonate resin (B) contained in the film of the present invention is preferably from 1 to 5% by mass, more preferably from 1.5 to 5% by mass, from the viewpoint that the absolute value of the retardation in the thickness direction is small. 4% by mass, more preferably 2 to 3% by mass.

The thickness of the film of the present invention is preferably 1 to 200 占 퐉, more preferably 10 to 50 占 퐉, and still more preferably 15 to 40 占 퐉.

The haze of the film of the present invention at a thickness of 40 占 퐉 is preferably 0.3% or less, more preferably 0.2% or less. Thereby, surface gloss and transparency are excellent. Further, in optical applications such as a liquid crystal protective film and a light guiding film, the utilization efficiency of the light source is increased, which is preferable. Further, it is preferable because the accuracy of the shape when performing the surface preparation is excellent.

The film of the present invention has an in-plane retardation (Re) at a thickness of 40 占 퐉 with respect to light having a wavelength of 590 nm of preferably 19 nm or less, more preferably 15 nm or less, further preferably 10 nm or less, Particularly preferably 5 nm or less, and most preferably 1 nm or less.

The film of the present invention preferably has a thickness direction retardation (Rth) at a thickness of 40 占 퐉 with respect to light having a wavelength of 590 nm of preferably -12 nm or more and 12 nm or less, more preferably -5 nm or more and 5 nm or less, More preferably -3 nm or more and 3 nm or less, particularly preferably -2 nm or more and 2 nm or less, and most preferably -1 nm or more and 1 nm or less.

The in-plane direction retardation Re and the thickness direction retardation Rth are values defined by the following equations, respectively.

_{Re = (n x - n y} ) × d

_{Rth = ((n x + n} y) / 2 - n z) × d

Here, n _x is the refractive index in the slow axis direction of the film, n _y is the refractive index in the fast axis direction of the film, n _z is the refractive index in the thickness direction of the film, and d [nm] The slow axis is the axis in the direction in which the refractive index in the film plane becomes maximum. The leading phase axis is a direction perpendicular to the slow axis in the plane.

The film of the present invention preferably has a photoelastic coefficient (beta) with respect to light having a wavelength of 590 nm of preferably not less than -3.0 x 10 ^-12 Pa- ^{1 and not} more than 3.0 x 10 ^-12 Pa- ¹ , 10 ^-12 ㎩ ^-1 than 2.0 × 10 ^-12 ㎩ ^-1 or less, more preferably -1.0 × 10 ^-12 ㎩ ^-1 than 1.0 × 10 ^-12 ㎩ ^-1 or less. In addition, the photoelastic coefficient (?) [10 ^-12 Pa- ¹ ] is calculated by the in-plane direction retardation Rin [nm] when the stress? Nm].

Rin =? X? D

When the in-plane direction retardation Re, the thickness direction retardation Rth, and the photoelasticity coefficient? Are within such a range, the influence on the display characteristics of the image display device caused by the retardation can be remarkably suppressed. More specifically, variations in the 3D image in the case of non-uniformity of interference or use in a liquid crystal display device for 3D display can be remarkably suppressed.

A functional layer may be formed on the surface of the film of the present invention. Examples of the functional layer include a hard coat layer, an antiglare layer, an antireflection layer, a sticking prevention layer, a diffusion layer, an antiglare layer, an antistatic layer, an antifouling layer and a slippery layer such as fine particles.

The film of the present invention has high transparency, low heat shrinkage, small dimensional change due to absorption, uniform thickness, and excellent surface smoothness. In addition, since the absolute value of the retardation in the thickness direction can be reduced and can be made thinner, it is possible to provide a retardation film, a polarizer protective film, a liquid crystal protection plate, a surface material of a portable information terminal, A transparent conductive film in which carbon nanotubes are applied to the surface, and a front plate for various displays. In particular, the film of the present invention is preferable for a polarizer protective film because the absolute value of the retardation in the thickness direction can be made small.

Since the film of the present invention has high transparency and heat resistance, it can be used as an IR cut film, a crime prevention film, a shatterproof film, a decorative film, a metal edible film, a solar cell back sheet, a front sheet for a flexible solar cell, Shrink films, and films for in-mold labeling.

The polarizing plate of the present invention has a polarizer and a film of the present invention laminated on the polarizer. The film of the present invention may be laminated on both sides of the polarizer, or may be laminated on one side. When the film of the present invention is laminated as a polarizer protective film on one side of a polarizer, an optical film other than the film of the present invention can be laminated on the other side. Examples of such an optical film include a polarizer protective film, a viewing angle adjusting film, a retardation film, and a luminance improving film. The lamination may be carried out through an adhesive layer.

For example, a polarizing plate according to a preferred embodiment of the present invention may be a polarizing plate obtained by laminating the film of the present invention, the easy-to-adhere layer, the adhesive layer, the polarizer, the adhesive layer, and the film of the present invention in this order, (See Fig. 1) laminated in the order of a film, an adhesive layer, an adhesive layer, a polarizer, an adhesive layer, and an optical film other than the film of the present invention.

The polarizer is a known optical element. Examples of the polarizer include those composed of a polyvinyl alcohol-based resin. The degree of polymerization of the polyvinyl alcohol-based resin used for the polarizer is preferably 100 to 5000, more preferably 1400 to 4000. The polyvinyl alcohol-based resin film can be produced by, for example, a casting method, a casting method, an extrusion method, or the like. The thickness of the polyvinyl alcohol-based resin film used for the polarizer can be suitably set according to the purposes and applications of the LCD in which the polarizing plate is used, but is typically 5 to 80 탆.

The adhesive layer that can be formed on the polarizing plate of the present invention is not particularly limited as far as it is optically transparent. As the adhesive constituting the adhesive layer, for example, an aqueous adhesive, a solvent adhesive, a hot melt adhesive, an active energy ray curable adhesive and the like can be used. Of these, water-based adhesives and active energy ray-curable adhesives are preferred.

The aqueous adhesive is not particularly limited. The aqueous adhesive may be in the form of an aqueous solution or in a latex form. Examples of the water-based adhesive include a vinyl polymer adhesive, a gelatin adhesive, a polyurethane adhesive, an isocyanate adhesive, a polyester adhesive, and an epoxy adhesive. Of these, an adhesive containing a vinyl polymer is preferable. As the vinyl polymer, a polyvinyl alcohol-based resin is preferable. The adhesive containing the polyvinyl alcohol-based resin may contain a water-soluble crosslinking agent such as boric acid, borax, glutaraldehyde, melamine, oxalic acid and the like. The adhesive containing a polyvinyl alcohol-based resin is preferable because it has excellent adhesion with a polarizer made of a polyvinyl alcohol-based resin film. An adhesive containing a polyvinyl alcohol-based resin having an acetoacetyl group is more preferably used because it improves the durability of the polarizing plate. The solid content contained in the water-based adhesive is usually 0.5 to 60 mass%. If necessary, additives such as a crosslinking agent, a catalyst such as an acid, and a metal compound filler can be added to the aqueous adhesive. The metallic compound filler can control the fluidity of the adhesive layer, stabilize the film thickness, obtain a polarizing plate having a good appearance, uniform surface irregularity, and no deviation in adhesion.

As the active energy ray-curable adhesive, a compound having a monofunctional or bifunctional or more (meth) acryloyl group or a compound having a vinyl group is used as a curing component, and an epoxy compound or an oxetane compound and a photoacid generator are mainly used Based curing component may be used.

As the active energy ray, an electron beam or ultraviolet ray can be used.

The method of forming the adhesive layer is not particularly limited. For example, it can be formed by applying the adhesive to an object, followed by heating or drying. The application of the adhesive may be applied to the polarizer protective film or to the polarizer. After the adhesive layer is formed, the polarizer-protective film and the polarizer can be pressed to laminate them. For lamination, a roll press machine, a flat press machine, or the like can be used. The heating drying temperature and drying time are appropriately determined depending on the kind of the adhesive. The thickness of the adhesive layer in the dried state is preferably 0.01 to 10 占 퐉, more preferably 0.03 to 5 占 퐉.

The easy adhesion layer which can be formed on the polarizing plate of the present invention is to improve the adhesion between the polarizing protective film and the surface on which the polarizing film is in contact. The adhesion facilitating layer can be formed by an easy adhesion treatment or the like. Examples of the adhesion facilitating treatment include surface treatments such as corona treatment, plasma treatment, and low-pressure UV treatment. The adhesion facilitating layer can be formed by a method of forming an anchor layer, or a combination of the above surface treatment and a method of forming an anchor layer. Among them, a corona treatment, a method of forming an anchor layer, and a method of using them in combination are preferable.

The anchor layer includes, for example, a silicon layer having a reactive functional group. The material of the silicon layer having a reactive functional group is not particularly limited, and examples thereof include alkoxysilane compounds containing isocyanate groups, amino group-containing alkoxysilanols, mercapto group-containing alkoxysilanols, carboxy-containing alkoxysilanols, Silanolols, vinyl-type unsaturated group-containing alkoxysilanols, halogen group-containing alkoxysilanols, and isocyanate group-containing alkoxysilanols. Of these, amino-based silanol is preferred. By adding a titanium-based catalyst or a tin-based catalyst for efficiently reacting silanol to the silanol, the adhesion can be strengthened. Other additives may be added to the silicon having the reactive functional group. Other additives include tackifier such as terpene resin, phenol resin, terpene-phenol resin, rosin resin and xylene resin; Stabilizers such as ultraviolet absorbers, antioxidants and heat-resistant stabilizers. As the anchor layer, a layer formed by saponifying a cellulose acetate butyrate resin is also exemplified.

The anchor layer is formed by applying and drying by a known technique. The thickness of the anchor layer in the dried state is preferably 1 to 100 nm, more preferably 10 to 50 nm. At the time of application, the chemical liquid for forming the anchor layer may be diluted with a solvent. The diluting solvent is not particularly limited, but alcohols may be mentioned. The dilution concentration is not particularly limited, but is preferably 1 to 5% by mass, and more preferably 1 to 3% by mass.

The optical film other than the film of the present invention is not particularly limited by the material constituting it. Examples of the material of the optical film include a cellulose resin, a polycarbonate resin, a cyclic polyolefin resin, and a methacrylic resin.

Cellulose resins are esters of cellulose and fatty acids. Specific examples of the cellulose ester-based resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Of these, cellulose triacetate is particularly preferable. Cellulose triacetate is commercially available in many products, and is advantageous in terms of availability and cost. Examples of commercially available products of cellulose triacetate include UV-50, UV-80, SH-80, TD-80U, TD-TAC and UZ- KC series manufactured by Konica Minolta Co., Ltd., and the like.

The cyclic polyolefin resin is a generic name of a resin polymerized using a cyclic olefin as a polymerization unit and includes, for example, those described in JP-A-1-240517, JP-A-3-14882, JP- 3-122137 and the like. Specific examples thereof include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and? -Olefins such as ethylene and propylene (typically, random copolymers) and unsaturated carboxylic acids Graft polymers modified with a carboxylic acid or a derivative thereof, and hydrides thereof. Specific examples of cyclic olefins include norbornene monomers.

As the cyclic polyolefin resin, various products are commercially available. Specific examples thereof include trade names "Zeonex", "Zeonor" manufactured by Nippon Zeon Corporation, "Aton" manufactured by JSR Corporation, "Topaz" manufactured by Polyplastics Corporation, and "APEL" .

As the methacrylic resin used for the optical film other than the film of the present invention, any suitable methacrylic resin may be employed as long as the effect of the present invention is not impaired. (Meth) acrylic acid copolymer, a methacrylic acid methyl- (meth) acrylic acid ester copolymer, a methacrylic acid methyl-acrylic acid ester-methacrylic acid ester-methacrylic acid ester- (Meth) acrylic acid copolymer, a (meth) acrylic acid methyl-styrene copolymer (MS resin and the like), and a polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl copolymer) have. As the methacrylic resin, for example, acrylate VH or acrylate VRL20A manufactured by Mitsubishi Rayon Co., Ltd., methyl methacrylate and maleimide-based monomer described in Japanese Patent Application Laid-open No. 2013-033237 or WO2013 / 005634 A Acrylic resin having a ring structure in the molecule described in WO2005 / 108438 A, methacrylic resin having a ring structure in the molecule described in JP-A-2009-197151, intramolecular crosslinking or intramolecular cyclization reaction And a high glass transition temperature (Tg) of methacrylic resin.

As the methacrylic resin used in the optical film other than the film of the present invention, a methacrylic resin having a lactone ring structure may be used. High heat resistance, high transparency, and high mechanical strength by biaxial stretching. Examples of the methacrylic resin having a lactone ring structure are disclosed in JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, JP-A-2002-254544, And a methacrylic resin having a lactone ring structure described in JP-A-2005-146084.

The polarizing plate of the present invention can be used in an image display apparatus. Specific examples of the image display device include self-emission type display devices such as an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED), a liquid crystal display . The liquid crystal display device has a liquid crystal cell and the polarizer disposed on at least one side of the liquid crystal cell.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. The measurement of the physical properties and the like was carried out by the following method.

(Polymerization conversion ratio)

A column (INERT CAP 1 (df = 0.4 탆, ID 0.25 mm, length 60 m) manufactured by GLC-G-230 Sciences Inc.) was connected to a gas chromatograph (GC-14A, manufactured by Shimadzu Corporation) The temperature was 180 캜, the detector temperature was 180 캜, and the column temperature was elevated from 60 캜 to 200 캜 at a rate of 10 캜 / min. The polymerization conversion rate was calculated based on the results.

≪ Composition of resin monomer &

Using a nuclear magnetic resonance apparatus (ULTRA SHIELD 400 PLUS, manufactured by Bruker), ¹ H-NMR spectrum was measured under the conditions of 1 ml of deuterated chloroform at room temperature and the cumulative number of times of 64 times with respect to 10 mg of the resin, The composition of the monomer units in the polymer was calculated.

(Photoelastic coefficient)

The unstretched film was cut into a size of 20 mm x 40 mm and the film piece was set in the ellipticity polarization measuring device with both ends in the long axis direction sandwiched therebetween. While the stress was applied in the major axis direction at 10 ⁶ to 10 ⁷ Pa, The in-plane retardation (Rin) of the film piece center in the light having a wavelength of 590 nm was measured under conditions of ± 2 ° C. and humidity of 50 ± 5%. Stress and the relationship between retardation (Rin = β × σ × d , Rin: stress (σ) [㎩] is the in-plane retardation [㎚] when, the β: photoelastic coefficient [10 ^-12 ㎩ ^-1], σ : The stress [Pa], d: the film thickness [nm]).

(Strength of unstretched film)

The unstretched film was cut into a size of 100 mm x 50 mm and the film piece was set in a cylindrical mandrel bending test machine equipped with a cylindrical mandrel having a diameter of 6 mm and the state of the film piece was evaluated when it was bent 180 degrees.

A: There was no change in the film, and the obtained state could be maintained.

B: The film is fragile and cracked.

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

Mw and Mw / Mn were calculated from the values converted to the molecular weights of standard polystyrene by measuring the chromatogram under gel-permeation chromatography (GPC) under the following conditions.

GPC apparatus: HLC-8320 manufactured by Tosoh Corporation

Detector: differential refractive index detector

Column: Two TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and SuperHZ4000 connected in series were used.

Eluent: tetrahydrofuran

Flow rate of eluent: 0.35 ml / min

Column temperature: 40 DEG C

Calibration curve: Created using 10 points of standard polystyrene

(Glass transition temperature (Tg))

The temperature was raised up to 250 ° C at one time by using a differential scanning calorimetry apparatus (DSC-50 (product number), manufactured by Shimadzu Corporation) in accordance with JIS K7121 and then cooled to room temperature. Lt; 0 > C / min. The midpoint glass transition temperature determined from the DSC curve is defined as the glass transition temperature in the present invention.

(Saturation absorption rate)

Using a injection molding machine (SE-180DU-HP, manufactured by Sumitomo Heavy Industries Co., Ltd.), the methacrylic resin obtained in Production Example was injection-molded at a cylinder temperature of 280 캜, a mold temperature of 75 캜 and a molding cycle of 1 minute, Mm, a width of 100 mm, and a thickness of 2 mm. The specimens were vacuum-dried for 3 days under the conditions of a temperature of 50 캜 and a pressure of 5 mmHg to measure the weight (W ₀ ) of the test piece during the absolutely dry condition. Thereafter, the full-bodied test piece was allowed to stand under conditions of a temperature of 60 DEG C and a humidity of 90% for 300 hours. Thereafter, the mass (W ₁ ) of the test piece was measured. The saturation absorption rate (%) was calculated by the following formula.

Saturation Absorption Rate (%) = {W ₁ - W ₀ } / W ₀ 100

(Melt Volume Flow Rate (MVR))

The MVR was measured in accordance with JIS K7210 under the conditions of 300 캜, 1.2 kg load, and 10 minutes.

(Total light transmittance (T _t ))

The total light transmittance was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) according to JIS K7361-1.

(Hayes (H))

Haze (H) was measured using a haze meter (HM-150 manufactured by Murakami Color Research Laboratory) in accordance with JIS K7136.

(Retardation Re in the in-plane direction)

A test piece of 40 mm x 40 mm was set in an automatic birefringence system (KOBRA-WR manufactured by Oji Scientific Instruments Co., Ltd.), and the phase difference at a temperature of 23 +/- 2 DEG C and a humidity of 50 +/- 5% was measured at a wavelength of 590 nm and an incident angle of 0 .

(Retardation in thickness direction Rth)

A test piece of 40 mm x 40 mm was set in an automatic birefringence system (KOBRA-WR manufactured by Oji Scientific Instruments Co., Ltd.), and the phase difference in the oblique direction at a wavelength of 590 nm and a temperature of 23 +/- 2 DEG C and a humidity of 50 +/- 5% and the values and an average refractive index (n) the refractive index (n _x, n _y and n _z) a, and also the phase difference (Rth) (= ((n x + n y) / 2 in the thickness direction is calculated from - n _z) × d). n _x is the refractive index in the in-plane slow axis direction, n _y is the refractive index in the perpendicular direction to the slow axis, and n _z is the refractive index in the thickness direction.

The thickness (d) [nm] of the test piece was measured using Digimatic Indicator (manufactured by Mitsutoyo Co., Ltd.). The average refractive index n required for calculation of the refractive indexes (n _x , n _y and n _z ) was measured with a digital precision refractometer (KPR-20, manufactured by Carl Zeiss Optics KK).

(Wet heat test)

In the case of a uniaxially stretched film, a test piece cut into 150 mm x 1 mm was prepared with the elongation direction as the long side and the biaxially stretched film as the long side in the machine direction (MD) of the film production. The test piece was vacuum dried at 40 DEG C for 12 hours at 5 Torr, and then left under high temperature and high humidity of 80 DEG C and 90% RH for 12 hours. The contraction length from 150 mm was calculated.

Moisture shrinkage ratio = (150 mm - length after test) / 150 mm x 100 (%)

(Yellow index (YI))

The resin compositions prepared in Examples and Comparative Examples were subjected to hot press molding to obtain a plate-shaped molded article having a thickness of 50 mm x 50 mm x 1.0 mm. These 1.0 mm thick yellow indices of the plate-shaped molded bodies were measured in accordance with JIS K7373 on the basis of values measured in accordance with JIS Z-8722 using an ultraviolet visible near infrared spectrophotometer (UV-3600, manufactured by Shimadzu Corporation) The yellow index (YI) was calculated.

In the description of this embodiment, methyl methacrylate is replaced with MMA, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane 8-yl (X in formula (1) is tricyclo [5.2.1.0 ^2,6 ] decane- (Compound of formula (1) in which isobornan-2-yl group) is replaced with IBMA, cyclohexyl methacrylate as CHMA, and methyl acrylate as MA Are omitted.

Production Example 1 < PMMA1 >

84 parts by mass of purified methyl methacrylate (MMA), 15 parts by mass of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (TCDMA), and 100 parts by mass of methyl methacrylate were placed in an autoclave equipped with a stirrer and a collecting tube. And 1 part by mass of methyl acrylate (MA) were added to prepare a monomer mixture. To the monomer mixture, 0.006 parts by mass of a polymerization initiator (AIBN, hydrogen-releasing ability: 1%, 1 hour half-life temperature: 83 ° C) and 0.38 parts by mass of chain transfer agent (n-octylmercaptan) were added and dissolved to obtain a raw material liquid. Oxygen gas in the production apparatus was extracted by nitrogen gas.

The raw material liquid was supplied from the autoclave at a constant flow rate so as to have an average residence time of 120 minutes in a continuous flow type shaping reactor controlled at a temperature of 140 캜, and bulk polymerization was carried out at a polymerization conversion rate of 57 mass%.

The liquid discharged from the molding reactor was heated to 250 DEG C, fed to a twin-screw extruder controlled at 260 DEG C at a constant flow rate, and adiabatically flushed at the extruder inlet. The volatiles (monomers, dimers, trimer, etc.) removed by the adiabatic flash were discharged from the open vents. Volatile matter containing the unreacted monomer as a main component was discharged from a reduced pressure vent at a pressure of 6 Torr downstream of the inlet of the twin screw extruder, and the remaining resin component was extruded into a stranded screw. The strand was cut into a pelletizer to obtain methacrylic resin < PMMA1 > in the form of pellets.

The obtained methacrylic resin had a structural unit derived from MMA of 85% by mass, a structural unit derived from TCDMA of 14% by mass, and a structural unit derived from MA of 1% by mass. The weight average molecular weight (Mw) was 67000, the molecular weight distribution (Mw / Mn) was 1.81, and the glass transition temperature (Tg) was 125 占 폚. Table 1 shows the results of analysis of the methacrylic resin.

Production Example 2 < PMMA2 >

To the autoclave were added 78 parts by mass of MMA, 22 parts by mass of TCDMA, 0.06 parts by mass of AIBN, 0.01 parts by mass of 1,1-bis (t-butylperoxy) cyclohexane, 0.22 parts by mass of n-octylmercaptan, 0 parts by mass of kistiopropionate, 200 parts by mass of water, 2.64 parts by mass of dispersant and 33 parts by mass of a pH adjuster. While stirring the autoclave, the liquid temperature was raised from room temperature to 70 占 폚 and held at 70 占 폚 for 180 minutes. Thereafter, the mixture was maintained at 120 DEG C for 60 minutes to effect polymerization reaction. The liquid temperature was lowered to room temperature, and the polymerization reaction liquid was withdrawn from the autoclave. The solid component was taken out from the polymerization reaction solution by filtration, washed with water and hot-air dried at 80 DEG C for 24 hours to obtain a beaded methacrylic resin [PMMA2]. Table 1 shows the results of analysis of the methacrylic resin.

Production Examples 3 to 11 <PMMA 3 to 11>

(MMA), methacrylic acid tricyclo [5.2.1.0 ^2,6 ] deca-8-yl (TCDMA), methyl acrylate (MA), isobornyl methacrylate (IBMA), cyclohexyl methacrylate Except that the amounts of hexyl (CHMA), n-octyl mercaptan (n-OM) and pentaerythritol tetrakisthiopropionate (PETP) were changed as shown in Table 1 or Table 2 To obtain methacrylic resin < PMMA3-11 &gt;. Table 1 and Table 2 show the results of analysis of the methacrylic resin.

Production Example 12 < PMMA12 >

40 parts by mass of methyl methacrylate (MMA) and 10 parts by mass of methyl 2- (hydroxymethyl) acrylate (MHMA) were placed in an internal 30 L reaction kettle equipped with a stirrer, a temperature sensor, , 50 parts by mass of toluene, and 0.025 parts by mass of an antioxidant (Adekastab 2112, manufactured by Asahi Denki Kogyo Co., Ltd.) were charged, and the temperature was raised to 105 占 폚 while allowing nitrogen to pass therethrough. 0.05 parts by mass of t-amylperoxy isoniconoate (trade name: Luperox 570, manufactured by Akemi Yoshitomi) was added and 0.10 parts by mass of t-amyl peroxy isonanoate was added to the mixture at 3 Solution polymerization was carried out under reflux at about 105 to 110 DEG C while being dripped over a period of time, and aging was further performed for 4 hours.

Next, 0.05 parts by mass of 2-ethylhexyl phosphate (Phoslex A-8, manufactured by Sakai Chemical Industry Co., Ltd.) as a catalyst for cyclization condensation reaction (cyclization catalyst) was added to the obtained polymerization solution, After the cyclization condensation reaction proceeded for 2 hours, the polymerization solution was heated by an autoclave at 240 ° C for 30 minutes to further proceed the cyclization condensation reaction.

Next, the obtained polymerization solution was passed through a screw with a vent having a barrel temperature of 240 DEG C, a rotational speed of 100 rpm, a rear vent set to a pressure of 13.3 to 400 hPa (10 to 300 mmHg) and four pores Was introduced into a twin-screw extruder (Φ = 29.75 mm, L / D = 30) at a treatment rate of 2.0 kg / hour in terms of a resin amount, and devolatilization was carried out. To obtain a methacrylic resin < PMMA12 > having a lactone ring in the main chain. Table 2 shows the results of analysis of the methacrylic resin < PMMA12 >.

Polycarbonate resin < PC1-3 > were prepared.

PC 1: manufactured by Sumikastar Theory Polycarbonate, SD POLYCA TR-2001 (part number) [Mw = 22000, MVR (300 캜, 1.2 Kg) = 200 cm 3/10 min]

(Mw = 35000, MVR (300 DEG C, 1.2 Kg) = 40 cm &lt; 3 &gt; / 10 min) manufactured by Sumika Star Theory Polycarbonate Co.,

(Mw = 58000, MVR (300 DEG C, 1.2 Kg) = 4 cm &lt; 3 &gt; / 10 min) manufactured by Sumika Star Theory Polycarbonate Co.,

Parodoid K125-P (manufactured by Dow Chemical Company) was prepared as a processing aid.

2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; LA-F70) was prepared as an ultraviolet absorber.

&Lt; Example 1 >

96 parts by mass of methacrylic resin < PMMA1 > and 4 parts by mass of polycarbonate resin < PC1 > were mixed and kneaded and extruded at 250 DEG C in a twin screw extruder (trade name: KZW20TW-45MG- 1].

The glass transition temperature (Tg) and the yellow index (YI) of the resin composition [1] were measured.

The resin composition [1] was hot-pressed to obtain a plate-shaped molded article having a thickness of 50 mm x 50 mm x 1.0 mm. The total light transmittance (T _t ) and haze (H) at a thickness of 1.0 mm were measured. The results are shown in Table 3.

The resin composition [1] was dried at 80 캜 for 12 hours. The resin composition [1] was extruded from a 150 mm wide T-die at a resin temperature of 260 占 폚 using a 20 mm? Single-axis extruder (manufactured by OCS) and rolled with a roller having a surface temperature of 110 占 폚, An undrawn film having a thickness of 80 탆 was obtained. The strength and the photoelastic coefficient (?) Of the unstretched film are shown in Table 3.

The unstretched film was cut into a size of 50 mm x 40 mm and set in a tensile tester (AG-IS 5kN manufactured by Shimadzu Corporation) so as to have a length of 20 mm between the chucks. The stretching temperature at the glass transition temperature + Minute, stretching uniaxially at an area elongation of 2 times in the longitudinal direction, holding for 10 seconds, and then quenched to obtain a monoaxially stretched film having a thickness of 40 占 퐉.

The uniaxial retardation thickness (d), the in-plane retardation (Re), the thickness direction of the stretched film (Rth), the total light transmittance _{(T t),} shows the measurement results of the haze value (H) and the wet heat shrinkage ratio are shown in Table 3.

&Lt; Examples 2 to 7 and Comparative Examples 1 to 10 >

The resin compositions [2] to [17] were prepared in the same manner as in Example 1 except that the composition shown in Table 3 or Table 4 was used. The physical properties of the resin compositions [2] to [17] are shown in Tables 3 or 4.

An unoriented film having a width of 110 mm and a thickness of 80 占 퐉 and a uniaxially stretched film having a thickness of 40 占 퐉 were obtained in the same manner as in Example 1 except that the resin compositions [2] to [17] were used in place of the resin composition [1]. The evaluation results of the unstretched film and the uniaxially stretched film are shown in Table 3 or 4. In Comparative Example 1 and Comparative Example 5, uniaxial stretching could not be performed due to the lack of strength of the unstretched film.

&Lt; Example 8 >

A resin composition [19] was prepared in the same manner as in Example 1 except that the composition shown in Table 5 was changed.

An unoriented film having a width of 110 mm was obtained in the same manner as in Example 1 except that the resin composition [19] was used in place of the resin composition [1], and the thickness of the obtained film was changed to 160 탆.

This unstretched film was cut into a size of 100 mm x 100 mm. The slice was set in a pantograph type biaxial stretching tester (manufactured by Toyobo Co., Ltd.) and stretched at a stretching temperature of 20 占 폚, a longitudinal stretching speed of 1000% / min, a transverse stretching speed of 1000% / min, Simultaneous biaxial stretching at a longitudinal stretching ratio of 2: 2 and a transverse stretching ratio of 2: 1 was carried out for 10 seconds and then quenched to obtain a biaxially oriented film having a thickness of 40 탆. Table 5 shows the evaluation results of the resin composition [19], the unoriented film and the biaxially oriented film.

&Lt; Comparative Example 11 &

A resin composition [18] was produced in the same manner as in Example 8 except that the composition shown in Table 5 was changed.

An unoriented film having a width of 110 mm and a thickness of 160 占 퐉 and a biaxially oriented film having a thickness of 40 占 퐉 was obtained in the same manner as in Example 8 except that the resin composition [18] was used instead of the resin composition [19]. Table 5 shows the evaluation results of the resin composition [18], the unoriented film and the biaxially oriented film. Since the saturated water absorption rate of PMMA12 was high, the moisture shrinkage rate was large.

&Lt; Examples 9 to 11 >

Resin compositions [20] to [22] were prepared in the same manner as in Example 8 except that the composition shown in Table 5 was changed.

An unoriented film having a width of 110 mm and a thickness of 160 占 퐉 and a biaxially oriented film having a thickness of 40 占 퐉 was obtained in the same manner as in Example 8 except that the resin compositions [20] to [22] were used instead of the resin composition [19]. Table 5 shows the evaluation results of the resin compositions [20] to [22], the unstretched film and the biaxially oriented film.

&Lt; Example 12 >

The resin composition [23] was prepared in the same manner as in Example 8 except that the composition shown in Table 5 was used.

An undrawn film having a width of 110 mm was obtained in the same manner as in Example 8 except that the resin composition [23] was used in place of the resin composition [19] and the thickness of the obtained film was changed to 80 탆. A biaxially oriented film was obtained in the same manner as in Example 8 except that the thickness of the obtained film was changed to 20 占 퐉. Table 5 shows the evaluation results of the resin composition [23], the unoriented film and the biaxially oriented film.

Example 13

A polyvinyl alcohol film having an average degree of polymerization of 2400, a degree of saponification of 99.9 mol% and a thickness of 75 mu m was immersed in hot water at 30 DEG C for 60 seconds to swell. Then, it was stretched to 3.5 times while dyeing in an iodine solution of 0.3 wt% (weight ratio: iodine / potassium iodide = 0.5 / 8) at 30 DEG C for 1 minute. Thereafter, the substrate was dipped in a 4 wt% boric acid aqueous solution at 65 캜 for 0.5 minutes, and the stretching ratio was increased to 6 times. After stretching, the film was dried in an oven at 70 DEG C for 3 minutes to obtain a polarizer having a thickness of 22 mu m.

16.8 g of polyester urethane (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 210, solid content: 33%) and 4.2 g of a crosslinking agent (oxazoline-containing polymer manufactured by Nippon Kogyo Co., trade name: Epochros WS-700, solid content: 25% 2.0 g of 1 wt% ammonia water, 0.42 g of colloidal silica (manufactured by Fuso Chemical Co., Ltd., Qwatron PL-3, solid content: 20 wt%) and 76.6 g of pure water were mixed to obtain an easy adhesive composition.

, 38.3 parts by mass of N-hydroxyethyl acrylamide (manufactured by Kojinsha), 19.1 parts by mass of tripropylene glycol diacrylate (Aronix M-220, manufactured by TOAGOSEI Co., Ltd.), 38.3 parts by mass of acryloylmorpholine And 1.4 parts by mass of a photopolymerization initiator (trade name: KAYACURE DETX-S, diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) were mixed and stirred at 50 DEG C for 1 hour to obtain an active energy ray curable adhesive.

The biaxially stretched film (hereinafter referred to as film a) obtained in Example 11 was subjected to corona discharge treatment. The easy adhesive composition was coated on the corona discharge treated surface of the film a with a bar coater so as to have a thickness of 100 nm after drying. Thereafter, the film was dried in a hot-air dryer (110 ° C) for about 5 minutes to form an easy-to-adhere layer on one side of the film a.

The active energy ray-curable adhesive was applied on the easy-adhesion layer of the film a so as to have a thickness of 500 nm after drying to form an adhesive layer.

On each of both surfaces of the polarizer, the film a was superimposed using a small laminator with the adhesive layer facing the polarizer side. The polarizing plate X, which was obtained by heating the film to a temperature of 50 占 폚 using an IR heater on both sides and irradiating ultraviolet rays at an integrated irradiation amount of 1000 / mJ / cm2 on both surfaces to cure the active energy ray curable adhesive, .

The polarizing plate X was allowed to stand in a thermostatic hygrostat at 80 DEG C and 90% RH for 100 hours. Thereafter, the polarizing plate X taken out from the thermo-hygrostat was visually observed. No deterioration of the polarizer was observed.

Comparative Example 12

A triacetylcellulose film having a thickness of 40 占 퐉 was saponified by immersing in a 10% aqueous solution of sodium hydroxide (60 占 폚) for 30 seconds. Thereafter, the film was washed with water for 60 seconds to obtain a film b.

100 parts by mass of an acetoacetyl group-containing polyvinyl alcohol-based resin (average degree of polymerization: 1200, saponification degree: 98.5 mol%, acetoacetyl group degree of deformation: 5 mol%) and 20 parts by mass of methylol melamine were heated at 30 DEG C And dissolved in pure water to obtain an adhesive composition having a solid content concentration of 0.5%.

The adhesive composition was allowed to stand under the environment of 30 캜 for 30 minutes. The adhesive composition was applied to the film b so as to have a thickness of 50 nm after drying to form an adhesive layer.

On each of both surfaces of the polarizer, the adhesive layer was laminated to the polarizer side, and the film b was superimposed using a small laminator. This was dried in a hot air dryer (70 ° C) for 5 minutes to obtain a polarizing plate Y comprising a film b laminated on both surfaces of the polarizer.

The polarizing plate Y was allowed to stand in a thermo-hygrostat at 80 DEG C and 90% RH for 100 hours. Thereafter, the polarizing plate Y taken out from the thermo-hygrostat was visually observed. Deterioration of the polarizer was observed.

11 Polarizer
12 adhesive layer
13 Adhesion facilitating layer
14 Polarizer protective film
15 Adhesive layer
16 optical film

Claims (13)

From 10 to 50 mass% of a structural unit (a1) derived from a methacrylic acid polycyclic aliphatic hydrocarbon ester, from 50 to 90 mass% of a structural unit (a2) derived from a methacrylic acid ester other than a methacrylic acid polycyclic aliphatic hydrocarbon ester, And 0 to 20% by mass of a structural unit (a3) derived from an acrylate ester, and a methacrylic resin (A)
The polycarbonate resin (B)
Wherein the mass ratio (A) / (B) of the methacrylic resin (A) to the polycarbonate resin (B) is 95/5 to 99.9 / 0.1. The method according to claim 1,
Wherein the methacrylic polycyclic aliphatic hydrocarbon ester is a compound represented by formula (1).

(In the formula (1), X is a polycyclic aliphatic hydrocarbon group having at least 10 carbon atoms) 3. The method of claim 2,
X is isobornan-2-yl group or tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group. 4. The method according to any one of claims 1 to 3,
And the methacrylic acid ester other than the methacrylic acid polycyclic aliphatic hydrocarbon ester is methyl methacrylate. 5. The method according to any one of claims 1 to 4,
And a mid-point glass transition temperature measured by JIS K7121 (heating rate: 20 占 폚 / min) of 120 占 폚 or higher. 6. The method according to any one of claims 1 to 5,
Wherein the total content of the methacrylic resin (A) and the polycarbonate resin (B) is 80 to 100% by mass. A film comprising the resin composition according to any one of claims 1 to 6. 8. The method of claim 7,
A film having a thickness of 10 to 50 占 퐉. 9. The method according to claim 7 or 8,
Biaxially stretched film with an area ratio of 1.5 to 8 times. 9. The method according to claim 7 or 8,
At least uniaxially stretched film. A polarizer protective film comprising the film according to any one of claims 7 to 10. A retardation film comprising the film according to any one of claims 7 to 10. A polarizer,
A polarizer having the film according to any one of claims 7 to 10 laminated on the polarizer.

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