TWI658085B - Methacrylic resin composition - Google Patents

Abstract

10 to 50% by mass of a structural unit (a1) derived from a polycyclic aliphatic hydrocarbon ester of methacrylic acid, and 50 to 90% by mass of a methacrylic acid ester derived from a polycyclic aliphatic hydrocarbon ester other than methacrylic The methacrylic resin (A) and the polycarbonate resin (B) formed from the structural unit (a2) and 0-20% by mass of the acrylate-derived structural unit (a3) are compared with the methacrylic resin (A). The polycarbonate resin (B) has a mass ratio (A) / (B) of 95/5 to 99.9 / 0.1, and is melt-kneaded to obtain a resin composition. This resin composition is molded by a well-known method to obtain a film.

Description

Methacrylic resin composition

The present invention relates to a methacrylic resin composition. More specifically, the present invention relates to a resin composition containing a methacrylic resin and a polycarbonate resin, which can easily obtain excellent heat resistance and transparency, has a small absolute value of a phase difference in a thickness direction, has a uniform thickness, and has a surface. Film with excellent smoothness.

A resin obtained by copolymerizing methyl methacrylate (MMA) and cyclohexyl methacrylate (CHMA) (hereinafter also referred to as MMA-CHMA resin) and a polycarbonate resin (hereinafter also referred to as PC resin) are blended Since the combined resin composition is excellent in transparency, it has been proposed to use the resin composition to produce optical films (Patent Documents 1, 2 and 3).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-167195

[Patent Document 2] Japanese Patent Laid-Open No. 2014-031459

[Patent Document 3] Japanese Patent Publication No. 2012-507040

[Patent Document 4] Japanese Patent Laid-Open No. 2002-12728 (Japanese invention

(Patent No. 3870670)

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

The object of the present invention is to provide a resin composition comprising a methacrylic resin and a polycarbonate resin, which can easily obtain excellent heat resistance and transparency, has a small absolute value of the phase difference in the thickness direction, and is excellent in high temperature and high humidity. Thin film with small shrinkage, uniform thickness and excellent surface smoothness.

The review was repeated in order to achieve the above object, and as a result, the present invention including the following aspects was finally completed.

[1] A resin composition comprising: 10 to 50% by mass of a structural unit (a1) derived from a methacrylic polycyclic aliphatic hydrocarbon ester; and 50 to 90% by mass of a methacrylic derived polycyclic fat A methacrylic resin (A) formed from a structural unit (a2) of methacrylic acid ester other than the group hydrocarbon ester and a structural unit (a3) derived from acrylate at 0 to 20% by mass, and a 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 polycyclic aliphatic hydrocarbon ester of methacrylic acid is a compound represented by formula (1);

(In the formula (1), X is a polycyclic aliphatic hydrocarbon group having 10 or more carbon atoms).

[3] The resin composition according to [2], wherein X is different Alk-2-yl or tricyclic [5.2.1.0 ^2,6 ] decane-8-yl.

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

[5] The resin composition according to any one of [1] to [4], wherein the intermediate point glass transition temperature measured by JIS K7121 (temperature rise 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% by mass.

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

[8] The film according to [7], which has a thickness of 10 to 50 μm.

[9] The film according to [7] or [8], which is biaxially extended to 1.5 to 8 times in an area ratio.

[10] The film according to [7] or [8], which is stretched at least uniaxially.

[11] A protective film for polarizing lenses, which comprises the above-mentioned [7] to [10] The film of any one of the items.

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

[13] A polarizing plate comprising: a polarizer; and the film according to any one of [7] to [10] laminated on the polarizer.

The resin composition of the present invention has a high glass transition temperature, high light transmittance, and low haze. By molding the resin composition of the present invention by a well-known method, excellent heat resistance and transparency can be easily obtained, the absolute value of the phase difference in the thickness direction is small, shrinkage under high temperature and humidity is small, the thickness is uniform, and the surface smoothness is excellent The film. By laminating the film and the polarizer of the present invention, a polarizing plate can be provided. The polarizing plate is used for manufacturing a liquid crystal display device having functions of high color, wide viewing angle, low color distortion, and the like.

11‧‧‧Polarizer

12‧‧‧ Adhesive layer

13‧‧‧ Easy to attach layer

14‧‧‧ Polarizer Protective Film

15‧‧‧ Adhesive layer

16‧‧‧ Optical Film

FIG. 1 is a diagram showing a configuration of a polarizing plate according to an embodiment of the present invention.

[Form of Implementing Invention]

A resin composition according to an embodiment of the present invention is made of a methacrylic resin (A) and a polycarbonate resin (B).

Methacrylic resin (A) contains structural unit (a1) , The structural unit (a2) and the structural unit (a3).

The structural unit (a1) is derived from a polycyclic aliphatic hydrocarbon methacrylate, and is preferably formed by an addition reaction of a methacrylfluorenyl group in the polycyclic aliphatic hydrocarbon methacrylate. The structural unit (a1) is specifically preferably a unit represented by formula (2);

Cy-based polycyclic aliphatic hydrocarbon group in formula (2)

The polycyclic aliphatic hydrocarbon group is not particularly limited, and examples thereof include octahydropentalen-1-yl, octahydropentalen-2-yl, and octahydro-1-1H-inden-4-yl. , Octahydro-1-1H-inden-5-yl, hexahydro-1,5-methylene-pentadiene-3A-yl, decahydronaphthalen-1-yl, decahydronaphthalen-2-yl, octa Hydrocyclopenta [c, d] pentaene-2A-2a (2H)-, 3a, 6a-dimethyloctahydropentalen-2-yl, tetradecahydroanthracene-9-yl, androstane- Condensed polycyclic aliphatic hydrocarbon groups such as 4-yl, cholestan-2-yl, and cholester-5-yl; Alk-2-yl, 2-methyl Alk-2-yl, 2-ethyl Alk-2-yl, 1,3,3-trimethyl Alk-2-yl, 1,2,3,3-tetramethyl Alk-2-yl, 1,3,3-trimethyl Alk-2-yl, iso Alk-2-yl, 2-methyliso Alk-2-yl, 2-ethyliso Alkan-2-yl, decahydro-2,5-methylene-7,10-methylenenaphthalene-1-yl, tricyclic [5.2.1.0 ^2,6 ] decane-8-yl, 8-methyl Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 8-ethyltricyclo [5.2.1.0 ^2,6 ] decane-8-yl, adamantane-1-yl, adamantane-2 -Yl, 2-methyladamantane-2-yl, 2-ethyladamantane-2-yl, decahydro-3,6-methylene-2,2,7,7-tetramethylnaphthalene-1 -Bridged cyclic aliphatic hydrocarbon groups; spirobicyclopentane-2-yl, spirobicyclopentane-3-yl, spirobicyclohexane-2-yl, spirobicyclohexane-3-yl, etc. Structure of polycyclic aliphatic hydrocarbon groups and the like.

The polycyclic aliphatic hydrocarbon methacrylate is preferably of formula (1) The compound shown.

X-series polycyclic fat having 10 or more carbon atoms in formula (1) The group hydrocarbon group is preferably a bridged cyclic aliphatic hydrocarbon group having 10 or more carbon atoms. Furthermore, the bridged cyclic aliphatic hydrocarbon system is an alicyclic hydrocarbon having a structure in which two non-adjacent carbon atoms constituting a ring are connected by a carbon chain composed of one or more carbon atoms. This bridged cyclic aliphatic hydrocarbon system may have a condensed ring structure and 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 10 to 20.

Examples of the polycyclic aliphatic hydrocarbon group having 10 or more carbon atoms include octahydrocyclopenta [c, d] pentaene-2A-2a (2H)-group and 3a, 6a-dimethyloctahydropentaene 2-yl, tetradecylanthracene-9-yl, androst-4-yl, cholestan-2-yl, cholestan-5-yl, 1,3,3-trimethyl Alk-2-yl, 1,2,3,3-tetramethyl Alk-2-yl, 1,3,3-trimethyl Alk-2-yl, iso Alk-2-yl, 2-methyliso Alk-2-yl, 2-ethyliso Alkan-2-yl, decahydro-2,5-methylene-7,10-methylenenaphthalene-1-yl, tricyclic [5.2.1.0 ^2,6 ] decane-8-yl, 8-methyl Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 8-ethyltricyclo [5.2.1.0 ^2,6 ] decane-8-yl, adamantane-1-yl, adamantane-2 -Yl, 2-methyladamantane-2-yl, 2-ethyladamantan-2-yl, decahydro-3,6-methylene-2,2,7,7-tetramethylnaphthalene-1 -Yl, spirobicyclohexane-2-yl, spirobicyclohexane-3-yl, and the like. Among these, 1,3,3-trimethyl Alk-2-yl, 1,2,3,3-tetramethyl Alk-2-yl, 1,3,3-trimethyl Alk-2-yl, iso Alk-2-yl, 2-methyliso Alk-2-yl, 2-ethyliso Alkan-2-yl, decahydro-2,5-methylene-7,10-methylenenaphthalene-1-yl, tricyclic [5.2.1.0 ^2,6 ] decane-8-yl, 8-methyl Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 8-ethyltricyclo [5.2.1.0 ^2,6 ] decane-8-yl, adamantane-1-yl, adamantane-2 -Yl, 2-methyladamantane-2-yl, 2-ethyladamantane-2-yl, more preferably iso Alkan-2-yl, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, particularly preferably tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (common name: dicyclopentyl ).

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

Examples of the methacrylate (a2) include a monocyclic aliphatic hydrocarbon methacrylate such as cyclohexyl methacrylate, cyclopentyl methacrylate, cycloheptyl methacrylate, and the like; methyl methacrylate , Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, third butyl methacrylate , Amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, etc. Chain aliphatic hydrocarbon esters of acrylic acid: 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, benzyl methacrylate, Phenoxyethyl methacrylate, phenyl methacrylate and the like. Among these, from the viewpoint of improving transparency and heat resistance, a chain methacrylic aliphatic hydrocarbon ester or a methacrylic monocyclic aliphatic hydrocarbon ester is preferable, and methyl methacrylate, Ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, third butyl methacrylate, and cyclohexyl methacrylate, most preferably methyl methacrylate.

The structural unit (a3) is derived from an acrylate, and is preferably formed by an addition reaction of an acrylofluorenyl group in the acrylate.

Examples of the acrylate include acrylic acid chain aliphatic hydrocarbon esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; and acrylic acid aromatic hydrocarbon esters such as phenyl acrylate. ; Cyclohexyl acrylate, acrylic acid drop Acrylic alicyclic hydrocarbon esters and the like. Among these, methyl acrylate, ethyl acrylate, and butyl acrylate are preferable from the viewpoint that thermal decomposition can be suppressed and film formation is easy, and methyl acrylate is particularly preferred.

The methacrylic resin (A) used in the present invention may contain a structural unit (a4) in addition to the structural units (a1), (a2), and (a3). The structural unit (a4) is derived from monomers other than methacrylate and acrylate. Examples of the monomer include monomers having only one polymerizable carbon-carbon double bond in one molecule, such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and styrene.

The methacrylic resin (A) used in the present invention is obtained from From the viewpoint of high glass transition temperature and small shrinkage at high temperature and high humidity, it usually contains 10 to 50% by mass of structural unit (a1), 50 to 90% by mass of structural unit (a2), and 0 to 20% by mass of structure. The unit (a3) preferably contains 15 to 40% by mass of the structural unit (a1), 60 to 85% by mass of the structural unit (a2), and 0 to 10% by mass of the structural unit (a3), and more preferably contains 20 to 30 The mass unit (a1), the mass unit (a2) of 70 to 80 mass%, and the mass unit (a3) of 0 to 5 mass%. The content of the structural unit (a4) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 2% by mass.

The methacrylic resin (A) used in the present invention is a The weight average molecular weight (hereinafter also referred to as "Mw") is preferably 60,000 to 200,000, more preferably 80,000 to 160,000, particularly preferably 90,000 to 150,000, and particularly preferably 100,000 to 130,000. Since the Mw is 60,000 or more, the obtained film has high strength, is difficult to break, and is easy to extend. Therefore, the film can be further thinned. In addition, since Mw is 200,000 or less and the methacrylic resin (A) -based molding processability is high, the thickness of the obtained film tends to be uniform and the surface smoothness is excellent.

The methacrylic resin (A) used in the present invention is a The ratio of Mw to the number average molecular weight (hereinafter also referred to as "Mn") (Mw / Mn: this value is also referred to as "molecular weight distribution" hereinafter) is preferably 1.2 to 5.0, more preferably 1.5 to 3.5. Since the molecular weight distribution is 1.2 or more, the fluidity of the methacrylic resin (A) is increased, and the resulting film tends to have excellent surface smoothness. Since the molecular weight distribution is 5.0 or less, the obtained film tends to be excellent in impact resistance and toughness. In addition, Mw and Mn are values obtained by converting a chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene.

The methacrylic resin (A) used in the present invention is a According to JIS K7210, the melt flow rate measured under the conditions of 230 ° C and a load of 3.8 kg is preferably 0.1 to 15 g / 10 minutes, more preferably 0.5 to 5 g / 10 minutes, and even more preferably 0.8 to 3 g / 10 minutes.

Glass of methacrylic resin (A) used in the present invention The glass transition temperature is preferably 120 ° C or higher, more preferably 123 ° C or higher, particularly preferably 124 ° C or higher, and particularly preferably 125 ° C or higher. The upper limit of the glass transition temperature of the methacrylic resin (A) is usually 140 ° C. The glass transition temperature can be controlled by adjusting the proportion of the structural units derived from the polycyclic aliphatic hydrocarbon methacrylate. When the glass transition temperature is within this range, the heat resistance of the obtained film is increased, and deformation such as heat shrinkage is unlikely to occur. Here, the glass transition temperature is an intermediate point glass transition temperature measured in accordance with JIS K7121 (temperature rise rate: 20 ° C / minute).

Preparation of methacrylic resin (A) used in the present invention The manufacturing method is not particularly limited. For example, it can manufacture by well-known polymerization methods, such as a radical polymerization method and an anion polymerization method. The methacrylic resin (A) can be adjusted to the aforementioned characteristic value by adjusting the polymerization conditions, specifically, the polymerization temperature, the polymerization time, the type or amount of the chain transfer agent, and the type or amount of the polymerization initiator. And so on. Adjusting the resin characteristics by adjusting the polymerization conditions in this manner is a technique well known to those having ordinary knowledge in the technical field to which the present invention pertains.

Preparation of methacrylic resin (A) used in the present invention In the production, when a radical polymerization method is used, a suspension polymerization method, a block polymerization method, a solution polymerization method, and an emulsion polymerization method can be selected. In this polymerization method, suspension polymerization is preferred from the viewpoints of productivity and thermal decomposition resistance. Method or block polymerization method. The block polymerization method is preferably performed in a continuous flow method.

The polymerization reaction is performed using a polymerization initiator, the aforementioned monomers, and optionally a chain transfer agent.

For the methacrylic resin (A) used in the present invention The production and polymerization initiators used in the radical polymerization method are not particularly limited as long as they are capable of generating reactive radicals. The 1-hour half-life temperature of the polymerization initiator used in the present invention is preferably 60 to 140 ° C, and more preferably 80 to 120 ° C.

Examples of the polymerization initiator include a third hexylperoxyisopropyl monocarbonate, a third hexylperoxy 2-ethylhexanoate, and 1,1,3,3-tetramethylbutylperoxy. 2-ethylhexanoate, third butyl peroxytrimethyl acetate, third hexyl peroxy trimethyl acetate, third butyl peroxy neodecanoate, third hexyl peroxy new Decanoate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, 1,1-bis (third hexylperoxy) cyclohexane, benzamyl peroxide, 3, 5,5-trimethylhexylfluorenyl peroxide, laurylfluorenyl peroxide, 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methyl Butyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), and the like. Of these, preferred are third hexylperoxy 2-ethylhexanoate, 1,1-bis (third hexylperoxy) cyclohexane, and dimethyl 2,2'-azobis (2-methyl Propionate).

These polymerization initiators can be used alone or in combination. Used above. The amount and method of addition of the polymerization initiator are not particularly limited as long as they are appropriately set in accordance with the purpose. For example, the amount of the polymerization initiator used in the suspension polymerization method is preferably 0.0001 to 0.1 parts by mass relative to 100 parts by mass of the total monomers used for the polymerization reaction, and more preferably It is 0.001 to 0.07 parts by mass.

For the methacrylic resin (A) used in the present invention The chain transfer agent used for the production and the radical polymerization method is not particularly limited. Examples include n-octyl mercaptan, n-dodecyl mercaptan, tertiary dodecyl mercaptan, 1,4-butanediol, 1,6-hexanedithiol, ethylene glycol dithiopropionic acid Ester, butanediol dithioglycolate, butanediol dithiopropionate, hexanediol dithioglycolate, hexanediol dithiopropionate, trimethylolpropane tri (β -Thiopropionate), alkyl mercaptans such as pentaerythritol and thiopropionate; α-methylstyrene dimer; terpine diene and the like. Among these, alkyl mercaptans such as n-octyl mercaptan and pentaerythritol thiopropionate are preferred. These chain transfer agents can be used alone or in combination of two or more.

100 parts by mass based on the total monomers for the polymerization reaction The use amount of the chain transfer agent is preferably 0.1 to 1 part by mass, more preferably 0.15 to 0.8 part by mass, even more preferably 0.2 to 0.6 part by mass, and most preferably 0.2 to 0.5 part by mass. In addition, the use amount of the chain transfer agent is preferably 2500 to 10,000 parts by mass, more preferably 3,000 to 9,000 parts by mass, and even more preferably 3500 to 6,000 parts by mass with respect to 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 moldability and high mechanical strength.

Production of methacrylic resin (A) used in the present invention Each of the monomers, the polymerization initiator, and the chain transfer agent used at the time may be all mixed and the mixture may be supplied to the reaction tank, or they may be separately supplied to the reaction tank. In the present invention, the method of mixing the whole and supplying the mixture to the reaction tank is preferred.

For the methacrylic resin (A) used in the present invention In the production and use of a solvent in the radical polymerization method, the solvent is not limited as long as the solvent can dissolve the monomer and the methacrylic resin (A), but aromatic hydrocarbons such as benzene, toluene, and ethylbenzene are preferred. These solvents may be used alone or in combination of two or more. The amount of the solvent used can be appropriately set from the viewpoint of the viscosity and productivity of the reaction solution. The usage-amount of a solvent is 100 mass parts with respect to the total amount of a polymerization reaction raw material, for example, Preferably it is 100 mass parts or less, More preferably, it is 50 mass parts or less.

For the methacrylic resin (A) used in the present invention The temperature at the time of production and radical polymerization reaction is preferably 50 to 180 ° C, and more preferably 60 to 140 ° C when the suspension polymerization is performed.

In the case of bulk polymerization, the temperature is preferably 100 to 200 ° C, and more preferably 110 to 180 ° C. Since the temperature during the block polymerization reaction is 100 ° C. or higher, the productivity tends to be improved due to an increase in the polymerization rate and a decrease in the viscosity of the polymerization solution. In addition, since the temperature at the time of the bulk polymerization reaction is 200 ° C. or lower, the control of the polymerization rate becomes easy, and the generation of by-products is suppressed, and the coloring of the resin composition of the present invention can be suppressed.

When the production of the methacrylic resin (A) used in the present invention is carried out by suspension polymerization, after the completion of the polymerization, the polymer is washed, dehydrated, and dried by a known method to obtain a granular polymer.

The radical polymerization system can be performed using a batch-type reaction apparatus or a continuous flow-type reaction apparatus. In a continuous flow type reaction, for example, a polymerization reaction raw material (a mixed liquid containing monomers, a polymerization initiator, a chain transfer agent, etc.) is prepared under a nitrogen atmosphere, etc., and is supplied to the reactor at a certain flow rate, corresponding to the Supply flow rate, withdraw reaction In the device. As the reactor, a tubular reactor capable of approaching a plug flow state and / or a tank reactor capable of approaching a completely mixed state can be used. In addition, continuous flow polymerization can be performed in one reactor, or continuous flow polymerization can be performed by connecting two or more reactors. In the present invention, at least one tank-type reactor using a continuous flow type is preferred. The amount of liquid in the tank-type reactor during the polymerization is preferably 1/4 to 3/4, and more preferably 1/3 to 2/3 with respect to the volume of the tank-type reactor. A stirring device is usually installed in the reactor. Examples of the stirring device include a static stirring device and a dynamic stirring device. Examples of the dynamic stirring device include a high-efficiency (maxblend) type stirring device, a stirring device having a grid-shaped wing that rotates around the vertical rotation shaft disposed at the center, a paddle type stirring device, and a screw type stirring device . Among these, from the standpoint of uniform mixing, it is preferable to use a high-efficiency stirring device.

After polymerization, remove unreacted monomers, etc. as needed Volatiles. The removal method is not particularly limited, but heating devolatilization is preferred. Examples of the devolatilization method include an equilibrium flash method and an adiabatic flash method. The devolatilizing temperature of the adiabatic flash evaporation method is preferably 200 to 280 ° C, and more preferably 220 to 260 ° C. The time for heating the resin in the adiabatic flash method is preferably 0.3 to 5 minutes, more preferably 0.4 to 3 minutes, and even more preferably 0.5 to 2 minutes. When devolatilization is performed in such a temperature range and a heating time, a methacrylic resin (A) with little coloring is easily obtained. The removed unreacted single system can be recovered and reused for polymerization. The yellow index of the recovered monomer may become high due to the heat applied during the recovery operation and the like. The recovered monomer is preferably refined by an appropriate method to reduce the yellow index.

Used in the production of the present invention by anionic polymerization As a method of the methacrylic resin (A), for example, a method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of a mineral salt such as a salt of an alkali metal or an alkaline earth metal (refer to Japanese Patent Publication No. 7-25859), a method of performing anionic polymerization in the presence of an organoaluminum compound using an organic alkali metal compound as a polymerization initiator (see Japanese Patent Application Laid-Open No. 11-335432), and combining rare earth metals As a polymerization initiator, a method of anionic polymerization (see Japanese Patent Application Laid-Open No. 6-93060) and the like.

For the production of the methacrylic resin (A) used in the present invention, in the anionic polymerization method, as the polymerization initiator, n-butyllithium, second butyllithium, isobutyllithium, and third butyl lithium are preferably used. Lithium alkyl and the like. From the viewpoint of productivity, it is preferable to coexist an 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, and an arane which may have a substituent Group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, or an N, N-disubstituted amino group. In addition, R ² and R ³ may be substituted by their bonds. (Arylenedioxy).

Specific examples of the organoaluminum compound include isobutylbis (2,6-di-third-butyl-4-methylphenoxy) aluminum, and isobutylbis (2,6-di-third-butyl) Phenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, and the like.

Further, in the anionic polymerization method, in order to control the polymerization reaction, an ether, a nitrogen-containing compound, or the like may be coexisted.

The polycarbonate resin (B) used in the present invention is not Special limitation. Examples of the polycarbonate resin (B) include polymers obtained by a reaction between a polyfunctional hydroxy compound and a carbonate-forming compound. In the present invention, an aromatic polycarbonate resin is preferred in terms of compatibility with the methacrylic resin (A) and the transparency of the obtained film is good.

The polycarbonate resin (B) used in the present invention is compatible with methacrylic resin (A), and the transparency and surface smoothness of the obtained film. MVR value is preferably 1 ~ 250cm ^3/10 min more preferably ³ ~ 230cm 3/10 min.

The polycarbonate resin (B) used in the present invention is obtained from From the viewpoints of compatibility with the methacrylic resin (A), transparency of the obtained film, surface smoothness, etc., the chromatogram measured by gel permeation chromatography (GPC) is converted into standard polybenzene The weight average molecular weight calculated from the molecular weight of ethylene is preferably 18,000 to 75,000, and more preferably 20,000 to 60,000. The MVR value or the weight average molecular weight of the polycarbonate resin (B) can be adjusted by adjusting the amount of the terminal terminator or the branching agent.

Glass of polycarbonate resin (B) used in the present invention The transition temperature is preferably 130 ° C or higher, more preferably 135 ° C or higher, and even more preferably 140 ° C or higher. The upper limit of the glass transition temperature of this polycarbonate resin is usually 180 ° C. Here, the glass transition temperature is an intermediate point glass transition temperature measured in accordance with JIS K7121 (temperature rise rate: 20 ° C / minute).

There is no particular method for producing the polycarbonate resin (B) The limit. Examples include phosgene method (interfacial polymerization method) and melt polymerization. Method (ester exchange method), etc. The aromatic polycarbonate resin that is preferably used in the present invention is a polycarbonate resin produced by a melt polymerization method, which can be treated by adjusting the amount of terminal hydroxyl groups.

Examples of the polyfunctional hydroxy compound used as a raw material for producing the polycarbonate resin (B) include 4,4'-dihydroxybiphenyls which may have a substituent; and bis (hydroxyphenyl) alkanes which may have a substituent. ; Bis (4-hydroxyphenyl) ethers which may have a substituent; Bis (4-hydroxyphenyl) sulfides which may have a substituent; Bis (4-hydroxyphenyl) subfluorenes which may have a substituent ; Bis (4-hydroxyphenyl) fluorenes which may have a substituent; bis (4-hydroxyphenyl) ketones which may have a substituent; bis (hydroxyphenyl) fluorenes which may have a substituent; may have a substitution Dihydroxy-p-bitriphenyls based on a group; dihydroxy-p-biquaterphenyls which may have a substituent; bis (hydroxyphenyl) pyridines which may have a substituent Types; bis (hydroxyphenyl) capanes that may have a substituent; bis [2- (4-hydroxyphenyl) -2-propyl] benzenes that may have a substituent; dihydroxynaphthalenes that may have a substituent Types; dihydroxybenzenes which may have a substituent; polysiloxanes which may have a substituent; dihydroperfluoroalkanes which may have a substituent; and the like.

Among these polyfunctional hydroxy compounds, preferred is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4 -Hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane , 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) fluorene, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 3,3-bis (4- Hydroxyphenyl) pentane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) ether, 4,4'-dihydroxydiphenyl ketone, 2, 2-bis (4-hydroxy-3-methoxyphenyl) 1,1,1,3,3,3-hexafluoropropane, α, ω-bis [3- (2-hydroxyphenyl) propyl] Juji Methylsiloxane, resorcinol, 2,7-dihydroxynaphthalene, and more preferably 2,2-bis (4-hydroxyphenyl) propane.

Examples of the carbonate-forming compound include phosgene. Various dihalogenated carbonyl groups, halobates such as chloroformates, and carbonate compounds such as bisaryl carbonates. The amount of this carbonate-forming compound can be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.

The reaction for producing polycarbonate resin (B) is usually It is carried out in a solvent in the presence of an acid binder. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide; or alkali metal carbonates such as sodium carbonate and potassium carbonate; or trimethylamine and triethyl. Tertiary amines such as amines, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline, trimethylbenzyl ammonium chloride, triethylbenzyl ammonium chloride, trichloride Tertiary ammonium salts of butylbenzyl ammonium, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, etc., tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, etc. Fourth grade osmium salt and so on. Furthermore, 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-binding agent can be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. For example, for each mole of the hydroxyl group of the polyfunctional hydroxy compound of the raw material, one equivalent or an excess amount of the acid binding agent may be used, and preferably 1 to 5 equivalents of the acid binding agent are used.

In the reaction for producing polycarbonate resin (B) It is possible to use well-known end-terminators or divergent agents. Examples of the terminal terminator include p-third butylphenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, and p- (perfluorohexyl) Phenyl) phenol, p-tertiary perfluorobutylphenol, 1- (p-hydroxybenzyl) Group) perfluorodecane, p- [2- (1H, 1H-perfluoroshendodecyloxy) -1,1,1,3,3,3-hexafluoropropyl] phenol, 3,5-bis ( Perfluorohexyloxycarbonyl) phenol, perfluorododecyl parahydroxybenzoate, p (1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H-perfluorononanoic acid, 1,1,1,3 , 3,3-tetrafluoro-2-propanol and so on.

Examples of the branching agent include resorcinol, pyrogallol, 4,6-dimethyl-2,4,6-gins (4-hydroxyphenyl) -2-heptene, 2,6-dimethyl-2,4,6-gins (4-hydroxyphenyl) -3-heptene, 2,4-dimethyl-2,4,6-ginseng (4-hydroxyphenyl) heptane, 1,3,5-ginseng (2-hydroxyphenyl) benzene, 1,3 , 5-gins (4-hydroxyphenyl) benzene, 1,1,1-gins (4-hydroxyphenyl) ethane, gins (4-hydroxyphenyl) phenylmethane, 2,2-bis [4, 4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis [2-bis (4-hydroxyphenyl) -2-propyl] phenol, 2,6-bis (2-hydroxy-5 -Methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, (4-hydroxyphenyl) methane, [(4 -(4-hydroxyphenylisopropyl) phenoxy] methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis (3-methyl-4-hydroxy Phenyl) -2-oxo-2,3-dihydroindole, 3,3-bis (4-hydroxyaryl) oxyindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromo isatin and the like.

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

In the resin composition of the present invention, a methacrylic tree The mass ratio (A) / (B) of the fat (A) to the polycarbonate resin (B) is usually 95/5 to 99.9 / 0.1, preferably 96/4 to 99/1, and most preferably 97/3 ~ 98/2. In this range, since the methacrylic resin (A) and the polycarbonate resin (B) are completely compatible, it is easy to obtain a resin having high transparency and good surface smoothness. film. Moreover, since it is in this range, the absolute value of the phase difference of the obtained stretched film can be reduced.

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

The resin composition of the present invention does not damage the present invention. Within the range of the effect, a filler may be contained as needed. Examples of the filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate. The amount of the filler that can be contained in the resin composition of the present invention is preferably 3% by mass or less, and more preferably 1.5% by mass or less.

The resin composition of the present invention may contain other polymers, if necessary, within a range that does not impair the effects of the present invention. Examples of other polymers include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polymer Polyolefin resins such as olefins; ethylene-based ionic polymers; polystyrene, styrene-maleic anhydride copolymer, high-impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, etc. Styrene resin; methyl methacrylate polymers other than methacrylic resin (A), methyl methacrylate-styrene copolymer; polyethylene terephthalate, polybutylene terephthalate Polyester resins such as diesters; Polyamides such as nylon 6, nylon 66, and polyamide elastomers; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyacetals, Polyvinylidene fluoride, polyurethane, modified polyphenylene ether, polyphenylene sulfide, polysiloxane modified resin; acrylic rubber, polysiloxane rubber; SEPS, SEBS, SIS and other styrene thermoplastic elastomers Body; olefin rubbers such as IR, EPR, EPDM, etc. The amount of other polymers that can be contained in the resin composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 0% by mass or less.

In the resin composition used in the present invention, Within the scope of the effects of the invention, antioxidants, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, slip agents, release agents, polymer processing aids, antistatic agents, flame retardants, dyes, pigments, Additives such as light diffusing agents, organic pigments, matting agents, impact modifiers, and phosphors.

Antioxidants have their elemental properties in the presence of oxygen Stop the effect of oxidative degradation of resin. Examples include phosphorus-based antioxidants, hindered phenol-based antioxidants, and thioether-based antioxidants. Among these, from the viewpoint of preventing deterioration of optical characteristics due to coloration, a phosphorus-based antioxidant or a hindered phenol-based antioxidant is preferable, and a phosphorus-based antioxidant and a hindered phenol-based antioxidant are more preferable. And use.

When a phosphorus-based antioxidant and a hindered phenol-based antioxidant are used in combination, a phosphorus-based antioxidant / hindered phenol-based antioxidant with a mass ratio of 0.2 / 1 to 2/1 is preferably used, and more preferably 0.5 / 1 to 1/1.

As the phosphorus-based antioxidant, 2,2-methylenebis (4,6-Di-tert-butylphenyl) octyl phosphite (produced by ADEKA Corporation; trade name: Adkstab HP-10), ginseng (2,4-di-tert-butylphenyl) phosphite ( Manufactured by BASF; trade names: IRGAFOS 168), 3,9-bis (2,6-di-third-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3, 9-Diphosphobispiro [5.5] undecane (manufactured by ADEKA; trade name: Adkstab PEP-36) and the like.

As the hindered phenol-based antioxidant, 3,5-dithion Tributyl-4-hydroxytoluene, pentaerythritol-penta [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Corporation; trade name IRGANOX 1010), 18 Methyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF Corporation; trade name IRGANOX 1076) and the like.

Thermal degradation preventives It can trap polymer free radicals generated when exposed to high heat, and can prevent thermal degradation of the resin.

As the thermal degradation preventing agent, 2-third butyl-6- (3'-third butyl-5'-methyl-hydroxybenzyl) -4-methylphenylacrylate (Sumitomo Chemical Manufactured by the company; trade name Sumilizer GM), 2,4-di-tertiarypentyl-6- (3 ', 5'-di-tertiarypentyl-2'-hydroxy-α-methylbenzyl) phenyl acrylate (Manufactured by Sumitomo Chemical Co., Ltd .; trade name Sumilizer GS).

UV absorber has the ability to absorb ultraviolet rays compound of. The ultraviolet absorber is mainly considered to have a function of converting light energy into heat energy.

Examples of the ultraviolet absorber include diphenyl ketones, benzotriazoles, and Type, benzoate type, salicylate type, cyanoacrylate type, taniline oxalate type, malonate type, formamidine type and the like. Among these, benzotriazoles, Similar to or similar to the ultraviolet absorber whose maximum absorption coefficient ε _max at a wavelength of 380 ~ 450nm is 100dm ³ ‧mol ^-1 cm ^-1 or less.

Benzotriazoles are inhibited by UV radiation The effect of lowering the optical characteristics such as coloration is high, and it is more suitable as an ultraviolet absorber for optical applications using the film of the present invention. As benzene Benzotriazoles, preferably 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN 329 ), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN 234), 2,2 '-Methylenebis [6- (2H-benzotriazol-2-yl) -4-third octylphenol] (manufactured by ADEKA Corporation; LA-31), 2- (5-octylthio-2H -Benzotriazol-2-yl) -6-tert-butyl-4-methylphenol and the like.

In addition, the ultraviolet absorber having a maximum Moire absorption coefficient ε _max at a wavelength of 380 to 450 nm is 1200 dm ³ ‧mol ^-1 cm ^-1 or less, is capable of suppressing discoloration of the obtained film. Examples of such an ultraviolet absorber include 2-ethyl-2'-ethoxy-oxalopidine (manufactured by CLARIANT Japan; trade name: Sundupore VSU).

Among these ultraviolet absorbers, benzotriazoles are more preferably used from the viewpoint of suppressing deterioration of the resin due to ultraviolet irradiation.

In addition, when it is necessary to efficiently absorb short wavelengths below 380 nm, three Class of UV absorbers. Examples of such an ultraviolet absorber include 2,4,6-ginseng (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-tris (Manufactured by ADEKA; LA-F70), or hydroxyphenyltris UV absorber (manufactured by BASF; TINUVIN 477 or TINUVIN 460), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-tris Wait.

The maximum value ε _max of the molar absorption coefficient of the ultraviolet absorber is measured as follows. 10.00 mg of an ultraviolet absorbent was added to 1 L of cyclohexane, and dissolved until no undissolved matter was visually observed. This solution was poured into a quartz glass tank of 1 cm × 1 cm × 3 cm, and an absorbance at a wavelength of 380 to 450 nm and an optical path length of 1 cm was measured using a U-3410 spectrophotometer manufactured by Hitachi, Ltd. From the molecular weight (M _UV ) of the ultraviolet absorber and the maximum value (A _max ) of the measured absorbance, the maximum value ε _{max of the} Moire absorption coefficient was calculated by the following formula.

ε _max = [A _max / (10 × 10 ^-3 )] × M _UV

In addition, in order to particularly effectively absorb light having a wavelength of 380nm to 400nm, it is more suitable to use WO2011 / 089794A1, WO2012 / 124395A1, JP 2012-012476, JP 2013-023461, and JP 2013-112790 Metal complexes of ligands having a heterocyclic structure disclosed in JP-A-2013-194037, JP-A-2014-62228, JP-A-2014-88542, JP-A-2014-88543, etc. A substance (for example, a compound having a structure represented by the formula (A)) is used as an ultraviolet absorber.

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

Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a divalent group (an oxygen atom, a sulfur atom, NH, NR ⁵ or the like) other than a carbon atom. R ^{5 is} each independently a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroarylalkyl group, an aralkyl group, and the like. The substituent may further have a substituent on the substituent.

Z ¹ and Z ² are each independently a trivalent group (nitrogen atom, CH, CR ⁶ and the like). R ^{6 is} each independently a substituent such as an alkyl group, an aryl group, a heteroaryl group, a heteroarylalkyl group, an aralkyl group, and the like. The substituent may further have a substituent on the substituent.

R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, a halogen group, an alkylsulfonyl group, a morpholinosulfonyl group, a piperidinylsulfonyl group Base, thiomorpholinosulfonyl, piperidine Substituents for sulfosulfenyl and the like. The substituent may further have a substituent on the substituent. a, b, c, and d each represent the number of R ¹ , R ² , R ^3, and R ⁴ and are any integer from 1 to 4].

Examples of the ligand of the heterocyclic structure include 2,2'-iminobisbenzothiazole and 2- (2-benzothiazolylamino) benzo. Azole, 2- (2-benzothiazolylamino) benzimidazole, (2-benzothiazolyl) (2-benzimidazolyl) methane, bis (2-benzo (Oxazolyl) methane, bis (2-benzothiazolyl) methane, bis [2- (N-substituted) benzimidazolyl] methane, etc. and their derivatives. As the central metal of such a metal complex, copper, nickel, cobalt, and zinc are preferably used. In addition, in order to use these metal complexes as ultraviolet absorbers, it is preferable to disperse the metal complexes in a medium such as a low molecular compound or a polymer. With respect to 100 parts by mass of the film of the present invention, the addition amount of the metal complex is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass. Due to the large molar absorption coefficient of the aforementioned metal complex at a wavelength of 380 nm to 400 nm, it is sufficient to add a small amount to obtain a sufficient ultraviolet absorption effect. If the addition amount is small, deterioration of the appearance of the resin film due to bleeding or the like can be suppressed. In addition, the metal complex is high in heat resistance, so that there is little deterioration or decomposition during the forming process. In addition, since the metal complex is high in light resistance, it can maintain ultraviolet absorption performance for a long period of time.

Light stabilizers are mainly thought to have the ability to capture light The function of free radicals generated by oxidation. Examples of suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.

Examples of the lubricant include stearic acid and behenic acid , Stearic acid, methylene distearylamine, triglyceride of hydroxystearate, paraffin, ketone wax, octanol, hardened oil, etc.

The release agent is used to release the formed product from the mold. For easy functioning compounds. Examples of the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol, and higher glycerin fatty acid esters such as monoglyceryl stearate and diglyceryl stearate. In the present invention, it is preferable to use a higher alcohol and a glycerin fatty acid monoester in combination as a release agent. When using higher alcohols and glycerol fatty acid monoesters, the quality of higher alcohols / glycerol fatty acid monoesters is better to use in the range of 2.5 / 1 ~ 3.5 / 1, more preferably to use in the range of 2.8 / 1 to 3.2 / 1 .

As a polymer processing aid, it is usually used by emulsification Polymerization method can produce polymer particles with a particle diameter of 0.05 to 0.5 μm. The polymer particles may be single-layer particles composed of polymers having a single composition ratio and a single limiting viscosity, and may also be multilayer particles composed of two or more polymers having different composition ratios or limiting viscosities. Among them, a polymer layer having a low limiting viscosity in the inner layer and the outer layer Particles having a two-layer structure in which a polymer layer having a high limiting viscosity of 5 dl / g or more is preferred. The limiting viscosity of the polymer processing aid system is preferably 3 to 6 dl / g.

Examples of the impact resistance modifier include acrylic acid. Core-shell type modifiers based on a core layer component of a rubber or diene rubber, modifiers including a plurality of rubber particles, and the like.

As the organic pigment, 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 or matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.

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

These additives can be used alone or in combination. Use. 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. The ester resin (B) 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, relative to the methacrylic resin (A), from the viewpoint of suppressing the appearance defect of the molded body. % Or less, particularly preferably 4 mass% or less.

There is no particular method for preparing the resin composition. The limit. For example, in the presence of a polycarbonate resin (B), a monomer mixture containing methyl methacrylate is polymerized to form a methyl group. A method of an acrylic resin (A), or a method of melt-kneading a methacrylic resin (A) and a polycarbonate resin (B). Among these, the melt-kneading method is preferable because the process is simple. When melt-kneading, other polymers or additives may be mixed as required, or after mixing methacrylic resin (A) with other polymers and additives, it may be mixed with polycarbonate resin (B). Mixing the polycarbonate resin (B) with other polymers and additives, and then mixing with the methacrylic resin (A) may be another method. Kneading can be performed using a known mixing device or kneading device such as a kneader, an extruder, a mixing roll, a Banbury mixer, and the like. Among these, a biaxial extruder is preferred. The temperature during mixing and kneading can be appropriately adjusted according to the melting temperature of the methacrylic resin (A) and the polycarbonate resin (B) used, but it is preferably 110 ° C to 300 ° C.

The resin composition of the present invention has a glass transition temperature The temperature is preferably 120 ° C or higher, more preferably 123 ° C or higher, particularly preferably 124 ° C or higher, and particularly preferably 125 ° C or higher. The upper limit of the glass transition temperature of the resin composition of the present invention is not particularly limited, but is preferably 135 ° C. Here, the glass transition temperature is an intermediate point glass transition temperature measured in accordance with JIS K7121 (temperature rise rate: 20 ° C / minute).

The resin composition of the present invention is determined by GPC measurement The Mw is preferably 70,000 to 200,000, more preferably 72,000 to 180,000, and even more preferably 75,000 to 150,000. The Mw / Mn determined by GPC measurement of the resin composition of the present invention is preferably 1.2 to 5.0, and more preferably 1.5 to 3.5. When Mw or Mw / Mn is within this range, the moldability of the methacrylic resin composition becomes good, and a molded body excellent in impact resistance or toughness is easily obtained.

The resin composition of the present invention is at 230 ° C and 3.8 kg load. The melt flow rate determined under heavy conditions is preferably 0.1 to 15 g / 10 minutes, more preferably 0.5 to 5 g / 10 minutes, and most preferably 1.0 to 3 g / 10 minutes.

The haze of the resin composition of the present invention having a thickness of 1.0 mm is preferably 1.0% or less, more preferably 0.7% or less, and even more preferably 0.5% or less.

The resin composition of the present invention can be formed into any shape such as pellets, granules, powder, etc., and is formed into a molded body such as a film.

The resin composition of the present invention can be molded into various molded bodies by a known method. Examples of the molding method include an extrusion molding method, an injection molding method, a calender molding method, a blow molding method, a compression molding method, and a solution casting method. Further, in order to obtain a composite molded body with other materials, a well-known method for manufacturing a composite molded body such as an insert molding method or a coating molding method can be used.

The preferable formed body in the resin composition of the present invention is a film.

The film of one embodiment of the present invention is not particularly limited by the method for producing the film. Examples of the film forming method include a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, and a blow molding method. Among these, an extrusion molding method is preferable. By the extrusion molding method, a film having excellent transparency, improved toughness, excellent handleability, and excellent balance between toughness and surface hardness and rigidity can be obtained. The temperature of the resin composition of the present invention discharged from the extruder is preferably set to 160 to 270 ° C, and more preferably 220 to 260 ° C.

In the extrusion molding method, from the viewpoint of obtaining a film with good surface smoothness, good specular gloss, and low haze, Preferably, the method includes a method of extruding the aforementioned resin composition from a T die in a molten state, and then holding it by two or more mirror rollers or mirror belts to perform molding. The mirror roll or mirror tape is preferably made of metal. The linear pressure between a pair of mirror rollers or mirror belts is preferably 10 N / mm or more, and more preferably 30 N / mm or more.

Further, the surface temperature of the mirror roll or the mirror belt is preferably both Below 130 ° C. Moreover, it is preferable that the surface temperature of at least one of a pair of mirror rolls or a mirror tape is 60 degreeC or more. If the surface temperature is set as described above, the resin composition discharged from the extruder can be cooled at a faster rate than natural cooling, and the film of the present invention having excellent surface smoothness and low haze can be easily produced.

The film of the present invention is preferably applied in at least one direction. There are extension handlers. By the stretching treatment, the mechanical strength is increased, and a film that is difficult to crack can be obtained. The method of the stretching treatment is not particularly limited, and examples thereof include a uniaxial stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method. From the viewpoint of uniformly stretching and obtaining a high-strength film, the temperature during stretching is preferably 100 to 200 ° C, and more preferably 120 to 160 ° C. Stretching is usually performed on a length basis at 100 to 5000% / minute. The area extension ratio is preferably 1.5 to 8 times. After stretching, a film with less thermal shrinkage can be obtained by applying a heat-set or relaxed film.

Absolute value of phase difference from transparency or thickness direction From a small viewpoint, 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 97% by mass, and even more preferably 85 to 95% by mass. . In addition, from the viewpoint that the absolute value of the retardation in the thickness direction is small, the amount of the polycarbonate resin (B) contained in the film system of the present invention is preferably 1 to 5 mass%, more preferably 1.5 to 4 Mass%, particularly preferably 2 to 3 mass%.

The thickness of the film of the present invention is preferably 1 to 200 μm, It is more preferably 10 to 50 μm, and particularly preferably 15 to 40 μm.

The haze of the film of the present invention having a thickness of 40 μm is preferably 0.3% or less, more preferably 0.2% or less. Thereby, surface gloss or transparency is excellent. Moreover, in optical applications such as a liquid crystal protective film and a light guide film, the use efficiency of a light source is high and it is preferable. Furthermore, it is preferable because the forming accuracy is excellent when surface forming is performed.

The film of the present invention is thick for light having a wavelength of 590 nm. The in-plane direction retardation Re of a degree of 40 μm is preferably 19 nm or less, more preferably 15 nm or less, particularly preferably 10 nm or less, particularly preferably 5 nm or less, and most preferably 1 nm or less.

The thickness direction retardation Rth of the film of the present invention with respect to light having a wavelength of 590 nm and a thickness of 40 μm is preferably -12 nm or more and 12 nm or less, more preferably -5 nm or more and 5 nm or less, particularly preferably -3 nm or more and 3 nm or less, and particularly preferably- 2 nm to 2 nm, preferably -1 nm to 1 nm.

The in-plane phase difference Re and the thickness direction phase difference Rth are each a value defined by the following formula.

Re = (n _x -n _y ) × d

Rth = ((n _x + n _y ) / 2-n _z ) × d

Here, n _x is the refractive index in the retardation axis direction of the film, n _y is the refractive index in the advance axis direction of the film, n _z is the refractive index in the thickness direction of the film, and d [nm] is the thickness of the film. The late-phase axis is the axis in the direction where the refractive index in the plane of the film becomes the largest, and the phase-advance axis is the axis in the plane that is perpendicular to the late-phase axis.

The thin film of the present invention has a photoelastic coefficient β of light with a wavelength of 590 nm, preferably -3.0 × 10 ^-12 Pa ^-1 or more and 3.0 × 10 ^-12 Pa ^-1 or less, more preferably -2.0 × 10 ^-12 Pa ^-1 The above is 2.0 × 10 ^-12 Pa ^-1 or less, particularly preferably -1.0 × 10 ^-12 Pa ^-1 or more and 1.0 × 10 ^-12 Pa ^-1 or less. The photoelastic coefficient β [10 ^-12 Pa ^-1 ] is as follows, and can be calculated from the relationship between the in-plane direction phase difference Rin [nm] and the film thickness d [nm] when the stress σ [Pa] is applied.

Rin = β × σ × d

If the in-plane direction retardation Re, the thickness direction retardation Rth, and the photoelastic coefficient β are in such ranges, the influence of the phase difference on the display characteristics of the image display device can be significantly suppressed. More specifically, it is possible to significantly suppress interference unevenness or distortion of a 3D image when used in a liquid crystal display device for a 3D display.

Function can also be set on the surface of the film of the present invention

Floor. Examples of the functional layer include slip resistance of a hard coating layer, an antiglare layer, an antireflection layer, an antisticking layer, a diffusion layer, an antiglare layer, an antistatic layer, an antifouling layer, and fine particles. Layers etc.

The film of the present invention has high transparency, small thermal shrinkage, small dimensional change due to water absorption, uniform thickness, and excellent surface smoothness. In addition, since the absolute value of the retardation in the thickness direction can be small and thinned, it is suitable for retardation film, polarizer protective film, liquid crystal protection plate, surface material of portable information terminal, and display window protection of portable information terminal. Film, light guide film, transparent coated with silver nanowires or nanotubes on the surface The use of conductive film and front panel of various displays. In particular, the film of the present invention is suitable for a polarizer protective film because the absolute value of the retardation in the thickness direction can be small.

The film of the present invention has high transparency and heat resistance. For applications other than optical applications, it can be used in IR cut films, crime prevention films, anti-scatter films, decorative films, metal decorative films, solar cell back plates, flexible solar cell front plates, shrink films, and in-mold labels With film.

The polarizing plate of the present invention has a polarizer and a laminate. The film of the present invention on a polarizer. The thin film of the present invention can be laminated on both sides of a polarizer, or can be laminated on one side. When a film of the present invention is laminated on one side of a polarizer as a protective film for a polarizer, an optical film other than the film of the present invention can be laminated on the other side. Examples of the optical film include a polarizer protective film, a viewing angle adjustment film, a retardation film, and a brightness enhancement film. Lamination can also be performed via an adhesive layer.

For example, a polarizing plate according to a preferred embodiment of the present invention It can be a laminate of the film, the easy-adhesion layer, the adhesive layer, the polarizer, the adhesive layer, and the film according to the present invention, or the film, the easy-adhesion layer, and the adhesive according to the present invention A layer, a polarizer, an adhesive layer, and an optical film other than the film of the present invention are laminated in this order (see Fig. 1).

Polarizers are well-known optical elements. As polarized light Examples of the mirror include a polyvinyl alcohol resin. The degree of polymerization of the polyvinyl alcohol resin used for the polarizer is preferably 100 to 5000, and more preferably 1400 to 4000. The polyvinyl alcohol resin film can be cast, cast, etc. Casting, extrusion, etc. The thickness of the polyvinyl alcohol-based resin film used for the polarizer can be appropriately set according to the purpose or application of the LCD using the polarizing plate, but it is typically 5 to 80 μm.

The adhesive layer that can be provided in the polarizing plate of the present invention is only If it is optically transparent, there is no particular limitation. Examples of the adhesive constituting the adhesive layer include water-based adhesives, solvent-based adhesives, hot-melt adhesives, and active energy ray-curable adhesives. Among these, an aqueous adhesive and an active energy ray-curable adhesive are preferable.

The water-based adhesive system is not particularly limited. Water system The form of the agent can be an aqueous solution or a latex. Examples of the water-based adhesive include vinyl polymer-based adhesives, gelatin-based adhesives, polyurethane-based adhesives, isocyanate-based adhesives, polyester-based adhesives, and epoxy-based adhesives. Among these, an adhesive containing a vinyl polymer is preferred. The vinyl polymer is preferably a polyvinyl alcohol-based resin. The adhesive containing a polyvinyl alcohol resin is a water-soluble crosslinking agent which may contain boric acid or borax, glutaraldehyde or melamine, oxalic acid, and the like. The adhesive containing a polyvinyl alcohol-based resin is preferable because it has excellent adhesion to a polarizer made of a polyvinyl alcohol-based resin film. An adhesive containing a polyvinyl alcohol-based resin having an ethyl acetofluorene group is more suitable for improving the durability of a polarizing plate. The solid content contained in the water-based adhesive is usually 0.5 to 60% by mass. In the water-based adhesive, additives such as a cross-linking agent, a catalyst such as an acid, and a metal compound filler may be blended as necessary. With the metal compound filler, the fluidity of the adhesive layer can be controlled, and the film thickness can be stabilized to obtain a polarizing plate having a good appearance, uniform in-plane, and no deviation in adhesion.

As active energy ray hardening adhesive, except for use A compound having a monofunctional or difunctional (meth) acrylfluorene group or a compound having a vinyl group as a hardening component, and an epoxy compound or an oxetane compound and a photoacid generator may be used as a main component. Photocationic hardening composition.

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

The method for forming the adhesive layer is not particularly limited. . For example, it can be formed by applying the above-mentioned adhesive to an object, followed by heating or drying. The adhesive may be applied to the polarizer protective film or to the polarizer. After the adhesive layer is formed, both of the polarizer protective film and the polarizer can be laminated by laminating. In the lamination, a roll press or a plate press can be used. The heating and drying temperature and drying time are appropriately determined according to the type of the adhesive. The thickness of the adhesive layer in the dry state is preferably 0.01 to 10 μm, and more preferably 0.03 to 5 μm.

The easy-adhesion layer that can be provided in the polarizing plate of the present invention is Improve the adhesion between the polarizer protective film and the contact surface of the polarizer. The easy-adhesion layer can be provided by an easy-adhesion process or the like. Examples of the easy-adhesion treatment include surface treatments such as corona treatment, plasma treatment, and low-pressure UV treatment. The easy-adhesion layer can be provided by a method of forming an anchor layer, or a combination of the aforementioned surface treatment and the method of forming an anchor layer. Among these, a method of corona treatment, formation of an anchor layer, and a method using these in combination are preferable.

Examples of the anchor layer include reactivity. Polysiloxane layer with functional groups. The material of the polysiloxane layer having a reactive functional group is not particularly limited, but examples thereof include alkoxysilanols containing an isocyanate group, alkoxysilanols containing an amine group, and Mercapto alkoxysilanols, carboxyl-containing alkoxysilanols, epoxy-containing alkoxysilanols, vinyl-type unsaturated alkoxysilanols, and halogen-containing Alkoxysilanols, alkoxysilanols containing isocyanate groups. Among these, an amino-based silanol is preferable. By adding a titanium-based catalyst or a tin-based catalyst for efficiently reacting silanol to the silanol, the adhesion force can be made strong. Moreover, you may add another additive to the said polysiloxane which has a reactive functional group. Examples of other additives include tackifiers such as terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins, and stabilizers such as ultraviolet absorbers, antioxidants, and heat-resistant stabilizers. Moreover, as an anchor layer, the layer which consists of a saponified cellulose acetate butyrate resin is also mentioned.

The anchoring layer is applied by well-known techniques , Formed by drying. The thickness of the anchor layer is preferably 1 to 100 nm, and more preferably 10 to 50 nm in a dry state. At the time of application, the chemical solution for anchor layer formation may be diluted with a solvent. The dilution solvent is not particularly limited, and examples thereof include alcohols. The dilution concentration is not particularly limited, but is preferably 1 to 5 mass%, and more preferably 1 to 3 mass%.

Optical films other than the film of the present invention are not structured The materials made of it are particularly limited. Examples of the material of the optical film include cellulose resin, polycarbonate resin, cyclic polyolefin resin, and methacrylic resin.

Cellulose resin is an ester of cellulose and fatty acids. As Specific examples of such a cellulose ester-based resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionic acid. Esters, etc. Among these, cellulose triacetate is particularly preferred. Many products of cellulose triacetate are commercially available, which is also advantageous in terms of availability or cost. Examples of commercially available products of cellulose triacetate include the brand names "UV-50", "UV-80", "SH-80", "TD-80U", and "TD" manufactured by Fujifilm Corporation. -TAC "," UZ-TAC ", or" KC Series "made by Konica-Minolta.

The cyclic polyolefin resin is a general term for a resin polymerized by using a cyclic olefin as a polymerization unit, and examples thereof include those disclosed in Japanese Patent Application Laid-Open No. 1-240517, Japanese Patent Application Laid-Open No. 3-14882, and Japanese Patent Application Laid-Open No. 3-122137. Of resin. Specific examples include ring-opened (co) polymers of cyclic olefins, addition polymers of cyclic olefins, and copolymers of cyclic olefins with α-olefins such as ethylene and propylene (typically random copolymerization) ), And these graft polymers modified with unsaturated carboxylic acids or their derivatives, and their hydrides and the like. Specific examples of cyclic olefins include Ethylene monomer.

As cyclic polyolefin resins, various products are marketed For sale. Specific examples include the trade names "Zeonex", "Zeonor", manufactured by Japan Zeon Corporation, "Arton", manufactured by JSR Corporation, "Topas" manufactured by Polyplastics Co., Ltd., and Mitsui Chemical Co., Ltd. Trade name "APEL".

Used as an optical film other than the film of the present invention As the methacrylic resin, any appropriate methacrylic resin can be used as long as the effects of the present invention are not impaired. Examples include methacrylate polymers such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic copolymer, and methyl methacrylate- (meth) acrylic acid. Ester copolymer, methyl methacrylate-acrylate- (meth) acrylic copolymer, methyl (meth) acrylate-styrene copolymer (MS resin, etc.), polymers having alicyclic hydrocarbon groups (for example, Methyl methacrylate-cyclohexyl methacrylate copolymer, etc.). Further, as the methacrylic resin, for example, Acrypet VH or Acrypet VRL20A manufactured by Mitsubishi Rayon Co., Ltd., as disclosed in JP 2013-033237 or WO2013 / 005634A, are copolymerized with methyl methacrylate and malein. An imine-based monomer acrylic resin, an acrylic resin having a ring structure in the molecule described in WO2005 / 108438A, a methacrylic resin having a ring structure in the molecule described in JP 2009-197151, and an intramolecular High glass transition temperature (Tg) methacrylic resin obtained by cross-linking or intramolecular cyclization.

Used as an optical film other than the film of the present invention As the methacrylic resin, a methacrylic resin having a lactone ring structure can also be used. This is because of its high heat resistance, high transparency, and high mechanical strength due to biaxial stretching. Examples of the methacrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, and JP 2005 A methacrylic resin having a lactone ring structure described in JP-146084 and the like.

The polarizing plate of the present invention can be used in an image display device. Home. Specific examples of the image display device include a self-luminous display device such as an electroluminescence (EL) display, a plasma display (PD), and a field emission display (FED: Field Emission Display), or a liquid crystal display device ( LCD) and so on. A liquid crystal display device includes a liquid crystal cell and the above-mentioned polarizing plate arranged on at least one side of the liquid crystal cell.

Hereinafter, the present invention will be specifically described with examples and comparative examples. Invention, but the present invention is not limited to the following examples. The measurement of physical properties and the like was performed by the following method.

(Polymerization conversion rate)

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

<Resin monomer composition>

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 with respect to 10 mg of resin, room temperature, and 64 times of accumulation, and the resin was calculated from the spectrum. The composition of monomer units in.

(Photoelasticity coefficient)

Cut out a size of 20mm × 40mm from the unstretched film, clamp the film sheet at both ends in the long axis direction, and fix it to an ellipsometry device. While applying a stress of 10 ⁶ to 10 ⁷ Pa to the long axis direction, the temperature is 23 ° C. Under the conditions of ± 2 ° C and 50 ± 5% humidity, the in-plane direction retardation Rin at the center of the thin film sheet of light having a wavelength of 590 nm was measured. Correlation between self-stress and phase difference (Rin = β × σ × d, Rin: in-plane phase difference [nm], β: photoelastic coefficient [10 ^-12 Pa ^-1 ] when stress σ [Pa] is applied, σ: stress [Pa], d: film thickness [nm]) The photoelastic coefficient β is calculated.

(Strength of unstretched film)

A size of 100 mm × 50 mm was cut out from the unstretched film, and the film piece was fixed to a cylindrical mandrel bending tester having a cylindrical mandrel having a diameter of 6 mm, and the state of the film piece at 180 ° bending was evaluated.

A: There is no change in the film, and the obtained state can be maintained.

B: The film is fragile and breaks.

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

Mw and Mw / Mn are measured by gel permeation chromatography (GPC) under the following conditions, and calculated from the value converted to the molecular weight of standard polystyrene.

GPC device: HLC-8320 manufactured by Tosoh Corporation

Detector: Differential refractive index detector

Column: Two TSKgel SuperMultipore HZM-M2 made by Tosoh Corporation and SuperHZ4000 are connected in series.

Eluent: Tetrahydrofuran

Eluent flow: 0.35ml / min

Column temperature: 40 ℃

Calibration curve: 10 points of standard polystyrene

(Glass transition temperature Tg)

According to JIS K7121, using a differential scanning calorimeter (DSC-50 (model) manufactured by Shimadzu Corporation), the temperature was raised to 250 ° C once, then cooled to room temperature, and then 20 ° C from room temperature to 230 ° C. The DSC curve was measured with the temperature being raised for 1 minute. The intermediate-point glass transition temperature obtained from the DSC curve was taken as the glass transition temperature in the present invention.

(Saturated water absorption)

Using an injection molding machine (SE-180DU-HP manufactured by Sumitomo Heavy Industries, Ltd.), the methacrylic resin obtained in the manufacturing example was injection-molded at a cylinder temperature of 280 ° C, a mold temperature of 75 ° C, and a molding cycle of 1 minute to obtain A test piece with a length of 290mm, a width of 100mm, and a thickness of 2mm. The test piece was vacuum-dried for 3 days under the conditions of a temperature of 50 ° C and 5 mmHg, and the mass W ₀ of the test piece at the time of absolute drying was measured. Then, the absolute dry test piece was left under conditions of a temperature of 60 ° C. and a humidity of 90% for 300 hours. Then, the mass W _{1 of the} test piece was measured. The saturated water absorption (%) was calculated by the following formula.

Saturated water absorption (%) = (W ₁ -W ₀ ) / W ₀ × 100

(Mel Volume Flow Rate (MVR))

MVR is measured under conditions of 300 ° C, 1.2 kg load, and 10 minutes in accordance with JIS K7210.

(Total light transmittance (T _t ))

The total light transmittance was measured in accordance with JIS K7361-1 using a haze meter (HM-150 manufactured by Murakami Color Research Institute).

(Haze (H))

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

(Phase difference in the plane direction (Re))

A 40 mm × 40 mm test piece was fixed to an automatic birefringence meter (KOBRA-WR, manufactured by Oji Measurement Co., Ltd.), and the phase at a wavelength of 590 nm and an incident angle of 0 ° was measured at a temperature of 23 ± 2 ° C and a humidity of 50 ± 5%. difference.

(Rh in the thickness direction)

A 40 mm × 40 mm test piece was fixed to an automatic birefringence meter (KOBRA-WR, manufactured by Oji Measurement Co., Ltd.), and the phase at a wavelength of 590 nm and a tilt angle of 40 ° was measured at a temperature of 23 ± 2 ° C and a humidity of 50 ± 5% Difference, calculate the emissivity n _x , n _y and n _z from its value and average refractive index n, and calculate the thickness direction phase difference Rth (= ((n _x + n _y ) / 2-n _z ) × d) . n _x is the refractive index in the plane of the retardation axis in the plane, n _y is the refractive index in the plane with respect to the retardation axis, and n _z is the refractive index in the thickness direction.

The thickness d [nm] of the test piece was measured using a Digimatic Indicator (manufactured by MITUTOYO Co., Ltd.). The average refractive index n required to calculate the refractive indices n _x , n _y and n _z was measured using a digital precision refractometer (KALNEW Optical Industry Co., Ltd. KPR-20).

(Damp heat test)

In the case of a uniaxially stretched film, the extension direction is taken as the long side, and in the case of the biaxially stretched film, the MD (Machine Direction) direction of the film is used as the long side, and a test piece of 150 mm × 1 mm is prepared to be cut out. . The test piece was vacuum-dried at 40 ° C. and 5 Torr for 12 hours, and then left to stand at 80 ° C. and 90% RH for 12 hours. Calculate the contracted length from 150mm.

Damp heat shrinkage rate = (150mm-length after test) / 150mm × 100 (%)

(Yellow Index (YI))

The resin compositions produced in the examples and comparative examples were hot-pressed to obtain a plate-shaped formed body having a thickness of 50 mm × 50 mm × 1.0 mm. Based on the value obtained by measuring the 1.0 mm thick yellow index of these plate-shaped formed bodies using an ultraviolet-visible near-infrared spectrophotometer (UV-3600, manufactured by Shimadzu Corporation) in accordance with JIS Z-8722, and calculated based on JIS K7373 The yellow index (YI) is shown.

In the description of this example, methyl methacrylate is briefly described as MMA, and tricyclo [5.2.1.0 ^2,6 ] decane-8-ester of methacrylate (X in formula (1) is tricyclic [5.2.1.0 ^2,6 ] decane-8-yl compound) is briefly described as TCDMA, Ester (X in formula (1) is iso An alkyl-2-yl compound) is abbreviated as IBMA, cyclohexyl methacrylate is abbreviated as CHMA, and methyl acrylate is abbreviated as MA.

Manufacturing Example 1 <PMMA1>

In an autoclave with a stirrer and a collection tube, put 84 parts by mass of purified methyl methacrylate (MMA) and 15 parts by mass of tricyclomethacrylic acid [5.2.1.0 ^2,6 ] decane-8 -Ester (TCDMA) and 1 part by mass of methyl acrylate (MA) to prepare a monomer mixture. To the monomer mixture, 0.006 parts by mass of a polymerization initiator (AIBN, hydrogen abstraction capacity: 1%, 1-hour half-life temperature: 83 ° C) and 0.38 parts by mass of a chain transfer agent (n-octyl mercaptan) were added to dissolve them. Thus, a raw material liquid is obtained. The oxygen in the manufacturing apparatus was driven out by nitrogen.

The raw material liquid was fed to the continuous flow-type tank reactor controlled at a temperature of 140 ° C. at a constant flow rate so that the average residence time became 120 minutes, and was made into a block with a polymerization conversion rate of 57% by mass. polymerization.

The liquid discharged from the tank-type reactor was heated to 250 ° C, and was supplied to a biaxial extruder controlled at 260 ° C at a certain flow rate, and the adiabatic flash was performed at the inlet of the extruder. The volatiles (monomer, dimer, trimer, etc.) removed by adiabatic flash evaporation are discharged from the opened exhaust port. The volatile components containing unreacted monomer as the main component are located further downstream than the inlet of the biaxial extruder. The exhaust port provided was decompressed to 6 Torr and discharged, and the remaining resin component was extruded into a strand shape by a screw. This strand was cut with a granulator to obtain pelletized methacrylic resin <PMMA1>.

The obtained methacrylic resin-based structural unit derived from MMA was 85% by mass, the structural unit derived from TCDMA was 14% by mass, and the structural unit derived from MA was 1% by mass. The weight average molecular weight (Mw) was 67,000, the molecular weight distribution (Mw / Mn) was 1.81, and the glass transition temperature (Tg) was 125 ° C. Table 1 shows the analysis results of the methacrylic resin.

Manufacturing Example 2 <PMMA2>

In an autoclave, put 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 (third butylperoxy) cyclohexanone, and 0.22 parts by mass of N-octyl mercaptan, 0 parts by mass of pentaerythritol thiopropionate, 200 parts by mass of water, 2.64 parts by mass of a dispersant, and 33 parts by mass of a pH adjuster. While stirring the inside of the autoclave, the liquid temperature was raised from room temperature to 70 ° C, and the temperature was maintained at 70 ° C for 180 minutes. Then, it was kept at 120 ° C. for 60 minutes to perform a polymerization reaction. The liquid temperature was lowered to room temperature, and the polymerization reaction liquid was drawn out from the autoclave. The solid component was filtered out from the polymerization reaction solution, washed with water, and dried in hot air at 80 ° C. for 24 hours to obtain a beaded methacrylic resin [PMMA2]. Table 1 shows the analysis results of the methacrylic resin.

Manufacturing Examples 3 to 11 <PMMA3 to 11>

In addition to methyl methacrylate (MMA), tricyclo [5.2.1.0 ^2,6 ] decane-8-ester (TCDMA), methyl acrylate (MA), Ester (IBMA), cyclohexyl methacrylate (CHMA), n-octyl mercaptan (n-OM), pentaerythritol and thiopropionate (PETP) were changed to something other than those shown in Table 1 or Table 2 In the same manner as in Production Example 2, methacrylic resins <PMMA3 to 11> were obtained. Tables 1 and 2 show the analysis results of the methacrylic resin.

Manufacturing Example 12 <PMMA12>

In a 30-liter reaction vessel equipped with a stirring device, a temperature sensor, a cooling tube, and a nitrogen introduction tube, 40 parts by mass of methyl methacrylate (MMA) and 10 parts by mass of 2- (hydroxymethyl) were added. Methyl acrylate (MHMA), 50 parts by mass of toluene, and 0.025 parts by mass of an antioxidant (Adkstab 2112 manufactured by Asahi Denka Kogyo Co., Ltd.) were heated to 105 ° C. while passing nitrogen gas thereto. At the beginning of the reflux with increasing temperature, 0.05 parts by mass of third pentyl peroxyisononanoate (manufactured by Arkema Kyoto, trade name: Luperox 570) was added, and 0.10 parts by mass of third pentyl group was added for 3 hours. The oxononanoate was subjected to solution polymerization under reflux at about 105 to 110 ° C, and was further aged for 4 hours.

Next, to the obtained polymerization solution, 0.05 parts by mass of 2-ethylhexyl phosphate (Phoslex A-8 manufactured by Sakai Chemical Industry) was added as a catalyst (cyclization catalyst) for the cyclization condensation reaction. After performing the cyclization condensation reaction under reflux at 110 ° C for 2 hours, the polymerization solution was heated in an autoclave at 240 ° C for 30 minutes, and then the cyclization condensation reaction was performed again.

Subsequently, the obtained polymerization solution was converted into a resin amount at a processing speed of 2.0 kg / hour, and introduced into a rear row having a cylinder temperature of 240 ° C, a rotation speed of 100 rpm, and a pressure reduction of 13.3 to 400 hPa (10 to 300 mmHg). The devolatilization was carried out in a screw twin-shaft extruder with an air vent and 4 front exhaust vents with a vent (Φ = 29.75mm, L / D = 30). A methacrylic resin <PMMA12> having a lactone ring in the main chain was obtained. Shown in Table 2 Analysis results of acrylic resin <PMMA12>.

Prepare polycarbonate resins <PC1 ~ 3>.

PC1: polycarbonate Sumika STYRON Corporation, SD POLYCA TR-2001 (model) [Mw = 22000, MVR ( 300 ℃, 1.2Kg) = 200cm 3/10 min.]

PC2: polycarbonate manufactured by Sumika STYRON, CALIBRE 301-40 (model), [Mw = 35000, MVR (300 ℃, 1.2Kg) = 40cm 3/10 min.]

PC3: polycarbonate manufactured by Sumika STYRON, CALIBRE 301-4 (model), [Mw = 58000, MVR (300 ℃, 1.2Kg) = 4cm 3/10 min.]

As a processing aid, Paraloid K125-P (manufactured by Dow Chemical Co., Ltd.) was prepared.

Prepare 2,4,6-ginseng (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-tris (Manufactured by ADEKA Corporation; LA-F70) as an ultraviolet absorbent.

<Example 1> Uniaxially stretched film

Mix 96 parts by mass of a methacrylic resin <PMMA1> and 4 parts by mass of a polycarbonate resin <PC1>, and use a biaxial extruder (manufactured by TECHNOVEL, trade name: KZW20TW-45MG-NH-600) at 250 ° C. Kneaded and extruded to produce a resin composition [1].

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

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

The resin composition [1] was dried at 80 ° C for 12 hours. Use 20mm A uniaxial extruder (manufactured by OCS) extrudes the resin composition [1] from a 150 mm wide T die at a resin temperature of 260 ° C, and is pulled by a roller with a surface temperature of 110 ° C to obtain a width of 110 mm and a thickness of 80 μm. Unstretched film. Table 3 shows the strength and photoelastic coefficient β of the unstretched film.

Cut out a size of 50mm × 40mm from the unstretched film, and fix it to a tensile tester so that the distance between the clamps becomes 20mm. AG-IS 5kN, manufactured by Shimadzu Corporation), is uniaxially stretched at a glass transition temperature + 15 ° C extension temperature, an extension speed of 500% / min, and a longitudinal area extension ratio of 2 times. It is held for 10 seconds, followed by rapid cooling to obtain Uniaxially stretched film with a thickness of 40 μm.

Table 3 shows the measurement results of the thickness d, the in-plane direction retardation Re, the thickness direction retardation Rth, the total light transmittance T _t , the haze H, and the wet heat shrinkage of the uniaxially stretched film.

<Examples 2 to 7, Comparative Examples 1 to 10> Uniaxially stretched film

A resin composition [2] to [17] was produced in the same manner as in Example 1 except that the blending composition shown in Table 3 or Table 4 was changed. The physical properties of the resin compositions [2] to [17] are shown in Table 3 or 4.

Except to replace resin composition [1], use resin composition Except for [2] to [17], in the same manner as in Example 1, an unstretched film having a width of 110 mm and a thickness of 80 μm and a uniaxially stretched film having a thickness of 40 μm were obtained. Table 3 or 4 shows the evaluation results of the unstretched film and the uniaxially stretched film. Furthermore, in Comparative Examples 1 and 5, the uniaxial stretching was not possible because the strength of the unstretched film was insufficient.

<Example 8> Biaxially stretched film

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

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

This unstretched film was cut into a size of 100 mm × 100 mm. This section was fixed to a pantagraph type biaxial elongation tester (manufactured by Toyo Seiki Co., Ltd.) at a glass transition temperature of + 20 ° C, an elongation temperature of 1000% / min, and a longitudinal elongation rate of 1000% / The horizontal stretching speed of 2 minutes, the vertical stretching ratio of 2 times, the horizontal stretching ratio of 2 times, and the biaxial stretching were maintained for 10 seconds, followed by rapid cooling to obtain a biaxially stretched film having a thickness of 40 μm. Table 5 shows the evaluation results of the resin composition [19], the unstretched film, and the biaxially stretched film.

<Comparative Example 11>

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

An unstretched film having a width of 110 mm and a thickness of 160 μm, and a biaxially stretched film having a thickness of 40 μm were obtained in the same manner as in Example 8 except that the resin composition [18] was used instead of the resin composition [19]. Table 5 shows the evaluation results of the resin composition [18], the unstretched film, and the biaxially stretched film. Because PMMA12 has a high saturated water absorption, it has a large wet heat shrinkage.

<Examples 9 to 11>

A resin composition [20] to [22] was produced in the same manner as in Example 8 except that the blend composition shown in Table 5 was changed.

Except that the resin composition [20] to [22] were used instead of the resin composition [19], an unstretched film having a width of 110 mm and a thickness of 160 μm and a biaxially stretched film having a thickness of 40 μm were obtained in the same manner as in Example 8. Table 5 shows the evaluation results of the resin compositions [20] to [22], the unstretched film, and the biaxially stretched film.

<Example 12>

A resin composition [23] was produced in the same manner as in Example 8 except that the blend composition shown in Table 5 was changed.

An unstretched film having a width of 110 mm was obtained in the same manner as in Example 8 except that the resin composition [23] was used instead of the resin composition [19] and the thickness of the obtained film was 80 μm. A biaxially stretched film was obtained in the same manner as in Example 8 except that the thickness of the obtained film was 20 μm. Table 5 shows the evaluation results of the resin composition [23], the unstretched film, and the biaxially stretched film.

Example 13

A polyvinyl alcohol film having an average degree of polymerization of 2400, a degree of saponification of 99.9 mole%, and a thickness of 75 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, it was extended to 3.5 times while dyeing in 0.3% by weight (weight ratio: iodine / potassium iodide = 0.5 / 8) in a 30 ° C iodine solution for 1 minute. Then, while immersing in a 4% by weight aqueous boric acid solution at 65 ° C. for 0.5 minutes, the total stretching ratio was extended to 6 times. After stretching, it was dried in an oven at 70 ° C. for 3 minutes to obtain a polarizer having a thickness of 22 μm.

16.8 g of polyester urethane (made by Daiichi Kogyo Pharma, trade name: Superflex 210, solid content: 33%), 4.2 g of cross-linking agent (containing Polymer of oxazoline, made by Japan Catalyst, trade name: Epocros WS-700, solid content: 25%), 2.0 g of 1% by weight ammonia water, 0.42 g of colloidal silica (manufactured by Fuso Chemical Industries, Quartron PL-3 , Solid content: 20% by weight) and 76.6 g of pure water to obtain an easy-adhesive composition.

38.3 parts by mass of N-hydroxyethyl acrylamide ( (Produced by Hingren Co., Ltd.), 19.1 parts by mass of tripropylene glycol diacrylate (trade name: Aronix M-220, manufactured by Toa Kosei Co., Ltd.), 38.3 parts by mass of propylene fluorenylmorpholine (produced by Hingren Co., Ltd.) A photopolymerization initiator (trade name: KAYACURE DETX-S, diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) was stirred at 50 ° C for 1 hour to obtain an active energy ray-curable adhesive.

For the biaxially stretched film obtained in Example 11 (hereinafter This is referred to as a thin film a) and is subjected to a corona discharge treatment. The said easy-adhesive composition was apply | coated on the corona-discharge-treated surface of the film a with a bar coater so that thickness after drying might become 100 nm. Then, it dried in the hot-air dryer (110 degreeC) for about 5 minutes, and the easy-adhesion layer was formed in the one side of the film a.

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

On both surfaces of the polarizer, each of the adhesive layers was oriented toward the polarizer side, and the aforementioned film a was laminated using a small-sized laminator. The IR heater was used to heat the two sides to 50 ° C, and the two sides were irradiated with ultraviolet rays with a cumulative irradiation amount of 1000 / mJ / cm ^{2 to} harden the active energy ray-curable adhesive to obtain a laminated film a formed on both sides of the polarizer. Of the polarizing plate X.

The polarizing plate X was left in a constant temperature and humidity chamber at 80 ° C and 90% RH for 100 hours. Then, the polarizing plate X taken out from the thermo-hygrostat was visually observed. No deterioration of the polarizer was observed.

Comparative Example 12

A triethylammonium cellulose film having a thickness of 40 μm was immersed in a 10% aqueous sodium hydroxide solution (60 ° C.) for 30 seconds to be saponified. Then, it washed with water for 60 seconds, and obtained the film b.

100 parts by mass of a vinyl alcohol-based polyvinyl alcohol-based resin (average degree of polymerization: 1200, degree of saponification: 98.5 mole%, degree of modification of ethyl acetate: 5 mole%) and 20 parts by mass The methylol melamine was dissolved in pure water at a temperature of 30 ° C to obtain an adhesive composition having a solid content concentration of 0.5%.

This adhesive composition was left in an environment at 30 ° C for 30 minutes. This adhesive composition was applied to the film b so that the thickness after drying became 50 nm to form an adhesive layer.

On both sides of the polarizer, each of the adhesive layers was oriented toward the polarizer side, and the aforementioned film b was laminated using a small laminator. This was dried in a hot-air dryer (70 ° C) for 5 minutes to obtain a polarizing plate Y formed by laminating a film b on both sides of a polarizer.

The polarizing plate Y was left in a constant temperature and humidity chamber at 80 ° C. and 90% RH for 100 hours. Then, the polarizing plate Y taken out from the thermo-hygrostat was visually observed. See the deterioration of the polarizer.

Claims (13)

A resin composition comprising a mass ratio (A) / (B) of a methacrylic resin (A) to a polycarbonate resin (B) of 96/4 to 99/1 and a methacrylic resin (A) Formed with polycarbonate resin (B), where methacrylic resin (A) contains 10 to 50% by mass of structural units (a1) derived from methacrylic polycyclic aliphatic hydrocarbon ester, 50 to 90% by mass The structural unit (a2) derived from a methacrylic acid ester other than the polycyclic aliphatic hydrocarbon ester of methacrylic acid, and the structural unit (a3) derived from an acrylic acid ester at 0 to 20% by mass. The resin composition according to claim 1, wherein the polycyclic aliphatic hydrocarbon methacrylate is a compound represented by formula (1); (In the formula (1), X is a polycyclic aliphatic hydrocarbon group having 10 or more carbon atoms). The resin composition of claim 2, wherein X is different Alk-2-yl or tricyclic [5.2.1.0 ^2,6 ] decane-8-yl. The resin composition according to any one of claims 1 to 3, wherein the methacrylic acid ester other than the methacrylic polycyclic aliphatic hydrocarbon ester is methyl methacrylate. The resin composition according to any one of claims 1 to 3, wherein the intermediate point glass transition temperature measured by JIS K7121 (temperature rise rate: 20 ° C / min) is 120 ° C or higher. The resin composition according to any one of claims 1 to 3, 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. The film of claim 7 has a thickness of 10 to 50 μm. If the film of item 7 or 8 is requested, the area ratio is extended to 1.5-8 times by biaxially. If the film of claim 7 or 8 is stretched at least uniaxially. 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 polarizing plate includes a polarizer and a film according to any one of claims 7 to 10 laminated on the polarizer.