KR20150093111A - Thermoplastic resin film, stretched film, polarizer protection film and polarizing plate - Google Patents

Abstract

The present invention relates to a thermoplastic resin film having excellent transparency and, more specifically, to a thermoplastic resin film, which comprises a resin composition containing 50-95 wt% of an acryl-based resin and 5-50 wt% of polycarbonate-based resin, with respect to 100 wt% of the total of the acryl-based resin and the polycarbonate-based resin, wherein the acryl-based resin is a resin comprising a copolymer obtained by polymerizing a monomer ingredient, which comprises 50-95 wt% of methacrylic acid methyl, 5-50 wt% of (met)acrylic acid ester represented as the chemical formula (I), and 0.1-20 wt% of a single-functional monomer besides the same. The present invention relates to a thermoplastic resin having the temperature of T_2500(°C) with shear viscosity of 2500 Pa·s of a resin composition, regarding a shear speed of 60 sec^-1, which satisfies the chemical formula (a).

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin film, a stretched film, a polarizer protective film and a polarizer,

The present invention relates to a thermoplastic resin film and a stretched film obtained by stretching the thermoplastic resin film. The present invention also relates to a polarizer protective film comprising the thermoplastic resin film or the stretched film, and a polarizer including the polarizer protective film and the polarizer.

The polycarbonate resin generally has excellent heat resistance, dimensional stability, impact resistance, rigidity, transparency and the like. However, scratch resistance and long-term UV resistance are insufficient, which also has the disadvantage of occurrence of stress birefringence. On the other hand, it is known that methacrylic resins such as polymethyl methacrylate have excellent transparency, surface hardness, UV resistance, weather resistance, chemical resistance and the like. However, dimensional stability, impact resistance, heat resistance and the like are insufficient.

Therefore, it is expected that the blend of the polycarbonate resin and the methacrylic resin will compensate for the individual defects of each component and obtain a usable material for various purposes. However, conventional blends of a polycarbonate resin and a methacrylic resin are opaque, and thus there is a problem that they can not be used for applications requiring transparency.

Therefore, as a transparent blend of a polycarbonate resin and a methacrylic resin, Patent Document 1 discloses an aromatic polycarbonate resin and a methacrylic acid monomer unit containing 5 to 95% by weight of a methacrylic acid monomer unit and methacrylic polymer having a carbon cyclic group in an ester group Discloses a resin composition containing a methacrylic resin obtained by polymerizing 5 to 95% by weight of an acid ester monomer unit and 0 to 40% by weight of an a, -unsaturated monomer unit.

Japanese Patent Application Laid-open No. Hei 1-1749

However, when the thermoplastic resin film is melt-extruded from the resin composition described in Patent Document 1, the obtained thermoplastic resin film becomes opaque and transparency may be lowered, and there is room for improvement in transparency of such a thermoplastic resin film .

In addition, a thermoplastic resin film or a stretched film formed by stretching a thermoplastic resin film may be provided with a surface treatment layer such as a hard coating layer on the surface of the film in order to impart a specific function. However, a thermoplastic resin film or a stretched film having a surface-treated layer is liable to be broken when gripped by a hand or a fixing member in a process such as carrying or joining with other members. Therefore, it is desired that the thermoplastic resin film and the stretched film have excellent toughness, which is difficult to be broken even if they are gripped by a hand or a fixing member when the surface treatment layer is provided.

A problem to be solved by the present invention is to provide a thermoplastic resin film having excellent transparency and excellent toughness and a stretched film obtained by stretching the thermoplastic resin film and to provide a polarizer protective film comprising the thermoplastic resin film or the stretched film, And a polarizing plate including the polarizer protective film and the polarizer.

In order to solve the above problems, the present invention provides the following invention.

<1> A resin composition comprising an acrylic resin and a polycarbonate resin in an amount of 50 to 95% by weight of an acrylic resin and 5 to 50% by weight of a polycarbonate resin based on 100% by weight of the total of the acrylic resin and polycarbonate resin Wherein the thermoplastic resin film is a thermoplastic resin film,

Wherein the acrylic resin comprises 50 to 95% by weight of methyl methacrylate and 50 to 95% by weight of a monomer represented by the following formula (I), based on 100%

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, an alkyl group substituted with a naphthyl group, a naphthyl group, a naphthyl group substituted with an alkyl group , An alkyl group substituted with a phenyl group, a phenyl group, a phenyl group substituted with an alkyl group, a dicyclopentanyl group or a dicyclopentenyl group)

And 5 to 50% by weight of a (meth) acrylic acid ester represented by the following general formula (1) and 0.1 to 20% by weight of a monofunctional monomer other than these:

Shear rate of 60sec ^- the shear viscosity of the resin composition according to ¹ to a temperature T ₂₅₀₀ (℃) is to 2500Pa · s formula (a)

(Wherein MVR _pc represents the melt volume ratio of the polycarbonate resin at 300 ° C, and W _a represents the weight percentage of the (meth) acrylic acid ester represented by the formula (I) in the monomer component And W _b represents the weight percentage of the polycarbonate resin in the resin composition)

By weight of the thermoplastic resin film.

<2> The thermoplastic resin film according to <1>, wherein the acrylic resin has a weight average molecular weight of 50,000 to 200,000.

&Lt; 3 > The resin composition according to any one of (1) to (3), wherein the (meth) acrylic acid ester represented by the formula (I) is selected from the group consisting of cyclohexyl methacrylate, phenyl methacrylate, naphthyl methacrylate, dicyclopentanyl methacrylate and dicyclopentenyl methacrylate 1 &gt; or &lt; 2 &gt;.

<4> The thermoplastic resin film according to any one of <1> to <3>, wherein the monofunctional monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.

<5> The thermoplastic resin film according to any one of <1> to <4>, which is produced by melt co-extrusion molding.

<6> The thermoplastic resin film according to any one of <1> to <5>, which has a surface treatment layer on at least one side.

<7> A stretched film obtained by stretching the thermoplastic resin film according to any one of <1> to <5>.

<8> The stretched film according to <7>, wherein the stretched film has a surface treatment layer on at least one side.

<9> A polarizer protective film comprising the thermoplastic resin film according to any one of <1> to <6>.

&Lt; 10 > A polarizer protective film comprising the stretched film according to < 7 > or < 8 >.

<11> A polarizing plate comprising a polarizer and a polarizer-protective film according to <9> or <10> disposed on at least one surface of the polarizer.

According to the present invention, a thermoplastic resin film having excellent transparency and excellent toughness, and a stretched film obtained by stretching the thermoplastic resin film can be obtained. The stretched film obtained by stretching the thermoplastic resin film and the thermoplastic resin film of the present invention is suitably used as a polarizer protective film.

The thermoplastic resin film of the present invention includes a resin composition containing a specific acrylic resin and a specific polycarbonate resin in a predetermined ratio.

&Lt; Acrylic resin &

The acrylic resin used in the present invention comprises 50 to 95% by weight of methyl methacrylate,

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, an alkyl group substituted with a naphthyl group, a naphthyl group, a naphthyl group substituted with an alkyl group , An alkyl group substituted with a phenyl group, a phenyl group, a phenyl group substituted with an alkyl group, a dicyclopentanyl group or a dicyclopentenyl group)

And 5 to 50% by weight of a (meth) acrylic acid ester represented by the following formula (1) and 0.1 to 20% by weight of a monofunctional monomer other than these.

Further, in the present specification, the term "(meth) acryl" means "acrylic" or "methacryl".

Commercially available methyl methacrylate may be used as it is, or may be synthesized separately according to conventionally known methods.

Methyl methacrylate is contained in a proportion of 50 to 95% by weight based on 100% by weight of the total of the monomer components constituting the copolymer contained in the acrylic resin from the viewpoint of improving the transparency and weatherability of the acrylic resin, Is contained in a proportion of 60 to 90% by weight.

In the above formula (I), R ¹ represents a hydrogen atom or a methyl group, preferably a methyl group.

The (meth) acrylic acid ester represented by the formula (I) (hereinafter sometimes referred to as a (meth) acrylic acid ester) has at least one alicyclic hydrocarbon group or aromatic hydrocarbon group, A separately synthesized product may be used according to a known method.

In the formula (I), R ² represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, an alkyl group substituted with a phenyl group, a phenyl group, Phenyl group "," alkyl group substituted with a naphthyl group "," naphthyl group "," naphthyl group substituted with an alkyl group "," dicyclopentanyl group "or" dicyclopentenyl group ".

As the "alkyl group" of the "alkyl group substituted with a cycloalkyl group" represented by R ² , an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a n-propyl group, Isobutyl group, tert-butyl group and the like, and the "cycloalkyl group" as the substituent thereof is preferably a cycloalkyl group having 5 to 12 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, An octyl group, and a cyclododecyl group. The number of the "cycloalkyl group" as the substituent and the substitution position in the alkyl group are not particularly limited. Examples of the "alkyl group substituted with a cycloalkyl group" represented by R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl (meth) acrylate group substituted with a cycloalkyl group having 5 to 12 carbon atoms in at least one hydrogen atom An n-butyl group, an isobutyl group, and a tert-butyl group.

The "cycloalkyl group" represented by R ² is preferably a cycloalkyl group having 5 to 12 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group, and a cyclododecyl group. Further, it may be further substituted with a substituent such as a hydroxyl group, an amino group, and a sulfone group, if necessary.

The "cycloalkyl group" of the "cycloalkyl group substituted with an alkyl group" represented by R ² is preferably a cycloalkyl group having 5 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group, An alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group Group, a tert-butyl group, and the like. There are no particular restrictions on the number of the "alkyl group" as the substituent and the substitution position in the cycloalkyl group. The "alkyl group substituted with an alkyl group" represented by R ² includes, for example, a cyclopentyl group in which at least one hydrogen atom (H) is substituted with an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a cyclobutyl group, A cycloheptyl group, a cyclooctyl group, and a cyclododecyl group.

The "alkyl group" of the "alkyl group substituted with a phenyl group" represented by R ² is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, Group, a tert-butyl group, and the like. There are no particular restrictions on the number of the "phenyl group" as the substituent and the substitution position in the alkyl group. Examples of the "alkyl group substituted with a phenyl group" represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group And tert-butyl group (for example, benzyl group, phenethyl group, etc.).

The "phenyl group" represented by R ² is not particularly limited and may be further substituted with a substituent such as a hydroxyl group, an amino group, or a sulfone group.

As the "alkyl group" which is a substituent of the phenyl group of the "phenyl group substituted with an alkyl group" represented by R ² , an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include a methyl group, ethyl group, n-propyl group, An isobutyl group, and a tert-butyl group. The number of the "alkyl group" as the substituent and the substitution position in the phenyl group are not particularly limited. Examples of the "phenyl group substituted with an alkyl group" represented by R ¹ include o-tolyl group, m-tolyl group, p-tolyl group and the like.

The "alkyl group" of the "alkyl group substituted with a naphthyl group" represented by R ² is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, ethyl group, n- Butyl group, tert-butyl group and the like. The number of the "naphthyl group" as the substituent and the substitution position in the alkyl group are not particularly limited. Examples of the "alkyl group substituted with a naphthyl group" represented by R ² include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, and tert-butyl group (for example, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylmethyl group, 2-naphthylethyl group and the like).

The "naphthyl group" represented by R ² is not particularly limited and may be further substituted with a substituent such as a hydroxyl group, an amino group, or a sulfone group.

As the "alkyl group" which is a substituent of the naphthyl group of the "naphthyl group substituted with an alkyl group" represented by R ² , an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include methyl group, ethyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. The number of the "alkyl group" as the substituent and the substitution position in the naphthyl group are not particularly limited. Examples of the "naphthyl group substituted with an alkyl group" represented by R ² include a methylnaphthyl group and an ethylnaphthyl group.

Further, the "dicyclopentanyl group" and "dicyclopentenyl group" represented by R ² may be further substituted with substituents such as an alkyl group, a hydroxyl group, an amino group, and a sulfone group, respectively. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group.

R ² is preferably a cycloalkyl group (preferably a cyclohexyl group), a phenyl group, a naphthyl group, a dicyclopentanyl group, or a dicyclopentenyl group, more preferably a cyclohexyl group and a phenyl group.

In the present invention, the (meth) acrylic acid ester is preferably cyclohexyl methacrylate, phenyl methacrylate, naphthyl methacrylate, dicyclopentanyl methacrylate or dicyclopentenyl methacrylate, more preferably Cyclohexyl methacrylate and phenyl methacrylate.

The (meth) acrylic esters may be used alone or in combination of two or more.

(Meth) acrylic acid ester is contained in a proportion of 5 to 50% by weight, preferably 10 to 40% by weight, based on 100% by weight of the total of the monomer components constituting the copolymer contained in the acrylic resin do. When the content of the (meth) acrylic acid ester is less than 5% by weight, the compatibility of the acrylic resin with the polycarbonate resin is lowered and the transparency of the thermoplastic resin film is lowered. On the other hand, when the content of the (meth) acrylic acid ester is more than 50% by weight, the weatherability of the thermoplastic resin film is lowered in addition to the lowering of the compatibility (transparency).

(Hereinafter may be referred to as monofunctional monomers) other than methyl methacrylate and the (meth) acrylic acid ester represented by the formula (I) may be used as they are, Or a mixture thereof.

The monofunctional monomer is not particularly limited as long as it is copolymerizable with methyl methacrylate and / or (meth) acrylic acid ester. Examples thereof include alkyl (meth) acrylates other than methyl methacrylate and (meth) (For example, acrylonitrile, methacrylonitrile, etc.), acrylic acid, methacrylic acid, and maleic anhydride. Of these, alkyl methacrylate or alkyl acrylate is preferable, and alkyl acrylate is particularly preferable.

Examples of the alkyl methacrylate include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, sec- Butyl isobutyl, 2-ethylhexyl methacrylate and the like. Among them, alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms is preferable. Examples of the alkyl acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, butyl acrylate (n-butyl acrylate, t-butyl acrylate, sec-butyl acrylate, isobutyl acrylate) And the like.

In the present invention, monofunctional monomers are preferably methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.

The monofunctional monomers may be used alone or in combination of two or more.

The monofunctional monomer is contained in an amount of 0.1 to 20% by weight, preferably 0.2 to 10% by weight, more preferably 0.3% by weight based on 100% by weight of the total of the monomer components constituting the copolymer contained in the acrylic resin. By weight to 5% by weight. If the content of the monofunctional monomer is less than 0.1% by weight, thermal decomposition of the acrylic resin tends to occur easily. On the other hand, if the content of the monofunctional monomer exceeds 20% by weight, the transparency and heat resistance of the thermoplastic resin film may be lowered.

As the monomer component constituting the acrylic resin, other than the above-mentioned methyl methacrylate, the (meth) acrylic acid ester represented by the formula (I) and monomers other than the monofunctional monomers are included so far as the effect of the present invention is not impaired .

The polymerization method for polymerizing the monomer component is not particularly limited and a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like can be adopted. A radical polymerization initiator is usually used for polymerization, and a radical polymerization initiator and a chain transfer agent are preferably used.

Examples of the polymerization initiator include azo compounds such as azobisisobutylonitrile, and radical polymerization initiators such as lauroyl peroxide and organic peroxides such as 1,1-di (t-butylperoxy) cyclohexane, Is used. The polymerization initiator may be used alone or in combination of two or more. The amount of the polymerization initiator may be appropriately determined depending on the type and ratio of the monomers.

As the chain transfer agent, for example, mercaptans such as n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, 2-ethylhexyl thioglycolate and the like are preferably used. The chain transfer agent may be used alone, or two or more kinds may be used in combination. The amount of the chain transfer agent may be appropriately determined depending on the type and ratio of the monomers.

The polymerization temperature, polymerization initiation and the like at the time of polymerizing the monomer component may be suitably set according to the kind of the monomer, the ratio of the monomers, and the like, and are not particularly limited.

The weight average molecular weight of the acrylic resin is preferably 50,000 to 200,000, and more preferably 80,000 to 200,000. When the acrylic resin has a weight average molecular weight in this range, the fluidity is excellent, and the resin composition is easily melted and kneaded at the time of producing the resin composition, which improves the processability. Further, the mechanical strength of the thermoplastic resin film obtained from the resin composition is improved.

The acrylic resin has a melt mass flow rate (MFR) of preferably 0.1 to 50 g / 10 min, more preferably 0.2 to 30 g / 10 min, at 230 캜, which is measured at a load of 3.8 kg. When the acrylic resin has an MFR in this range, the resin has excellent flowability and is easily melted and kneaded when the resin composition is produced. Further, the mechanical strength of the thermoplastic resin film obtained from the resin composition is improved.

The acrylic resin may contain an additive such as a releasing agent, an ultraviolet absorber, a dye, a pigment, a polymerization inhibitor, an antioxidant, a flame retardant, and a reinforcing agent in a range that does not impair the effects of the present invention, in addition to the copolymer obtained by polymerizing the monomer component However, the content of the copolymer relative to 100 parts by weight of the total amount of the acrylic resin is preferably 95 to 99.995 parts by weight.

<Polycarbonate-based resin>

Examples of the polycarbonate resin include resins obtained by reacting a divalent phenol and a carbonylating agent with an interfacial polycondensation method or a melt ester exchange method; Those obtained by polymerizing a carbonate prepolymer with a solid-phase ester exchange method or the like; And those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

Examples of the divalent phenol include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) Methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) (Bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2- Bis {(4-hydroxy-3,5-dibromo) phenyl} propane, 2,2-bis { (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis -Isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- (4-hydroxyphenyl) -o-diisopropylbenzene,?,? '- bis (4-hydroxyphenyl) diisopropylbenzene,?,? '- bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, and the like. These may be used alone, or two or more of them may be used in combination.

Among these divalent phenols, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2- Hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2- 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and?,? '- bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferable. Particularly, the use of bisphenol A alone or a combination of bisphenol A with 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis { ) Phenyl} propane, and?,? '-Bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferably used in combination with at least one member selected from the group consisting of?

Examples of the carbonylating agent include carbonyl halide (such as phosgene), carbonate ester (such as diphenyl carbonate), and haloformate (dihaloformate of divalent phenol). These may be used alone, or two or more of them may be used in combination.

The polycarbonate resin used in the present invention has a weight average molecular weight of preferably 20,000 to 60,000, and more preferably 22,000 to 400,000. When the polycarbonate resin has a weight average molecular weight in this range, it is excellent in fluidity, and is easily melted and kneaded at the time of producing the resin composition, so that the processability is improved. In addition, the impact resistance and heat resistance of the thermoplastic resin film obtained from the resin composition are improved.

The polycarbonate resin has a melt volume ratio (MVR) of preferably 8 to 100 cm 3/10 min, more preferably 10 to 85 cm 3/10 min at 300 캜, which is measured at a load of 1.2 kg. When the polycarbonate resin has an MVR in this range, it has excellent flowability, and is easily melted and kneaded when the resin composition is produced. Further, the mechanical strength of the thermoplastic resin film obtained from the resin composition is improved.

Additives such as a release agent, an ultraviolet absorber, a dye, a pigment, a polymerization inhibitor, an antioxidant, a flame retardant, and a reinforcing agent may be added to the polycarbonate resin within the range not to impair the effects of the present invention.

<Resin composition>

The resin composition contains an acrylic resin and a polycarbonate resin in an amount of 50 to 95% by weight of the acrylic resin and 5 to 50% by weight of the polycarbonate resin based on 100% by weight of the total of the acrylic resin and the polycarbonate resin. When the content of the polycarbonate resin is less than 5% by weight, the mechanical strength of the thermoplastic resin film obtained from the resin composition becomes insufficient. On the other hand, when the content of the polycarbonate resin exceeds 50% by weight, the transparency of the resin composition and the thermoplastic resin film is lowered. The acrylic resin is preferably contained in a proportion of 50 to 80% by weight, and the polycarbonate resin is preferably contained in a proportion of 20 to 50% by weight.

The resin composition of the present invention may contain an ultraviolet absorbent, an antioxidant, a compatibilizing agent, a stabilizer, a colorant, a foaming agent, a lubricant, a releasing agent, an antistatic agent, a flame retardant, , And a flame-retardant additive may be added. A small amount of other thermoplastic resin or the like may also be added. These additives may be added at the time of melt-kneading a resin mixture containing an acrylic resin and a polycarbonate resin, or may be added before or after melt-kneading. When the additive is added, the total content of the acrylic resin and polycarbonate resin relative to 100 parts by weight of the total amount of the resin composition is preferably 70 to 99.995 parts by weight.

Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. These may be used alone, or two or more of them may be used in combination.

Examples of the triazine ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- 2,4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4- Triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- -Triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine and the like.

Examples of the benzophenone-based UV absorbers include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy- -Dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-hydroxy-4-methoxy-benzophenone, 2,2'-di Hydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4'-tetrahydroxy-benzophenone, and the like.

Examples of the benzotriazole ultraviolet absorber include 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'- Triazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'- Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- 3'- (3 ", 4 &quot;, 5 &quot;, 6 &quot;, 2 ' -hydroxy- -Tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole (2'-hydroxy-3 ', 5' -trifluoromethyl-2'-yl) phenol) (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, -Hydroxy-3 ', 5'-di-tert- Butylphenyl) -5-chlorobenzotriazole, (2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole and the like.

Examples of the benzoate-based ultraviolet absorbers include 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, 2,6- Phenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di- , 5-di-t-butyl-4-hydroxybenzoate, and the like.

Examples of the cyanoacrylate ultraviolet absorber include 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3- (3 ', 4'- Oxyphenyl) -acrylate, and the like.

As ultraviolet absorbers, for example, triazine-based ultraviolet absorbers such as "Kemisorb 102" manufactured by Chemipro Kasei Kabushiki Kaisha, "Adekastab LAF70" manufactured by ADEKA Kabushiki Kaisha, As the ultraviolet absorber for a sol, there is also a commercially available product such as &quot; Adecastab LA31 &quot; manufactured by Adeka Kabushiki Kaisha.

The ultraviolet absorber has a weight average molecular weight of preferably 500 to 1000, more preferably 550 to 700. When the weight average molecular weight is too small, it tends to volatilize during molding. When the molecular weight is too large, compatibility with acrylic resins or polycarbonate resins tends to be lowered.

The ultraviolet absorber has a molar absorptivity of preferably 10 L / mol · cm or more, more preferably 15 L / mol · cm or more at a wavelength of maximum absorption. When the molar absorptivity of the ultraviolet absorber is within the above-mentioned predetermined range, the ultraviolet absorptivity is more excellent and the content of the ultraviolet absorber can be reduced.

Examples of the antioxidant include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. These may be used alone, or two or more of them may be used in combination.

Examples of the hindered phenol-based antioxidant include "Irganox 1010", "Irganox 1035", "Irganox 1076", "Irganox 1222", " "Antigene P", "Antigen 3C", "Antigen FR", "Smilizer S", "Smiliger GA 80" manufactured by Sumitomo Chemical Co., Ltd., "Adekastab AO 70" , &Quot; Adecastab AO80 &quot;, and &quot; Adecastab AO503 &quot;.

Examples of the phosphorus antioxidant include tris (2,4-di-t-butylphenyl) phosphate, 2- [[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [ f] [1,3,2] dioxaphospepin-6-yl] oxy] -N, N-bis [2- [[2,4,8,10-tetrakis (1,1-dimethylethyl) di Benzo [d, f] [1,3,2] dioxaphospepin-6-yl] oxy] -ethyl] ethanamine, diphenyl tridecyl phosphate, triphenyl phosphate, 2,2- Butylphenyl) octyl phosphate, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and the like. Of these, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphate is preferred.

Examples of the sulfur-based antioxidant include dimethyl disulfide, diethyl disulfide, di-n-propyl disulfide, di-n-butyl disulfide, di- -tert-amyl disulfide, dicyclohexyl disulfide, di-tert-octyl disulfide, di-n-dodecyl disulfide, and di-tert-dodecyl disulfide. Of these, di-tert-alkyl disulfides are preferable, and di-tert-dodecyl disulfide is more preferable.

The resin composition can be obtained, for example, by melt-kneading a resin mixture containing an acrylic resin and a polycarbonate resin.

In order to uniformly melt and knead these resins, melt kneading is usually carried out at a temperature of 180 to 320 ° C, preferably 200 to 300 ° C, at a shear rate of usually 10 to 200 sec ^-1 , preferably 30 to 150 sec ^-1 Shear rate.

As a device used for melt kneading, a usual mixer, kneader and the like can be used. Specific examples thereof include a uniaxial kneading extruder, a twin-screw kneading extruder, a ribbon blender, a Henschel mixer, a Banbury mixer, and a drum tumbler. Among them, a biaxial kneading extruder is preferable. The melt kneading can be carried out in an atmosphere of an inert gas such as nitrogen gas, argon gas or helium gas, if necessary.

In this way, a resin composition excellent in transparency can be obtained. A thermoplastic resin film is obtained from the resin composition as described later, but the present invention is not limited to this, and the resin composition is processed into a desired shape to obtain a molded article. Such a molded article is also excellent in transparency.

For example, a resin composition obtained by melt-kneading an acrylic resin and a polycarbonate resin may be used as it is, or the resin composition may be formed into a predetermined shape such as pellet or the like, It can also be used. The molding processing method is not particularly limited, and examples thereof include an injection molding method, a press molding method, and a melt extrusion molding method.

The molded article is useful, for example, as an electro-optical material (a material such as a lens, an optical disk substrate, or a light guide plate), a cover material (a material such as a cover such as a display), a resin glazing material,

&Lt; Thermoplastic resin film &

The thermoplastic resin film of the present invention has a shear rate of 60sec ^- has a shear viscosity of the resin composition in the ^first to the temperature T ₂₅₀₀ (℃) 2500Pa · s is a need to satisfy the formula (a).

In the formula, MVR _pc represents the melt volume ratio of the polycarbonate resin at 300 ° C, W _a represents the weight percentage of the (meth) acrylic acid ester represented by the formula (I) in the monomer component, And W _b represents the weight percentage of the polycarbonate resin in the resin composition.

By satisfying the formula (a), occurrence of turbidity is suppressed, and a thermoplastic resin film having excellent transparency can be obtained. When the formula (a) is not satisfied, a thermoplastic resin film which is easily clouded and has excellent transparency can not be obtained.

As a method of obtaining a thermoplastic resin film from a resin composition, a melt extrusion molding method is preferable as described later. In the melt extrusion molding method, the resin composition is melted and kneaded by an extruder, and the melted resin is continuously extruded from the die into a film to form a film. During the period from the time when the molten resin is extruded from the die, the molten resin is usually given a shear stress of a shear rate of 60 sec &lt; ^{-1 &} gt ;. When the shear stress is applied, it is desired that the viscosity of the molten resin (i.e., the shear viscosity) is usually 2500 Pa · s or less so that the molten resin can be easily extruded. The shear viscosity can be set to a desired value by controlling the temperature of the molten resin when the shear stress is applied. When the shear viscosity is made smaller, the temperature of the molten resin can be increased. When the shear viscosity is made larger, The temperature can be reduced.

The inventors of the present invention have studied the relationship between the occurrence of turbidity in the obtained thermoplastic resin film and the resin composition and found that when the temperature of the molten resin at the time of applying the shearing stress is increased, the thermoplastic resin film is likely to be clouded The inventors of the present invention have found that when the temperature T ₂₅₀₀ at which the shear viscosity of the resin composition at a shear rate of 60 sec ^-1 becomes ₂₅₀₀ Pa · s is lower than a predetermined value, It has been found that a thermoplastic resin film having excellent transparency can be obtained when it satisfies the above formula (a).

The reason why the thermoplastic resin film having excellent transparency can be obtained when the resin composition satisfies the above formula (a) can be considered for the following reasons.

First, the present inventors have found that the resin composition has a cloud point and this cloud point is substantially equivalent to a value calculated from the right side of the above-mentioned formula (a). Further, the inventors of the present invention have found that when the temperature of the molten resin at the time of applying the shearing stress is higher than the melting point of the resin composition, the thermoplastic resin film is likely to be clouded. Value is the shear viscosity of the resin composition at the ^first temperature T ₂₅₀₀ is a 2500Pa · s is calculated from the right side of the formula (a) ^- From the above, temperatures, i.e., a shear rate of 60sec of the molten resin of when a shearing stress given It is considered that melt-extrusion molding can be carried out at a temperature lower than the melting point of the resin composition, whereby occurrence of turbidity is suppressed and a thermoplastic resin film having excellent transparency is obtained.

In the present specification, the melting point of the resin composition means that the thermoplastic resin film is produced while raising the set temperature of the die by the melt extrusion molding method, and the obtained thermoplastic resin film is sequentially measured for total light transmittance according to JIS K7361-1 Means the set temperature of the die when the thermoplastic resin film having the total light transmittance of 85% or less is melt-extruded.

The thickness of the thermoplastic resin film is preferably 10 to 1000 占 퐉, more preferably 20 to 500 占 퐉, and still more preferably 20 to 300 占 퐉.

As a method for obtaining a thermoplastic resin film from a resin composition, for example, a resin composition containing an acrylic resin and a polycarbonate resin is first obtained, and then the resin composition is melt-extruded, A pressing method or the like. Among them, the melt extrusion molding method is preferable.

As the melt extrusion molding method, for example, first, an acrylic resin and a polycarbonate resin are mixed, and if necessary, the above-mentioned other components are further mixed to obtain a resin composition, and the resulting resin composition is then extruded through a single- And the molten resin is continuously extruded from the T die into a film and the molten resin continuously extruded from the T die is sandwiched between rolls of a metal having a smooth surface, By cooling, a polarizer protective film is obtained. The mixing method of the acrylic resin, the polycarbonate resin and the other components as necessary is not particularly limited and any known method may be used. A super mixer or Banbury mixer may be used, They may be melted and kneaded by a twin-screw extruder, or they may be combined.

The thermoplastic resin film is preferably a film having a single-layer structure, but may be a film having a multilayer structure of two or more layers as long as the effect of the present invention is not impaired. When the thermoplastic resin film is a multilayer film, each layer may be formed of a resin composition having the same composition or may be formed of a resin composition of a different composition. The resin compositions of different compositions include all kinds of resins including different types of resins, different kinds of resins but different kinds of resins, different types of resins and different additives, and the like .

The thermoplastic resin film can be suitably used as a polarizer protective film. In addition to the polarizer protective film, the thermoplastic resin film may be laminated on a display member such as a lighting member for a building such as a window or carport roof, a mattress for a vehicle such as a window, a mining member for agriculture such as a greenhouse, Can be used.

<Stretched film>

The stretched film is formed by stretching a thermoplastic resin film. Since the stretched film is formed by stretching a thermoplastic resin film, similarly to the thermoplastic resin film, occurrence of turbidity is suppressed, and transparency is excellent. In addition, the stretched film is excellent in mechanical properties in that it is stretched.

Examples of the stretching include uniaxial stretching and biaxial stretching. Among them, biaxial stretching is preferable. Examples of biaxial stretching include longitudinal stretching and simultaneous biaxial stretching. Examples of the stretching direction include a machine direction of an unstretched film (i.e., a thermoplastic resin film), a direction orthogonal to the machine flow direction, and a direction of slackening in the machine flow direction. The stretching magnification is preferably 1.1 to 3.0 times. Herein, in the present specification, the machine direction is defined as a longitudinal direction, the longitudinal direction is defined as longitudinal stretching, and the direction orthogonal to the machine flow direction is defined as transverse direction and the transverse direction is defined as transverse stretching.

The stretched film can be suitably used as a polarizer protective film. In addition to the polarizer protective film, the stretched film can be laminated on a display member such as a construction light member such as a window or carport roof member, a vehicle light member such as a window, an agricultural mining member such as a greenhouse, an illumination member, .

The thermoplastic resin film or stretched film of the present invention may have a surface treatment layer on at least one side of the film, preferably on one side. By giving the surface treatment layer to the thermoplastic resin film or the stretched film, a specific function according to the kind of the surface treatment layer can be given. Examples of the surface treatment layer include, for example,

(a) a hard coat layer for preventing surface scratches,

(b) an antistatic layer,

(c) an antireflection layer,

(d)

(e) an anti-glare layer for improving visibility, preventing projection of external light, and reducing moire due to interference between the prism sheet and the color filter

to be.

The thermoplastic resin film or stretched film having a surface treatment layer on at least one side of the present invention is excellent in toughness because it is suppressed from occurrence of turbidity and is excellent in transparency and is not easily broken even if it is held by a hand or a fixing tool.

When the surface treatment layer is provided on both sides of the thermoplastic resin film or the stretched film, the types of the surface treatment layers on both sides and the composition constituting the surface treatment layer may be the same or different.

(Hard coat layer)

The hard coat layer has a function of increasing the surface hardness of the thermoplastic resin film or the stretched film and is formed for the purpose of preventing scratches on the surface. The hard coat layer is subjected to a pencil hardness test (optical with hard coat layer) specified in JIS K 5600-5-4: 1999 "General Test Methods for Paints - Part 5: Mechanical Properties of Coating Films - Part 4: Scratch Hardness The film is placed on a glass plate and measured).

The hard coat layer can be formed by applying a curable paint to at least one side of a thermoplastic resin film or a stretched film to form a curable coating film and subsequently curing the coating film.

The material forming the hard coat layer is generally cured by heat or light. For example, organic hard coating materials such as organic silicon-based, melamine-based, epoxy-based, acrylic-based, and urethane acrylate-based materials, and inorganic hard coating materials such as silicon dioxide. Of these, a urethane acrylate-based or polyfunctional acrylate-based hard coat material is preferably used because it has good adhesion to a thermoplastic resin film or a stretched film and is excellent in productivity.

The hard coating layer may contain various fillers for the purpose of adjusting the refractive index, improving the flexural modulus, stabilizing the volume shrinkage ratio, and further improving the heat resistance, antistatic property, and anti-scattering property. The hard coat layer may also contain additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a leveling agent, and an antifoaming agent.

(Antistatic layer)

The antistatic layer is formed for the purpose of imparting conductivity to the surface of the thermoplastic resin film or the stretched film and suppressing the influence of static electricity. For forming the antistatic layer, for example, a method of applying a resin composition containing a conductive material (antistatic agent) on a thermoplastic resin film or a stretched film can be employed. For example, an antistatic hard coat layer can be formed by providing an antistatic agent in the hard coat material used for forming the hard coat layer described above.

(Antireflection layer)

The antireflection layer is a layer for preventing the reflection of external light and is formed directly on the surface of the thermoplastic resin film or the stretched film or through another layer such as a hard coat layer. The thermoplastic resin film or stretched film having the antireflection layer preferably has a reflectance of 2% or less at an incident angle of 5 DEG with respect to light having a wavelength of 430 to 700 nm and preferably has a reflectance at the same incident angle with respect to light having a wavelength of 550 nm of 1% Is more preferable.

The thickness of the antireflection layer may be about 0.01 to 1 mu m, preferably 0.02 to 0.5 mu m. The antireflection layer preferably includes a low refractive index layer having a refractive index smaller than that of the layer (thermoplastic resin film, stretched film, or hard coating layer) on which the antireflection layer is formed, specifically, a refractive index of 1.30 to 1.45, And a thin film of a high refractive index layer containing an inorganic compound are alternately stacked in this order.

The material for forming the low refractive index layer is not particularly limited as long as the refractive index is small. For example, a resin material such as an ultraviolet ray-curable acrylic resin; A hybrid material in which inorganic fine particles such as colloidal silica are dispersed in a resin; A sol-gel material containing an alkoxysilane, and the like. Such a low refractive index layer may be formed by applying a polymer that has been polymerized, or may be formed by applying the monomer in the form of a monomer or oligomer as a precursor and then polymerizing and curing the polymer. In addition, each of the materials preferably contains a compound having a fluorine atom in the molecule in order to impart antifouling properties.

As the sol-gel material for forming the low refractive index layer, those having fluorine atoms in the molecule are suitably used. A typical example of a sol-gel material having fluorine atoms in its molecule is polyfluoroalkylalkoxysilane. The polyfluoroalkylalkoxysilane can be, for example,

, Wherein R represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 12. Among them, a compound in which n in the above formula is 2 to 6 is preferable.

Specific examples of the polyfluoroalkylalkoxysilane include the following compounds.

3,3,3-trifluoropropyltrimethoxysilane,

3,3,3-trifluoropropyltriethoxysilane,

3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltrimethoxysilane,

3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxysilane,

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl trimethoxysilane,

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl triethoxysilane etc.

The low refractive index layer may be composed of a cured product of a thermosetting fluorine-containing compound or an active energy ray-curable fluorine-containing compound. The cured product preferably has a dynamic friction coefficient in the range of 0.03 to 0.15, and preferably has a contact angle to water in the range of 90 to 120 °. As the curable fluorine-containing compound, a polyfluoroalkyl group-containing silane compound (for example, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, 10,10-heptadecafluorodecyltriethoxysilane, etc.), and fluorine-containing polymers having a crosslinkable functional group.

The fluorine-containing polymer having a crosslinkable functional group can be prepared by copolymerizing 1) a monomer containing a fluorine-containing monomer and a monomer having a crosslinkable functional group, or 2) a method of copolymerizing a monomer containing a fluorine-containing monomer with a monomer having a functional group, And then adding a compound having a malfunctioning group.

Examples of the fluorine-containing monomer include fluoroolefins such as fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and perfluoro-2,2-dimethyl-1,3-dioxol ; Partially or completely fluorinated alkyl ester derivatives of (meth) acrylic acid; (Meth) acrylic acid, and partially or fully fluorinated vinyl ethers of (meth) acrylic acid.

Examples of the monomer having a crosslinkable functional group or the compound having a crosslinkable functional group include monomers having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate; Monomers having a carboxyl group such as acrylic acid or methacrylic acid; Monomers having a hydroxyl group such as hydroxyalkyl acrylate or hydroxyalkyl methacrylate; Monomers having an alkenyl group such as allyl acrylate or allyl methacrylate; A monomer having an amino group; Sulfonic acid group-containing monomers.

The material for forming the low refractive index layer may be composed of a sol in which inorganic compound fine particles such as silica, alumina, titania, zirconia, magnesium fluoride, etc. are dispersed in an alcohol solvent from the viewpoint of improving scratch resistance . The inorganic fine particles to be used for this purpose preferably have a smaller refractive index from the viewpoint of antireflection property. The inorganic fine particles may have voids, and hollow fine particles of silica are particularly preferable. The average particle diameter of the hollow fine particles is preferably in the range of 5 to 2000 nm, more preferably 20 to 100 nm. The average particle diameter referred to herein is the number average particle diameter determined by transmission electron microscope observation.

(Stratum corneum)

The antifouling layer is formed to impart water repellency, oil repellency, cold resistance, antifouling property and the like. A suitable material for forming the antifouling layer is a fluorine-containing organic compound. Examples of the fluorine-containing organic compound include fluorocarbon, perfluorosilane, and these high-molecular compounds. The method of forming the antifouling layer may be physical vapor deposition, chemical vapor deposition, wet coating, or the like, which is exemplified by vapor deposition or sputtering, depending on the material to be formed. The average thickness of the antifouling layer is usually about 1 to 50 nm, preferably 3 to 35 nm.

(Antiglare layer)

The antiglare layer is a layer having a fine concavo-convex shape on the surface, and is preferably formed using the hard coating material described above.

The antiglare layer having a fine concavo-convex shape on its surface can be obtained by (1) forming a coating film containing fine particles on a thermoplastic resin film or a stretched film and forming concavo-convex based on the fine particles, (2) A method of forming a coating film on a thermoplastic resin film or a stretched film and then transferring the concavoconvex shape to a surface (a roll or the like) provided with a concave-convex shape on the surface (also referred to as an embossing method).

In the method (1), an antiglare layer can be formed by applying a curable resin composition containing a curable transparent resin and fine particles on a thermoplastic resin film or a stretched film and curing the coating layer by light irradiation such as ultraviolet rays or heating have. The curable transparent resin is preferably selected from a material having a high hardness (hard coat). As such a curable transparent resin, a photo-curable resin such as an ultraviolet-curable resin, a thermosetting resin, an electron-ray-curable resin, or the like can be used, but from the viewpoints of productivity and hardness of the resulting antiglare layer, Is an ultraviolet curing resin. When a photocurable resin is used, the curable resin composition further includes a photopolymerization initiator.

As the photo-curable resin, a polyfunctional acrylate is generally used. Specific examples thereof include di- or tri-acrylates of trimethylolpropane; Tri- or tetra-acrylates of pentaerythritol; And a polyfunctional urethane acrylate which is a reaction product of an acrylate having at least one hydroxyl group in the molecule and a diisocyanate. These polyfunctional acrylates may be used singly or in combination of two or more as necessary.

Further, a mixture of a polyfunctional urethane acrylate, a polyol (meth) acrylate and a (meth) acrylic polymer having an alkyl group containing two or more hydroxyl groups may be used as the photo-curing resin. The polyfunctional urethane acrylate constituting the photo-curable resin is prepared using, for example, (meth) acrylic acid and / or (meth) acrylic acid ester, polyol and diisocyanate. Specifically, a hydroxy (meth) acrylate having at least one hydroxyl group in a molecule is prepared from (meth) acrylic acid and / or a (meth) acrylate ester and a polyol and reacted with a diisocyanate to obtain a polyfunctional urethane acrylic Rate can be produced. The polyfunctional urethane acrylate produced in this manner is also the photo-curing resin itself exemplified above. The (meth) acrylic acid and / or the (meth) acrylic acid ester may be used individually or in combination of two or more in the preparation thereof, or one kind of the polyol and the diisocyanate may be used in the same manner, Two or more species may be used in combination.

The (meth) acrylic acid ester which is one raw material of the polyfunctional urethane acrylate may be a straight chain or cyclic alkyl ester of (meth) acrylic acid. Specific examples thereof include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl Acrylate and cycloalkyl (meth) acrylate such as methacrylate.

The polyol which is another raw material of the polyfunctional urethane acrylate is a compound having at least two hydroxyl groups in the molecule. Examples of the solvent include ethylene glycol, propylene glycol, 1,3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol esters of hydroxypivalic acid, Hexane dimethanol, 1,4-cyclohexanediol, spiroglycol, tricyclodecane dimethylol, hydrogenated bisphenol A, ethylene oxide addition bisphenol A, propylene oxide addition bisphenol A, trimethylol ethane, trimethylol propane, glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, glycoses and the like.

The diisocyanate which is another raw material of the polyfunctional urethane acrylate is a compound having two isocyanato groups (-NCO) in the molecule, and various aromatic, aliphatic or alicyclic diisocyanates can be used. Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl 4,4'-diphenyl diisocyanate, xylylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and a nuclear hydrogen addition product of a diisocyanate having an aromatic ring therebetween.

The polyol (meth) acrylate constituting the photo-curing resin together with the polyfunctional urethane acrylate is a (meth) acrylate of a compound (that is, a polyol) having at least two hydroxyl groups in the molecule. Specific examples thereof include pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Diol di (meth) acrylate, and the like. The polyol (meth) acrylate may be used alone or in combination of two or more. The polyol (meth) acrylate preferably comprises pentaerythritol triacrylate and / or pentaerythritol tetraacrylate.

The (meth) acrylic polymer having an alkyl group containing two or more hydroxyl groups, which constitutes the photo-curable resin together with these polyfunctional urethane acrylate and polyol (meth) acrylate, has a structure in which two or more hydroxyl groups Containing alkyl group. For example, a polymer containing 2,3-dihydroxypropyl (meth) acrylate as a constituent unit or a polymer containing 2,3-dihydroxypropyl (meth) Acrylate as a constituent unit, and the like.

By using the (meth) acrylic photocurable resin as described above, the adhesiveness to the thermoplastic resin film or the stretched film is improved, the mechanical strength is improved, and the antiglare film Can be obtained.

As the fine particles, it is preferable to use one having an average particle diameter of 0.5 to 5 占 퐉 and a difference in refractive index from cured transparent resin after curing of 0.02 to 0.2. By using fine particles having an average particle diameter and a refractive index difference within this range, it is possible to effectively develop haze. The average particle diameter of the fine particles can be obtained by a dynamic light scattering method or the like. In this case, the average particle diameter is the weight average particle diameter.

The fine particles may be organic fine particles or inorganic fine particles. As the organic fine particles, resin particles are generally used, and examples thereof include crosslinked polyacrylic acid particles, methyl methacrylate / styrene copolymer resin particles, crosslinked polystyrene particles, crosslinked polymethyl methacrylate particles, silicone resin particles, polyimide particles And the like. As the inorganic fine particles, silica, colloidal silica, alumina, alumina sol, aluminosilicate, alumina-silica composite oxide, kaolin, talc, mica, calcium carbonate, calcium phosphate and the like can be used.

As the photopolymerization initiator, various photopolymerization initiators such as acetophenone, benzophenone, benzoin ether, amine, and phosphine oxide may be used. Examples of compounds classified as acetophenone photopolymerization initiators are 2,2-dimethoxy-2-phenylacetophenone (aka benzyldimethyl ketal), 2,2-diethoxyacetophenone, 1- (4-isopropylphenyl) 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-2-morpholino-1- (4-methylthiophenyl) . Examples of compounds classified as benzophenone-based photopolymerization initiators include benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone. Examples of compounds classified as benzoin ether photopolymerization initiators include benzoin methyl ether, benzoin propyl ether. Examples of compounds classified as amine based photopolymerization initiators include N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone (alias Michler ketone). Examples of the phosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. In addition, a xanthone compound or a thioxanthone compound can also be used as a photopolymerization initiator.

These photopolymerization initiators are commercially available. Examples of typical commercial products include "Irgacure 907", "Irgacure 184", and "Lucillin TPO" sold by BASF of Germany.

The curable resin composition may contain a solvent as required. As the solvent, for example, any organic solvent capable of dissolving each component constituting the curable resin composition such as ethyl acetate or butyl acetate can be used. Two or more kinds of organic solvents may be mixed and used.

The curable resin composition may contain a leveling agent, for example, a fluorine-based or silicone-based leveling agent. Silicone leveling agents include reactive silicones, polydimethylsiloxanes, polyether-modified polydimethylsiloxanes, and polymethylalkylsiloxanes. Among silicone leveling agents, preferred are leveling agents based on reactive silicones and siloxanes. When a leveling agent containing reactive silicon is used, slipperiness is imparted to the surface of the antiglare layer, and excellent scratch resistance can be maintained for a long period of time. When a siloxane leveling agent is used, film formability can be improved.

On the other hand, in the case of forming an antiglare layer having a fine surface irregularity shape by the method (embossing method) described in 2) above, the mold having the fine irregularities formed thereon can be used to change the shape of the mold to a thermoplastic resin film or a resin layer . In the case of forming the fine irregular surface shape by the embossing method, the resin layer to which the irregular shape is transferred may contain fine particles or may not contain fine particles. The resin constituting the resin layer is preferably a photo-curing resin as exemplified in the method 1), more preferably an ultraviolet curing resin. However, by appropriately selecting a photopolymerization initiator instead of the ultraviolet ray hardening resin, a visible light hardening resin which can be cured to visible light having a longer wavelength than ultraviolet ray can be used.

In the embossing method, a curable resin composition containing a photo-curable resin such as an ultraviolet ray-curable resin is coated on a (meth) acrylic resin film, and the coated layer is cured while being pressed against the uneven surface of the metal mold, / RTI &gt; More specifically, the curable resin composition is coated on a (meth) acrylic resin film, and light such as ultraviolet rays is irradiated from the (meth) acrylic resin film side in a state in which the coating layer is in contact with the uneven surface of the mold, And then the (meth) acrylic resin film having the coating layer (antiglare layer) after curing is peeled from the mold, thereby transferring the concave-convex shape of the mold to the antiglare layer.

The thickness of the antiglare layer is not particularly limited, but is generally 2 to 30 占 퐉, preferably 3 占 퐉 or more, and more preferably 20 占 퐉 or less. If the antiglare layer is too thin, the hardness tends not to be obtained and the surface tends to be damaged. On the other hand, if the antiglare layer is too thick, it tends to be fragile or the film is curled due to curing shrinkage of the antiglare layer, have.

The haze value of the thermoplastic resin film or stretched film having the antiglare layer is preferably in the range of 5 to 50%. When the haze value is too small, sufficient anti-glare performance can not be obtained, and when a polarizing plate having a thermoplastic resin film or a stretched film having an antiglare layer is applied to an image display apparatus, the projection of external light is likely to occur on the screen. On the other hand, if the haze value is too large, the projection of the external light can be reduced, but the display of black display is reduced. The haze value is a ratio of the diffusion transmittance to the total light transmittance, and is measured in accordance with JIS K 7136: 2000 &quot; Method for determining haze of plastic-transparent material &quot;.

<Polarizer>

A thermoplastic resin film or a stretched film may be disposed on at least one surface of the polarizer as a polarizer protective film to form a polarizing plate. The polarizing plate includes a polarizer and a polarizer protective film disposed on at least one side of the polarizer. It is preferable that the polarizer protective film and the polarizer are bonded.

The polarizer is a step of uniaxially stretching a polyvinyl alcohol thermoplastic resin film according to a known method, a step of staining the polyvinyl alcohol thermoplastic resin film with a dichroic dye to thereby adsorb the dichroic dye, a step of dichroic dye A step of treating the adsorbed polyvinyl alcohol thermoplastic resin film with an aqueous solution of boric acid, and a step of washing with water after treatment with an aqueous solution of boric acid. The thus obtained polarizer has an absorption axis in the uniaxially stretched direction.

As the polyvinyl alcohol-based resin, a saponified polyvinyl acetate-based resin can be used. Examples of the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The saponification degree of the polyvinyl alcohol-based resin is preferably 85 to 100 mol%, more preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehyde may be used. Further, the degree of polymerization of the polyvinyl alcohol-based resin is preferably from 1,000 to 10,000, more preferably from 1,500 to 5,000.

Such a polyvinyl alcohol-based resin film is used as a raw film of a polarizer. The method of forming the polyvinyl alcohol-based resin is not particularly limited and a known method is employed. The film thickness of the polyvinyl alcohol based textile film is preferably 10 to 150 mu m.

The uniaxial stretching of the polyvinyl alcohol thermoplastic resin film can be performed before, simultaneously with, or after dyeing with a dichroic dye. In the case where uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. In addition, uniaxial stretching may be performed at a plurality of these steps.

The uniaxial stretching may be carried out by passing between spaced rolls having different peripheral velocities, or may be performed by sandwiching the rolls with a heat roll. The uniaxial stretching may be dry stretching in which stretching is performed in the air, or wet stretching in which stretching is performed while swelling the polyvinyl alcohol thermoplastic resin film using a solvent such as water or an organic solvent. The stretching magnification is preferably 3 to 8 times.

The dyeing by the dichroic dye of the polyvinyl alcohol thermoplastic resin film can be performed by, for example, a method of immersing a polyvinyl alcohol thermoplastic resin film in an aqueous solution containing a dichroic dye. As the dichroic dye, iodine or a dichroic organic dye is used. It is preferable that the polyvinyl alcohol thermoplastic resin film is immersed in water before the dyeing process.

When iodine is used as the dichroic dye, a method of dying a polyvinyl alcohol thermoplastic resin film in an aqueous solution containing iodine and potassium iodide is generally employed. The content of iodine in the aqueous solution is preferably 0.01 to 1 part by weight per 100 parts by weight of water, and the combined flow rate of potassium iodide is preferably 0.5 to 20 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution used for dyeing is preferably 20 to 40 캜. The immersion time (dyeing time) in this aqueous solution is preferably 20 to 1800 seconds.

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of dying a polyvinyl alcohol-based thermoplastic resin film in an aqueous solution containing a water-soluble dichroic organic dye is generally employed. The content of the dichroic organic dye in the aqueous solution is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 1 part by weight per 100 parts by weight of water. The aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the dichroic dye aqueous solution used for dyeing is preferably 20 to 80 캜. The immersion time (dyeing time) in this aqueous solution is preferably 10 to 1800 seconds.

The boric acid treatment after dyeing with the dichroic dye can be carried out by dipping the dyed polyvinyl alcohol thermoplastic resin film in an aqueous solution containing boric acid. The amount of boric acid in the boric acid-containing aqueous solution is preferably 2 to 15 parts by mass, more preferably 5 to 12 parts by mass per 100 parts by mass of water. When iodine is used as the dichroic dye, it is preferable that the aqueous solution containing boric acid contains potassium iodide. The amount of potassium iodide in the boric acid-containing aqueous solution is preferably 0.1 to 15 parts by weight, more preferably 5 to 12 parts by weight, per 100 parts by weight of water. The immersion time in the boric acid-containing aqueous solution is preferably 60 to 1200 seconds, more preferably 150 to 600 seconds, further preferably 200 to 400 seconds. The temperature of the boric acid-containing aqueous solution is preferably 50 占 폚 or higher, more preferably 50 占 폚 to 85 占 폚, and still more preferably 60 占 폚 to 80 占 폚.

The polyvinyl alcohol-based thermoplastic resin film after boric acid treatment is usually subjected to water washing treatment. The water washing treatment is carried out, for example, by immersing a boric acid-treated polyvinyl alcohol-based thermoplastic resin film in water. The temperature of the water in the water washing treatment is preferably 5 to 40 캜. The immersion time is preferably 1 to 120 seconds.

After washing with water, a drying treatment is carried out to obtain a polarizer. The drying treatment can be performed using a hot-air dryer or a far-infrared heater. The temperature of the drying treatment is preferably 30 to 100 캜, more preferably 50 to 80 캜. The drying treatment time is preferably 60 to 600 seconds, more preferably 120 to 600 seconds.

By the drying treatment, the water content of the polarizer is reduced to a practically acceptable level. The water content thereof is preferably 5 to 20% by weight, more preferably 8 to 15% by weight. If the moisture content is less than 5% by weight, the flexibility of the polarizer is lost, and the polarizer may be damaged or broken after drying. On the other hand, when the moisture content exceeds 20% by weight, the thermal stability of the polarizer may be insufficient.

The thickness of the polarizer in which the dichroic dye is adsorbed and oriented in the polyvinyl alcohol thermoplastic resin film thus obtained is preferably 5 to 40 mu m.

When a polarizer protective film is disposed on one surface of the polarizer, a transparent thermoplastic resin film may be disposed on the other surface. It is preferable that the transparent thermoplastic resin film and the polarizer are bonded in the same manner as in the case of the polarizer protective film and the polarizer. Examples of the transparent thermoplastic resin film include a triacetylcellulose film, a polycarbonate film, a polyethylene terephthalate film, an acrylic thermoplastic resin film, a laminated film of an acrylic resin and a polycarbonate resin, an olefinic thermoplastic resin film, .

It is preferable to use an adhesive for bonding the polarizer protective film and the polarizer and for bonding the polarizer and the transparent thermoplastic resin film. By using an adhesive, the polarizer protective film, the polarizer and the polarizer, and the transparent thermoplastic resin film are bonded to each other through the adhesive layer. Prior to the bonding, it is preferable that at least one of the bonding surfaces is subjected to a corona discharge treatment, a plasma irradiation treatment, an electron beam irradiation treatment, and other surface activation treatment.

The adhesive for forming the adhesive layer may be arbitrarily selected from those which exhibit an adhesive force with respect to each member. Typically, an aqueous adhesive, that is, an active energy ray-curable adhesive containing a component dissolved in water or an adhesive component dispersed in water, or a component cured by irradiation with an active energy ray can be mentioned. Among these, from the viewpoint of productivity, an active energy ray-curable adhesive is preferable.

As the water-based adhesive, for example, a composition using a polyvinyl alcohol-based resin or urethane resin as a main component may be mentioned as a preferable adhesive.

When a polyvinyl alcohol-based resin is used as the main component of the water-based adhesive, examples of the polyvinyl alcohol-based resin include, for example, partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetoacetyl- And modified polyvinyl alcohol-based resins such as alcohol, methylol modified polyvinyl alcohol, and amino-modified polyvinyl alcohol. When a polyvinyl alcohol-based resin is used as an adhesive component, the adhesive is often produced as an aqueous solution of a polyvinyl alcohol-based resin. The concentration of the polyvinyl alcohol-based resin in the aqueous adhesive solution is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of water.

In order to improve the adhesiveness, it is preferable to add a curing component such as glyoxal or a water-soluble epoxy resin or a crosslinking agent to an aqueous adhesive containing a polyvinyl alcohol resin as a main component. Examples of water-soluble epoxy resins include polyamides obtained by reacting epichlorohydrin with polyamide polyamines obtained by the reaction of polyalkylene polyamines such as diethylene triamine and triethylene tetramine with dicarboxylic acids such as adipic acid And polyamine epoxy resins. As the polyamide polyamine epoxy resin, a commercially available product may be used. For example, "Sumirez Resin 650" and "Sumirez Resin 675" manufactured by Sumika Chemicals Co., And the like. The amount of the curable component or crosslinking agent to be added is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, based on 100 parts by weight of the polyvinyl alcohol-based resin. When the addition amount is small, the adhesive property improving effect is small. On the other hand, when the addition amount is large, the adhesive layer may become brittle.

When a urethane resin is used as a main component of the water-based adhesive, a mixture of a polyester-based ionomeric urethane resin and a compound having a glycidyloxy group can be mentioned as an example of a suitable adhesive composition. The polyester-based ionomer-type urethane resin referred to herein is a urethane resin having a polyester skeleton, and a small amount of an ionic component (hydrophilic component) is introduced into the urethane resin. The ionomeric urethane resin is preferably used as an aqueous adhesive since it emulsifies directly in water without using an emulsifier to form an emulsion.

When an activating energy ray-curable adhesive is used, examples of the component (hereinafter, simply referred to as &quot; curable component &quot;) that is cured by irradiation of an active energy ray constituting the activating energy ray include an epoxy compound, an octacene compound, have. When a cationic polymerizable compound such as an epoxy compound or an octacene compound is used, a cationic polymerization initiator is incorporated. When a radical polymerizable compound such as an acrylic compound is used, a radical polymerizable initiator is blended. Among them, an adhesive that makes the epoxy compound one of the curable components is preferable, and an adhesive that makes the alicyclic epoxy compound having the epoxy group directly bonded to the saturated carbon ring as one of the curable components is more preferable. It is also possible to use an oxetane compound in combination therewith.

As the epoxy compound, commercially available products can be used. Examples thereof include "Epicoat" series manufactured by Japan Epoxy Resin Co., Ltd., "Epiclon" series manufactured by DIC Corporation, "Epotohto" manufactured by TODO KASEI KABUSHIKI Co., Series manufactured by Nippon Kayaku Co., Ltd., "Adeka Resin" series manufactured by Adeka Corporation, "Denacol" series manufactured by Nagase Chemtex Co., Ltd., "Dow Epoxy" series manufactured by Dow Chemical Co., &Quot; Tepic &quot;

As the alicyclic epoxy compound having a direct epoxy group bonded to the saturated carbon ring, commercially available products may be used. For example, a &quot; celloxide &quot; series and a &quot; cychroma &quot; series manufactured by Daicel Chemical Industries, &Quot; Sara Cure &quot;

As the oxetane compound, a commercially available product may be used, for example, "AARON OXETAN" series manufactured by Toagosei Co., Ltd. and "ETERNACOLL" series manufactured by UBE CORPORATION.

As the cationic polymerization initiator, commercially available products can be used. For example, a cationic polymerization initiator such as a "Kaya Rad" series manufactured by Nippon Kayaku Kabushiki Kaisha, a "Sara Cure" series manufactured by Union Carbide, "CPA" series, "TAZ", "BBI" and "DTS" which are photoacid generators manufactured by Midori Kagaku Co., Ltd., "Adeka Optomer" series manufactured by Adeka Co., Ltd., "Rodosil RHODORSIL &quot; series.

The active energy ray-curable adhesive may contain a photosensitizer as required. By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured layer can be further improved. Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfates, redox compounds, azo and diazo compounds, anthracene compounds, halogen compounds, and light reducing pigments.

Various kinds of additives may be added to the active energy ray-curable adhesive within a range that does not impair the adhesiveness thereof. Examples of the additive include ion trapping agents, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, defoamers and the like. In addition, a curing component that is cured by a reaction mechanism other than the cation polymerization may be added within a range that does not impair the adhesiveness.

The above-mentioned active energy ray-curable adhesive may have the same composition or different compositions, but it is preferable to conduct the irradiation of active energy rays for curing the both at the same time.

Examples of the active energy ray include X-rays, ultraviolet rays, visible rays, and the like. Among them, ultraviolet rays are preferable from the viewpoints of easiness of use, easiness of production of active energy ray-curable adhesive, stability and curing performance. Examples of ultraviolet light sources include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, chemical lamps, black light lamps, microwave excited mercury lamps, and metal halide lamps.

The thickness of the adhesive layer obtained by using the active energy ray-curable adhesive is preferably 1 to 50 mu m, more preferably 1 to 10 mu m.

The polarizing plate can be a liquid crystal panel bonded to a liquid crystal cell and used in a liquid crystal display device. It is preferable that the polarizing plate and the liquid crystal cell are bonded to each other through a pressure-sensitive adhesive layer using a pressure-sensitive adhesive. The pressure-sensitive adhesive layer is generally formed of an acrylic pressure-sensitive adhesive having acrylic acid ester as a main component and an acrylic resin copolymerized with an acrylic monomer containing a functional group as a pressure-sensitive adhesive component. A liquid crystal panel in which a polarizing plate is bonded to a liquid crystal cell via a pressure-sensitive adhesive layer can be used for a liquid crystal display device.

<Examples>

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples.

Various physical properties of the obtained resin composition were measured and evaluated by the following methods.

&Lt; Glass transition temperature (Tg) >

According to JIS K7121: 1987, the extrapolated glass transition intermediate temperature measured at a heating rate of 10 캜 / minute by differential scanning calorimetry was defined as a glass transition temperature (Tg).

&Lt; Temperature at which the shear viscosity becomes ₂₅₀₀ Pa · s (T ₂₅₀₀ )>

The shear rate was fixed at 60 sec ^-1 using a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd., barrel radius: 9.55 mmφ, capillary L / D: 10) to measure, to obtain a relational expression between shear viscosity and temperature, from the equation shear rate of 60sec ^- the shear viscosity of the resin composition in the ^first calculated the temperature T is ₂₅₀₀ to 2500Pa · s. In addition, the relational expression is an approximate expression of the measurement result by an exponential function, and a least squares method is applied to the expression.

(Synthesis Example 1: Synthesis of acrylic resin)

As shown in Table 1, a monomer component was obtained by mixing 79.0 wt% methyl methacrylate (MMA), 20.0 wt% cyclohexyl methacrylate (CHMA), and 1.0 wt% methyl acrylate (MA). 0.2 part by weight of lauryl peroxide was added as a polymerization initiator to 100 parts by weight of the monomer component and 1-dodecylmercaptan as a chain transfer agent was added in an amount of 0.50 part by weight based on 100 parts by weight of the monomer component, A mixture was obtained. On the other hand, to the ion-exchanged water, 0.05 part by weight of sodium polyacrylate as a suspension stabilizer with respect to 100 parts by weight of ion-exchanged water, 0.24 parts by weight of sodium monophosphate anhydrous with respect to 100 parts by weight of ion- And 0.28 parts by weight of a heptahydrate were added to 100 parts by weight of ion exchange water, and these were dissolved to obtain a suspension polymerization water (water) phase. Subsequently, 150 parts by weight of the monomer mixture was added to 100 parts by weight of the suspension polymerization aqueous monomer component, and suspension polymerization was carried out. The reaction liquid on the obtained slurry was dehydrated and washed with a dehydrator, and then dried to obtain an acrylic resin beads. Table 1 shows the weight average molecular weights (Mw) of the acrylic resin obtained by GPC measurement and calculated as polymethyl methacrylate.

(Synthesis Examples 2 to 3: Synthesis of acrylic resin)

An acrylic resin in the form of pellets was obtained in the same procedure as in Synthesis Example 1, except that the components listed in Table 1 were used in the ratios shown in Table 1. The weight average molecular weight (Mw) of the obtained acrylic resin is shown in Table 1.

Table 2 shows the weight average molecular weight (Mw) and MVR of the polycarbonate resin (PC) used. All of these are polycarbonates from Sumikastaron Polycarbonate Corporation. Hereinafter, as shown in Table 2, Gulliver 301-40 may be abbreviated as PC-40 in some cases. Table 2 shows the weight average molecular weights (Mw) of the obtained polycarbonate resins obtained by GPC measurement and calculated in terms of polystyrene.

(Example 1: Production of resin composition)

As shown in Table 3, 70 parts by weight of the acrylic resin obtained in Synthesis Example 1 and 30 parts by weight of polycarbonate resin (PC-15) were mixed and kneaded in a twin-screw kneading extruder (Nippon Shekou Co., Ltd., TEX And the ratio (L / D) of the screw length (L) to the screw diameter (D) was -30 SS, the screw temperature was 250 ° C and the number of revolutions was 100 rpm. The melt was extruded into a strand shape, cooled, and cut with a strand cutter to obtain a pellet-shaped resin composition. Tg and T ₂₅₀₀ were determined for the obtained resin composition. Further, the value of (1.5 x MVR _pc x W _a x W _a ) / (W _b W _b ) +245 was calculated for the obtained resin composition. The results are shown in Table 3.

(Examples 2 to 5 and Comparative Example 1: Production of Resin Composition)

A pellet-shaped resin composition was obtained in the same procedure as in Example 1, except that the components listed in Table 3 were used in the ratios shown in Table 3. Tg and T ₂₅₀₀ were determined for the obtained resin composition. Further, the value of (1.5 x MVR _pc x W _a x W _a ) / (W _b W _b ) +245 was calculated for the obtained resin composition. The results are shown in Table 3.

(Examples 1 to 5 and Comparative Example 1: Production of thermoplastic resin film)

Each of the obtained resin compositions was melt-kneaded by a single screw extruder equipped with a vent having a screw diameter of 65 mm, and the molten resin was supplied to the T die. The temperature of the T die was set to a temperature not exceeding the value of the result of the calculation of the resin composition described in Table 3 (except for Comparative Example 1), with the T die temperature described in Table 4. Subsequently, the supplied molten resin is extruded continuously from the T-die into a film and the molten resin continuously extruded from the T-die is sandwiched between rolls of a metal having a smooth surface and molded and cooled To obtain a thermoplastic resin film having a thickness of 120 占 퐉. With respect to the obtained thermoplastic resin film, the total light transmittance (Tt) was measured by the following method. The results are shown in Table 4.

&Lt; Total light transmittance (Tt) >

The total light transmittance (Tt) was measured in accordance with JIS K7361-1 using a transmittance meter (HR-100, manufactured by Murakami Color Research Laboratory Co., Ltd.).

(Examples 1 to 5 and Comparative Example 1: Production of biaxial oriented film)

Each of the obtained thermoplastic resin films was subjected to biaxial stretching. First, each thermoplastic resin film was passed between two pairs of nip rolls provided before and after the hot air circulation type furnace to perform longitudinal drawing. The first region at the inlet side is at room temperature, the second region thereafter is at the same temperature as the Tg of each resin composition, the third region thereafter, and the second region after the outlet region, Side was set at a temperature 10 DEG C higher than Tg. The length of the film passing through the nip roll on the inlet side was 2 mm / min, and the speed of the film passing through the nip roll on the exit side was 4.4 mm / min. .

Subsequently, the prepared longitudinally stretched film was cut so that its longitudinal length was 1 m, and a longitudinally stretched film having a length of 1 m was obtained. A longitudinally stretched film having a length of 1 m in the longitudinal direction was introduced into a tenter transverse stretching machine Transverse stretching was performed. The transverse stretching was carried out in a hot-air circulating furnace having a length of 4 m, and the furnace temperature was set at a temperature 10 캜 higher than Tg. The speed of passing through the furnace was 1 mm / min, and the draw ratio was doubled. Thus, a biaxially oriented film having a longitudinal stretching magnification of 2.2, a transverse stretching magnification of 2, and a thickness of 40 m was obtained. The high-temperature tensile modulus of elasticity of the obtained biaxially stretched film was measured by the following method. The results are shown in Table 4.

&Lt; High temperature tensile modulus &

A tensile test at 80 DEG C was conducted on each of the biaxially stretched films to measure the tensile modulus at high temperature. The biaxially stretched film was cut into a rectangle having a length of 120 mm in the longitudinal direction and a length of 25 mm in the transverse direction with the longitudinal stretching direction as the long side and the tensile test was carried out at a stretching speed of 5 mm / . The high temperature tensile modulus of elasticity was calculated from the slope of the stress-strain curve in the region where the tensile strength was 3 MPa to 6 MPa. The higher the high temperature tensile modulus of elasticity is, the more difficult it is to shrink in a high temperature environment.

(Production of hardenable paint)

25 parts of dipentaerythritol hexaacrylate (&quot; NK Ester A-DPH &quot; manufactured by Shin-Nakamura Chemical Co., Ltd.), 25 parts of a photopolymerization initiator (IRGACURE 184 manufactured by Ciba Specialty Chemicals Co., ), 10 parts of an antimony pentoxide pentoxide sol ("ELCOM V-4514" manufactured by Shokuba Kasei Kogyo Co., Ltd., solid concentration 20%), 24 parts of 1-methoxy-2-propanol, 24 parts of alcohol and 15 parts of diacetone alcohol were mixed to prepare a curing paint.

(Examples 1 to 5 and Comparative Example 1: Production of hard coat film)

Each of the obtained biaxially stretched films was cut into a size of 300 mm x 200 mm and a coating film of a curable paint was formed on one side by a bar coating method. Subsequently, the film was dried at room temperature for one minute and further dried in a hot air oven at 50 DEG C for 3 minutes to volatilize the solvent. The coating film was irradiated with ultraviolet rays of 0.5 J / cm2 using a high pressure mercury lamp of 120 W To obtain a hard coating film which was a thermoplastic resin film having a hard coat layer having a thickness of 3.5 mu m on one side. The obtained hard coat film was evaluated for toughness by the following method. The results are shown in Table 4.

<Bending crack resistance>

In order to evaluate the toughness of the hard coating film, a bending crack resistance test was conducted. The resultant hard coating film was folded with the fingers on the outside with the cured coating formed on the outside, and the case where the hard coating film was not broken was evaluated as &amp; cir &amp; and the case where the hard coating film was broken was evaluated as x.

Claims (11)

A resin composition containing an acrylic resin and a polycarbonate resin in an amount of 50 to 95% by weight of an acrylic resin and 5 to 50% by weight of a polycarbonate resin based on 100% by weight of the total of the acrylic resin and polycarbonate resin A thermoplastic resin film,
Wherein the acrylic resin comprises 50 to 95% by weight of methyl methacrylate and 50 to 95% by weight of the following structural formula (I) based on 100% by weight of the total of the monomer components:

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, an alkyl group substituted with a naphthyl group, a naphthyl group, a naphthyl group substituted with an alkyl group , An alkyl group substituted with a phenyl group, a phenyl group, a phenyl group substituted with an alkyl group, a dicyclopentanyl group or a dicyclopentenyl group)
And 5 to 50% by weight of a (meth) acrylic acid ester represented by the following general formula (1) and 0.1 to 20% by weight of a monofunctional monomer other than these:
A temperature T ₂₅₀₀ (占 폚) at which the shear viscosity of the resin composition at a shear rate of 60 sec ^-1 becomes ₂₅₀₀ Pa 占 퐏 is represented by the following formula (a)

(Wherein MVR _pc represents the melt volume ratio of the polycarbonate resin at 300 ° C, and W _a represents the weight percentage of the (meth) acrylic acid ester represented by the formula (I) in the monomer component And W _b represents the weight percentage of the polycarbonate resin in the resin composition)
By weight of the thermoplastic resin film. The thermoplastic resin film according to claim 1, wherein the acrylic resin has a weight average molecular weight of 50,000 to 200,000. The composition according to claim 1 or 2, wherein the (meth) acrylic acid ester represented by the formula (I) is at least one selected from cyclohexyl methacrylate, phenyl methacrylate, naphthyl methacrylate, dicyclopentanyl methacrylate and dicyclohexyl methacrylate And pentenyl. The thermoplastic resin film according to claim 1, wherein the thermoplastic resin film is a thermoplastic resin film. The thermoplastic resin film according to any one of claims 1 to 3, wherein the monofunctional monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. The thermoplastic resin film according to any one of claims 1 to 4, which is produced by melt co-extrusion molding. The thermoplastic resin film according to any one of claims 1 to 5, which has a surface treatment layer on at least one side. A stretched film obtained by stretching the thermoplastic resin film according to any one of claims 1 to 5. The stretched film according to claim 7, further comprising a surface treatment layer on at least one side. A polarizer protective film comprising the thermoplastic resin film according to any one of claims 1 to 6. 9. A polarizer protective film comprising the stretched film according to claim 7 or 8. A polarizer comprising the polarizer and the polarizer-protective film according to claim 9 or 10, which is disposed on at least one side of the polarizer.