KR20170089916A - Resin composition, film and display device - Google Patents

Abstract

Provided is a resin composition capable of forming a film having a high dielectric constant and capable of maintaining transparency even when used for a long time under a high temperature and high humidity environment. (Meth) acrylic resin and vinylidene fluoride resin, wherein the (meth) acrylic resin and the vinylidene fluoride resin are contained in an amount of 35 to 45% by mass and the vinylidene fluoride resin And the weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000, at least one of the resins contained in the resin composition contains an alkali metal and is contained in the resin composition Wherein the content of the alkali metal is 50 ppm or less per 100 parts by mass of the total amount of the resin and the alkali metal.

Description

RESIN COMPOSITION, FILM AND DISPLAY DEVICE,

The present invention relates to a resin composition, a film, and a display device.

2. Description of the Related Art In recent years, a display device such as a smart phone, a portable game machine, an audio player, and a tablet terminal has been increasingly equipped with a touch screen. Although a glass sheet is usually used on the surface of such a display device, a plastic sheet which is a substitute for a glass sheet has been developed in view of the tendency of the display device to be lightweight and the workability. For example, Patent Document 1 discloses a transparent sheet comprising a methacrylic resin and a vinylidene fluoride resin as a plastic sheet to be a substitute for a glass sheet, and the transparent sheet satisfies transparency and relative dielectric constant sufficiently .

On the other hand, display devices have recently been required to have durability in harsh environments such as high temperature and high humidity, because they are used in various environments from their high versatility.

Japanese Unexamined Patent Application Publication No. 2013-244604

The conventional transparent sheet as described in Patent Document 1, for example, is sometimes opaque in a high temperature and high humidity environment such as a temperature of 60 ° C. and a relative humidity of 90%, and there is room for improvement in durability.

The present invention has been made in view of the above problems. That is, the present invention includes the invention described in the following [1] to [20].

[1] A resin composition comprising a (meth) acrylic resin and a vinylidene fluoride resin,

(Meth) acrylic resin and 65 to 55% by mass of a vinylidene fluoride resin per 100 mass% of the total of the (meth) acrylic resin and the vinylidene fluoride resin, and the (meth) acrylic resin Has a weight average molecular weight (Mw) of 100,000 to 300,000,

Wherein at least one of the resins contained in the resin composition contains an alkali metal and the content of the alkali metal is 50 ppm or less per 100 parts by mass of the total amount of the resin and the alkali metal contained in the resin composition.

[2] The resin composition according to [1], wherein the (meth) acrylic resin is the resin (a1) or (a2)

(a1) a homopolymer of methyl methacrylate,

(a2) a structural unit derived from methyl methacrylate in an amount of 50 to 99.9 mass%

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₁ is R _2, when one hydrogen atom is represents an alkyl group having 1 to 8 carbon atoms, when the R ₁ group R ₂ represents an alkyl group having a carbon number of 2 to 8 .)

And 0.1 to 50 mass% of at least one structural unit derived from a (meth) acrylic acid ester represented by the following general formula (1).

[3] The resin composition according to [1] or [2], wherein the weight average molecular weight (Mw) of the (meth) acrylic resin is 120,000 to 250,000.

[4] The resin composition according to any one of [1] to [3], wherein the vinylidene fluoride resin is polyvinylidene fluoride.

[5] The resin composition according to any one of [1] to [4], wherein the vinylidene fluoride resin has a melt mass-flow rate of 0.1 to 30 g / 10 min.

[6] The resin composition according to any one of [1] to [5], further comprising a colorant.

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

[8] A film according to [7], wherein the thickness is 100 to 2000 μm.

[9] A film according to [7] or [8], further comprising a thermoplastic resin layer.

[10] A film according to any one of [7] to [9], wherein a thermoplastic resin layer is provided on both sides of a layer formed of a resin composition.

[11] The film according to [9] or [10], wherein the thermoplastic resin layer is a (meth) acrylic resin layer or a polycarbonate resin layer.

[12] The film according to any one of [9] to [11], wherein the thermoplastic resin layer is a layer formed of a resin containing 50 parts by mass or more of a (meth) acrylic resin per 100 parts by mass of the total resin forming the thermoplastic resin layer. .

[13] A film according to [11] or [12], wherein the (meth) acrylic resin contained in the thermoplastic resin layer has a weight average molecular weight of 50,000 to 300,000.

[14] The membrane described in any one of [9] to [13], wherein the thermoplastic resin layer has a thickness of 10 to 200 μm.

[15] The membrane described in any one of [9] to [14], wherein the thermoplastic resin layer has a Vicat softening temperature of 100 to 160 ° C.

[16] A film comprising a (meth) acrylic resin and a vinylidene fluoride resin, wherein when the film is exposed for 120 hours under an environment of 60 ° C. and a relative humidity of 90%, haze of the film is not more than 2% Or more.

[17] The optical information recording medium according to any one of [7] to [16], further comprising a coating layer for imparting at least one function selected from the group consisting of scratch prevention, antireflection, antiglare, ≪ / RTI >

[18] A display device comprising the film described in any one of [7] to [17].

[19] A polarizing plate with a film laminated with the film according to any one of [7] to [17] and a polarizing plate.

[20] A display device comprising the polarizer with a film according to [19].

The layer formed from the resin composition of the present invention and the film containing the same can be used as a front plate of a display device because they can maintain transparency even when used for a long time under a high temperature and high humidity environment while having a high dielectric constant.

1 is a schematic view of an apparatus for producing a membrane of the present invention used in Examples.
2 is a schematic cross-sectional view showing an example of a layer structure of one preferred form of the liquid crystal display device according to the present invention.

<Resin composition>

The resin composition of the present invention is a resin composition comprising at least a (meth) acrylic resin and a vinylidene fluoride resin, and contains a (meth) acrylic resin and a (meth) acrylic resin per 100 mass% (Meth) acrylic resin has a weight average molecular weight (Mw) of 100,000 to 300,000, and a vinylidene fluoride resin, At least one of the resins contained in the resin composition contains an alkali metal, and the content of the alkali metal is 100 ppm or less per 100 parts by mass of the total resin and the alkali metal contained in the resin composition. Hereinafter, the present invention will be described.

The resin composition preferably contains 37 to 45% by mass of a (meth) acrylic resin and 55 to 63% by mass of a vinylidene fluoride resin per 100 mass% of the total of the (meth) acrylic resin and the vinylidene fluoride resin, (Meth) acrylic resin, 38 to 43% by mass of a (meth) acrylic resin, and 57 to 62% by mass of a vinylidene fluoride resin do. In addition to the (meth) acrylic resin and the vinylidene fluoride resin, the resin composition may contain other resins as long as the transparency is not impaired.

At least one of the resins contained in these resin compositions contains an alkali metal. The alkali metal may be, for example, sodium or potassium derived from an emulsifier remaining in the resin when the (meth) acrylic resin or the vinylidene fluoride resin is obtained by emulsion polymerization. The smaller the content of the alkali metal is, the more preferable that the film containing the layer formed of the resin composition tends not to be lowered in transparency when it is used for a long time under an environment of high temperature and high humidity.

The content of the alkali metal is usually 50 ppm or less per 100 parts by mass of the total amount of all resins and alkali metals contained in the resin composition. The content of the alkali metal is preferably 30 ppm or less, more preferably 10 ppm or less, still more preferably 1 ppm or less, particularly preferably substantially no content. In order to keep the content of the alkali metal in the resin within the above range, the amount of the alkali metal-containing compound used in polymerization of the resin may be reduced, or the cleaning process after polymerization may be increased to remove the alkali metal-containing compound. The content of the alkali metal can be determined, for example, by inductively coupled plasma mass spectrometry (ICP / MS). As the inductively coupled plasma mass spectrometry, for example, the sample pellets to be measured are subjected to an appropriate method such as a high-temperature ashing melting method, a high-temperature painting acid dissolution method, a Ca addition painting acid dissolution method, a combustion absorption method, By measuring the amount of alkali metal by inductively coupled plasma mass spectrometry, the sample can be analyzed by dissolving it in an acid, and this solution can be determined.

((Meth) acrylic resin)

Examples of the (meth) acrylic resin include homopolymers of (meth) acrylic monomers such as (meth) acrylic acid esters and (meth) acrylonitrile, copolymers of two or more (meth) acrylic monomers, And copolymers of monomers other than monomers. In the present specification, the term "(meth) acrylic" means "acrylic" or "methacryl".

 As the (meth) acrylic resin, methacrylic resin is preferably used because it has excellent hardness, weather resistance, transparency and the like. The methacrylic resin is a polymer of a monomer mainly composed of methacrylic acid ester (alkyl methacrylate), and includes, for example, a homopolymer of methacrylic acid ester (polyalkyl methacrylate), two or more methacrylic acid esters , Copolymers of 50 mass% or more of methacrylic acid ester and 50 mass% or less of methacrylic acid ester and other monomers. In the case of a copolymer of a methacrylate ester and a monomer other than a methacrylate ester, the methacrylate ester is preferably 70% by mass or more based on the total amount of the monomers, and the other monomer is 30% More preferably, the methacrylate ester is 90 mass% or more, and the other monomer is 10 mass% or less.

Examples of the monomer other than the methacrylic acid ester include an acrylic acid ester and a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule.

Examples of monofunctional monomers include styrene monomers such as styrene,? -Methylstyrene and vinyltoluene; Cyanated alkenyl such as acrylonitrile and methacrylonitrile; Acrylic acid; Methacrylic acid; Maleic anhydride; N-substituted maleimides; And the like. Further, from the viewpoint of heat resistance, N-substituted maleimide such as phenylmaleimide, cyclohexylmaleimide and methylmaleimide may be copolymerized, and a lactone ring in the molecular chain (also referred to as main chain or main chain in the polymer) Structure, a glutaric anhydride structure, or a glutarimide structure may be introduced.

As the (meth) acrylic resin, more specifically, it is preferably a resin of the following (a1) or (a2).

(a1) a homopolymer of methyl methacrylate.

(a2) a copolymer comprising 50 to 99.9 mass% of a structural unit derived from methyl methacrylate, and 0.1 to 50 mass% of at least one structural unit derived from a (meth) acrylic acid ester represented by the following formula (1). Here, the content of the structural unit can be calculated by analyzing the obtained polymer by pyrolysis gas chromatography and measuring the peak area corresponding to each monomer.

In the formula _(1), R 1 is a hydrogen atom or a methyl group, R ₁ is when the hydrogen atom R ₂ represents an alkyl group having 1 to 8 carbon atoms, when the R ₁ group R ₂ has a carbon number of 2 to 8 Alkyl group. Examples of the alkyl group having 2 to 8 carbon atoms represented by R ₂ include an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group .

(Meth) acrylic resin has a melt mass flow rate (hereinafter sometimes referred to as MFR) at 230 캜, which is measured at a load of 3.8 kg, is usually 0.1 to 20 g / 10 min, 5 g / 10 min, and more preferably 0.5 to 3 g / 10 min. If the MFR is too large, the strength of the resulting film tends to decrease. If the MFR is too small, the film-forming property tends to decrease. The MFR can be measured in accordance with the method specified in JIS K 7210: 1999 "Testing method of melt-mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastics". For the poly (methyl methacrylate) type material, measurement at a temperature of 230 캜 and a load of 3.80 kg (37.3 N) is prescribed in this JIS.

The (meth) acrylic resin preferably has a weight average molecular weight (hereinafter sometimes referred to as Mw) of 100,000 to 300,000, more preferably 120,000 to 250,000, and 150,000 to 200,000, as measured by GPC More preferable. The larger the Mw is, the higher the transparency of the obtained film when exposed under a high-temperature and high-humidity environment such as 60 ° C and a relative humidity of 90%. However, if it is too large, the film-forming property tends to decrease.

The (meth) acrylic resin preferably has a Vicat softening temperature (hereinafter sometimes referred to as VST) of 90 ° C or higher, more preferably 100 ° C or higher, more preferably 102 ° C or higher, from the viewpoint of heat resistance Do. The VST can be measured by the B50 method described in accordance with JIS K 7206: 1999. VST can be appropriately set by adjusting the kind and the ratio of the monomers.

 The (meth) acrylic resin can be prepared by polymerizing the above monomers by a known method such as suspension polymerization or bulk polymerization. At that time, MFR, Mw, VST, etc. can be adjusted to a desirable range by adding a suitable chain transfer agent. As the chain transfer agent, a suitable commercially available product can be used. The amount of the chain transfer agent to be added may be appropriately determined depending on the type and proportion of the monomers, the desired characteristics, and the like. The obtained (meth) acrylic resin preferably has a low alkali metal content. The content of the alkali metal can be adjusted by reducing the amount of the alkali metal-containing compound used during polymerization or by increasing the number of cleaning steps after polymerization to remove the alkali-metal-containing compound.

(Vinylidene fluoride resin)

The vinylidene fluoride resin is preferably at least one selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and ethylene, from the viewpoint of transparency of the obtained film. A polymer obtained by copolymerizing a monomer of the species with vinylidene fluoride, and a polymer (polyvinylidene fluoride) obtained by polymerizing vinylidene fluoride alone, and preferably polyvinylidene fluoride.

The vinylidene fluoride resin has a melt mass flow rate (MFR) of usually from 0.1 to 30 g / 10 min, preferably from 0.1 to 25 g / 10 min, at 230 캜, which is measured at a load of 3.8 kg. The lower limit of the MFR is more preferably 0.2 g / 10 min, and more preferably 0.5 g / 10 min. The upper limit of the MFR is more preferably 20 g / 10 min, more preferably 5 g / 10 min, and particularly preferably 2 g / 10 min. If the MFR is too large, the transparency tends to decrease when the obtained film is used for a long period of time. If the MFR is too small, the film-forming property tends to decrease.

The vinylidene fluoride resin preferably has a weight average molecular weight (Mw) measured by GPC measurement of 100,000 to 500,000, more preferably 150,000 to 450,000, further preferably 200,000 to 450,000, and most preferably 350,000 to 450,000 Particularly preferred. The larger the Mw is, the higher the transparency of the obtained film when exposed under a high temperature and high humidity environment of 60 DEG C and a relative humidity of 90%. When the Mw is too large, the film forming property tends to decrease.

The vinylidene fluoride resin is industrially produced by cation polymerization or emulsion polymerization. The suspension polymerization is carried out by using water as a medium, dispersing the monomer as a dispersant in a medium as droplets, and polymerizing the organic peroxide dissolved in the monomer as a polymerization initiator, and a granular polymer having a particle size of 100 to 300 μm . The suspension polymer is preferable because it is simple in the production process as compared with the emulsion polymer, has excellent handleability of the powder, and does not contain an emulsifier or salting agent containing an alkali metal such as an emulsion polymer. It is preferable that the obtained vinylidene fluoride resin has a low alkali metal content. The content of the alkali metal can be adjusted by reducing the amount of the alkali metal-containing compound used during polymerization or by increasing the number of cleaning steps after polymerization to remove the alkali-metal-containing compound.

As the vinylidene fluoride resin, a commercially available product may be used. Examples of preferred commercially available products include T # 1300, T # 1100, T # 1000, T # 850, W # 850, W # 1000, W # 1100 and W # 1300 of KF Polymer (registered trademark) 6012, 6010 and 6008 of "SOLEF (registered trademark)" of Solvay (trade name).

(Other additives)

Various additives generally used may be added to the resin composition of the present invention within a range that does not impair the effect of the present invention. Examples of additives include additives such as stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, lubricants, release agents, antistatic agents, flame retardants, release agents, polymerization inhibitors, flame retarding agents, reinforcing agents, nucleating agents, And the like.

Examples of the colorant include a compound having an anthraquinone skeleton and a compound having a phthalocyanine skeleton. Among them, a compound having an anthraquinone skeleton is preferable from the viewpoint of heat resistance.

When the resin composition contains a coloring agent, the content of the coloring agent in the resin composition can be appropriately selected depending on the purpose, kind of the coloring agent, and the like. When a bluing agent is used as the coloring agent, the content thereof may be about 0.01 to 10 ppm per 100 parts by mass of the resin composition. The content thereof is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, still more preferably 7 ppm or less, still more preferably 5 ppm or less, still more preferably 4 ppm or less, And preferably 3 ppm or less. The blueing agent may be any of those known in the art and may be suitably used, for example, under the trade names of Mark Rolex (registered trademark) Blue RR (manufactured by Bayer), Markorox (registered trademark) Blue 3R (manufactured by Bayer), Sumiplast Diaresin Violet D, Diaresin Blue G and Diaresin Blue N (all manufactured by Mitsubishi Chemical Corporation) can be used.

These additives may be contained in a resin such as a (meth) acrylic resin or a vinylidene fluoride resin, or may be added at the time of melt-kneading a (meth) acrylic resin and a vinylidene fluoride resin to be described later, May be added after the melt-kneading of the vinylidene fluoride resin, or may be added at the time of producing the film using the resin composition.

The resin composition of the present invention is usually obtained by kneading a (meth) acrylic resin and a vinylidene fluoride resin. Such kneading can be carried out by, for example, a method including a step of melting and kneading at a temperature of 150 to 350 DEG C at a shear rate of 10 to 1000 / sec.

If the temperature at the time of melt kneading is less than 150 캜, there is a fear that the resin is not melted. On the other hand, when the temperature at the time of performing melt kneading exceeds 350 DEG C, the resin may be thermally decomposed. If the shear rate when the melt kneading is performed is less than 10 / sec, there is a fear that the kneading is not sufficiently performed. On the other hand, when the shearing rate at the time of melt kneading exceeds 1000 / sec, the resin may be decomposed.

In order to obtain a resin composition in which each component is more uniformly mixed, melt kneading is preferably performed at a temperature of 180 to 300 캜, more preferably 200 to 300 캜, preferably 20 to 700 / Lt; RTI ID = 0.0 &gt; 30/500 / sec. &Lt; / RTI &gt;

As a device used for melt kneading, a usual mixer or kneader can be used. Specific examples thereof include a uniaxial kneader, a twin-screw kneader, a twin-screw extruder, a Henschel mixer, a Banbury mixer, a kneader, and a roll mill. When the shear rate is increased within the above range, a high-shear machining apparatus or the like may be used.

<Act>

The film of the present invention preferably includes a layer formed from the resin composition of the present invention (hereinafter sometimes referred to as A layer), and may be a single layer film of A layer, It may be a film of two or more layers. The thickness of the film is preferably 500 to 2000 占 퐉, more preferably 500 to 1500 占 퐉, still more preferably 100 to 1500 占 퐉, and particularly preferably 100 to 1000 占 퐉.

This film preferably further comprises a thermoplastic resin layer from the viewpoints of heat resistance, surface hardness, and adhesion with a coating layer described later. The thermoplastic resin layer may be laminated on at least one side of the layers formed of the resin composition of the present invention and may be laminated via another layer. However, the thermoplastic resin layer is in contact with the layer formed of the resin composition of the present invention, It is preferable to be laminated. From the viewpoint of maintaining the shape of the film, it is preferable to include a thermoplastic resin layer on both surfaces of the A layer contained in the film.

The thickness of the thermoplastic resin layer is preferably 10 to 200 mu m, more preferably 50 to 150 mu m. When the thermoplastic resin layer is included in both surfaces of the layer A contained in the film, the thickness and the composition of each thermoplastic resin layer may be the same or different from each other, but are preferably substantially the same as each other from the viewpoint of maintaining the film shape.

The thermoplastic resin layer is formed of a thermoplastic resin. The thermoplastic resin preferably has a Vicat softening temperature of 100 to 160 占 폚, more preferably 102 to 155 占 폚, more preferably 102 to 152 占 폚, of the thermoplastic resin measured in accordance with JIS K 7206: 1999 Do. The Vicat softening temperature of the thermoplastic resin is a Vicat softening temperature of the resin when the thermoplastic resin is composed of one kind of resin and the thermoplastic resin is a softening temperature of the thermoplastic resin formed of a plurality of resins when the thermoplastic resin contains a plurality of resins Vicat softening temperature. Examples of the thermoplastic resin layer include a (meth) acrylic resin layer, a polycarbonate resin layer, and a cycloolefin resin layer. Preferably, it is a (meth) acrylic resin layer or a polycarbonate resin layer.

The (meth) acrylic resin layer may be formed of one or more (meth) acrylic resins or a composite resin of one or more (meth) acrylic resins and one or more thermoplastic resins other than (meth) acrylic resin. These (meth) acrylic resins preferably contain 50 parts by mass or more of (meth) acrylic resin per 100 parts by mass of the total resin forming the (meth) acrylic resin layer. The weight average molecular weight (Mw) of the (meth) acrylic resin contained in the (meth) acrylic resin layer is preferably 50,000 to 300,000, more preferably 70,000 to 250,000. The (meth) acrylic resin contained in the (meth) acrylic resin layer may be the same as or different from the (meth) acrylic resin contained in the layer formed of the resin composition of the present invention. It is preferable that the thermoplastic resin layer does not substantially contain a vinylidene fluoride resin.

As the thermoplastic resin other than the (meth) acrylic resin, a thermoplastic resin compatible with the (meth) acrylic resin is preferable. From the viewpoint of heat resistance, the thermoplastic resin other than the (meth) acrylic resin preferably has a Vicat softening temperature measured according to JIS K 7206: 1999 of 115 ° C or higher, more preferably 117 ° C or higher, desirable.

When the thermoplastic resin is a (meth) acrylic resin, the pencil hardness of the thermoplastic resin layer is preferably not less than HB, more preferably not less than F, and more preferably not less than H.

The polycarbonate resin layer can be formed of a composite resin of at least one polycarbonate resin or at least one polycarbonate resin and at least one thermoplastic resin other than polycarbonate resin. The polycarbonate resin (hereinafter also referred to, MVR.) 300 ℃ temperature and load melt volume rate measured under the conditions of 1.2kg of 3 to preferably 120cm ^3/10 minutes. MVR is, more preferably, 30 ~ 80cm ^3/10 minutes and, more preferably 4 ~ 40cm ^3/10 minutes, particularly preferably 10 ~ 40cm ^3/10 minutes. When the MVR is less than ³ cm &lt; ³ &gt; / 10 minutes, the flowability is lowered, so that the molding process such as melt co-extrusion molding tends to be difficult and appearance defects may occur. In addition, there is a tendency that the MVR exceeds 120cm ^3/10 minutes, a deterioration of mechanical properties such as strength of the polycarbonate resin layer be. The MVR can be measured under the condition of 300 DEG C under a load of 1.2 kg in accordance with JIS K 7210.

The polycarbonate resin is a polymer obtained by, for example, a phosgene method in which various dihydroxy diaryl compounds are reacted with phosgene, or an ester exchange method in which a dihydroxy diaryl compound is reacted with a carbonic ester such as diphenyl carbonate, Typical examples include polycarbonate resins made of 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

Examples of the dihydroxy diaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2- (4-hydroxy-3-propylphenyl) propane, 2,2-bis (4-hydroxy- (Hydroxyaryl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3,5-dichlorophenyl) (Hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy- Dihydroxydiaryl ethers such as 3'-dimethyl diphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'- 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide, And dihydroxydiarylsulfone such as 4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

These may be used alone or in admixture of two or more. In addition to them, piperazine, dipiperidylhydroxynone, resorcin, 4,4'-dihydroxydiphenyl and the like may be mixed and used.

The dihydroxyaryl compound may be mixed with a trivalent or higher phenol compound as shown below. Examples of the trivalent or higher phenol include fluoroglucine, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1- Bis- [4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane, and the like.

In the case where the polycarbonate resin layer is formed of a composite resin of one or more polycarbonate resins and one or more thermoplastic resins other than polycarbonate resin, the thermoplastic resin other than the polycarbonate resin may be blended within a range that does not impair transparency . As this thermoplastic resin, for example, a (meth) acrylic resin compatible with a polycarbonate resin is preferable, and a methacrylic resin having an aromatic ring or a cycloolefin in its structure is more preferable. When the polycarbonate resin includes such a tricryl resin, the surface hardness of the obtained polycarbonate resin layer can be made higher than that when the polycarbonate resin is formed solely.

Examples of the polycarbonate resin other than the above polycarbonate resin include polycarbonates synthesized from isosorbide and aromatic diol. For example, DURABIO (registered trademark) made by Mitsubishi Chemical may be cited.

The polycarbonate resin may contain additives such as a releasing agent, an ultraviolet absorber, a dye, a pigment, a polymerization inhibitor, an antioxidant, a flame retardant, a reinforcing agent, etc., a polymer other than the polycarbonate resin within the range that does not impair the effect of the present invention do.

As the polycarbonate resin, a commercially available product may be used. Examples of commercially available products include 301-4, 301-10, 301-15, 301-22, 301-30, 301-40, SD2221W, SD2201W (trade names) of "Kaliba (registered trademark)" manufactured by Sumikastaronic Polycarbonate , TR2201, and the like.

The film of the present invention is transparent when observed with naked eyes and has a total light transmittance (Tt) measured according to JIS K7361-1: 1997 of preferably 88% or more, more preferably 90% or more to be. The total light transmittance of the film is maintained in this range even if the film is exposed for 120 hours under an environment of 60 DEG C and a relative humidity of 90%.

The film of the present invention includes a (meth) acrylic resin and a vinylidene fluoride resin. The film of the present invention can have a haze (blur value) measured according to JIS K7136: 2000 of not more than 2.0% when exposed to an environment at 60 캜 and a relative humidity of 90% for 120 hours, Index: YI value) can be set to 1.5 or less. The haze is more preferably 1.8% or less, and still more preferably 1.5% or less. In addition, the YI value can be calculated in accordance with JIS Z 8722: 2009. Is preferably 1.4 or less, and more preferably 1.2 or less, than the vinylidene fluoride resin.

Further, the film of the present invention was allowed to stand for 24 hours under an environment of 23 占 폚 and a relative humidity of 50% in accordance with JIS K 6911: 1995, and the dielectric constant at 3 V and 100 kHz measured by the automatic equilibrium bridge method under this environment was normal 3.5 or more, and preferably 4.0 or more. For the measurement, a commercially available instrument may be used. For example, it can be measured with a "precision LCR meter HP4284A" manufactured by Agilent Technologies.

The layer A contained in the film of the present invention can be produced by molding the resin composition of the present invention by, for example, a melt extrusion molding method, a solution softening film forming method, a hot pressing method, an injection molding method or the like. Among them, an injection molding method and a melt extrusion molding method are preferable, and a melt extrusion molding method is more preferable.

When the film of the present invention further comprises a thermoplastic resin layer, the layer A formed by molding the resin composition of the present invention by the above-described molding and the separately formed thermoplastic resin layer are bonded to each other via, for example, a pressure- However, it is preferable to produce the resin composition of the present invention by laminating and integrating a thermoplastic resin such as a (meth) acrylic resin and a polycarbonate resin by melt co-extrusion molding. Such a film produced by melt co-extrusion molding generally tends to be easily secondary molded, compared with a film produced by bonding.

In the melt co-extrusion molding, for example, the resin composition of the present invention and a thermoplastic resin such as a (meth) acrylic resin or a polycarbonate resin are separately introduced into two or three single-screw or twin-screw extruders, respectively Melt-kneaded, and thereafter the layer formed of the resin composition of the present invention and the thermoplastic resin layer are laminated and united by a feed block die, a multi-manifold die or the like, and extruded. It is preferable that the obtained film is cooled and solidified by, for example, a roll unit or the like.

It is preferable that the film of the present invention further has a coating layer on at least one surface thereof for imparting at least one function selected from the group consisting of anti-scratch, anti-reflection, anti-glare and anti-fingerprint. As the coating layer, for example, a cured coating film described in JP-A-2013-86273 can be used.

The thickness of the coating layer is preferably 1 to 100 占 퐉, more preferably 3 to 80 占 퐉, and still more preferably 5 to 70 占 퐉. If it is thinner than 1 탆, it is difficult to manifest its function, and if it is thicker than 100 탆, cracking of the coating layer is concerned.

If necessary, the surface of the coating layer may be subjected to an anti-reflection treatment by a coating method, a sputtering method, a vacuum deposition method, or the like. Further, for the purpose of imparting an antireflection effect, a separately produced antireflection sheet may be bonded to one or both surfaces thereof.

When the layer formed of the resin composition of the present invention is described as A layer, the thermoplastic resin layer as B layer, and the coating layer as C layer, examples of the layer structure of the film of the present invention include the following (1) to have. Taking into account the adhesiveness and scratch resistance between the coating layer and the film, considering the fact that the thermoplastic resin layer is present in the surface layer and the shape change when exposed under a high temperature and high humidity environment of 60 占 폚 and a relative humidity of 90% ), (4), (10) or (12) is preferable, and the configuration of (3) or (10) is more preferable.

(1) A layer

(2) Layer A / layer B

(3) Layer B / layer A / layer B

(4) B layer / A layer / B layer / A layer / B layer

(5) A layer / C layer

(6) C layer / A layer / C layer

(7) Layer A / layer B / layer C

(8) C layer / A layer / B layer / C layer

(9) B layer / A layer / B layer / C layer

(10) C layer / B layer / A layer / B layer / C layer

(11) B layer / A layer / B layer / A layer / B layer / C layer

(12) C layer / B layer / A layer / B layer / A layer / B layer / C layer

&Lt; Transparent conductive sheet &

A transparent conductive film may be formed on at least one surface of the film of the present invention to obtain a transparent conductive sheet.

The method of forming the transparent conductive film on the surface of the film of the present invention may be a method of forming a transparent conductive film directly on the surface of the film of the present invention or a method of laminating a transparent conductive film on the surface of the film of the present invention, Or a method of forming a film.

As the film substrate of the plastic film in which the transparent conductive film has been formed in advance, a transparent film can be used as the transparent film, and for example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylic resin, polyamide, Laminates and the like. It is also effective to coat the film before forming the transparent conductive film for the purpose of improving the surface hardness, preventing Newton ring, imparting antistatic property, and the like.

A method of laminating a film on which a transparent conductive film has been formed in advance on the surface of the film of the present invention may be any method as long as it is free from bubbles and is uniform and can obtain a transparent sheet. A lamination method using an adhesive which is cured at room temperature, heating, ultraviolet rays or visible light may be used, or a transparent adhesive tape may be used.

As a film formation method of the transparent conductive film, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, or the like are known, and these methods can suitably be used depending on the required film thickness.

In the case of the sputtering method, for example, a normal sputtering method using an oxide target, a reactive sputtering method using a metal target, or the like is used. At this time, oxygen, nitrogen, or the like may be introduced as the reactive gas, or means such as ozone addition, plasma irradiation, and ion assist may be used in combination. If necessary, a bias such as DC, AC, or high frequency may be applied to the substrate. Examples of the transparent conductive metal oxide used for the transparent conductive film include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide and indium-zinc composite oxide . Of these, an indium-tin composite oxide (ITO) is preferable from the viewpoints of environmental stability and circuit processability.

As a method for forming the transparent conductive film, a method of applying a coating agent containing various conductive polymers capable of forming a transparent conductive film and curing the film by irradiation with ionizing radiation such as heat or ultraviolet rays may be applied . As the conductive polymer, polythiophene, polyaniline, polypyrrole, and the like are known, and these conductive polymers can be used.

The thickness of the transparent conductive film is not particularly limited, but when a transparent conductive metal oxide is used, it is usually from 50 to 2000 angstroms, and preferably from 70 to 000 angstroms. In this range, both conductivity and transparency are excellent.

The thickness of the transparent conductive sheet is not particularly limited, and it is possible to select the optimum thickness according to the specifications of the display product specification.

<Touch sensor panel>

The film and transparent conductive sheet of the present invention can be suitably used as a transparent electrode such as a display panel face plate, a touch screen and the like. Specifically, the film of the present invention can be used as a touch screen window sheet, and the transparent conductive sheet can be used as an electrode substrate of a resistive film type or capacitive type touch screen, respectively. By disposing the touch screen on the front surface of a liquid crystal display or an organic EL display, an externally mounted touch sensor panel having a touch screen function is obtained.

<Display device>

The film of the present invention can be applied to a flat panel display apparatus other than liquid crystal display and liquid crystal display apparatus, and can be used, for example, as a front plate disposed on the outermost surface of a display apparatus. Examples of the flat panel display device other than the liquid crystal display device include an organic EL display device, a plasma display display device, a field emission display (FED), a SED type flat display, and an electronic paper. For example, when applied to a liquid crystal display device, the film of the present invention can be laminated on a polarizing plate via an optical point adhesive (adhesive agent) such as an adhesive and a pressure-sensitive adhesive. As the adhesive or pressure-sensitive adhesive, any known one may be used.

2 is a schematic cross-sectional view of an example of a liquid crystal display device to which the film of the present invention is applied. The film 10 of the present invention can be laminated on the polarizing plate 11 via an optical point adhesive, and this laminate can be disposed on the viewer side of the liquid crystal cell 13. [ On the back side of the liquid crystal cell, a polarizing plate is usually disposed. The liquid crystal display device 15 is composed of such members. 2 is an example of a liquid crystal display device, and the present invention is not limited to this configuration.

Example

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.

In the examples, the Vicat softening temperature, the alkali metal content, the MFR, the MVR, the total light transmittance, the haze, and the YI value were measured by the following methods, respectively.

The Vicat softening temperature was measured in accordance with JIS K 7206: 1999 " Plastics-thermoplastic plastic-Vicat softening temperature (VST) test method " The Vicat softening temperature was measured by a Heat Distortion Tester ("148-6 type" manufactured by YATSU KOGYO CO., LTD.). The test pieces at this time were press molded to a thickness of 3 mm and measured.

The content of the alkali metal was measured by inductively coupled plasma mass spectrometry.

The MFR was measured according to the method specified in JIS K 7210: 1999 &quot; Test Method of Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastic Plastics &quot;. For the poly (methyl methacrylate) type material, measurement at a temperature of 230 캜 and a load of 3.80 kg (37.3 N) is prescribed in this JIS.

MVR was measured under the condition of 300 占 폚 under a load of 1.2 kg with "Semi-auto melt indexer 2A" manufactured by Toyo Seiki Seisakusho Co., Ltd., which conforms to JIS K 7210.

The total light transmittance and haze can be measured using a haze transmittance meter according to JIS K 7361-1: 1997 "Testing method for total light transmittance of plastic transparent materials - Part 1: Single beam method" ("HR -100 "].

The YI value was measured with "Spectrophotometer SQ2000" manufactured by Nihon Denshoku Kogyo Co., Ltd.

(Production Example 1)

98.5 parts by mass of methyl methacrylate and 1.5 parts by mass of methyl acrylate were mixed, and 0.16 parts by mass of a chain transfer agent (octylmercaptan) and 0.1 part by mass of a release agent (stearyl alcohol) were added to obtain a monomer mixture. Further, 0.036 part by mass of a polymerization initiator [1,1-di (tert-butylperoxy) 3,3,5-trimethylcyclohexane] was added to 100 parts by mass of methyl methacrylate to obtain an initiator mixture. The mixture was continuously fed into a complete mixing type polymerization reactor so that the flow rate ratio of the monomer mixture liquid and the initiator mixture liquid was 8.8: 1, and the polymerization was carried out at an average polymerization time of 20 minutes at a temperature of 175 ° C to an average polymerization rate of 54%. The resulting partial polymer was heated to 200 DEG C and introduced into a vented devolatilizing extruder. The unreacted monomer was deflected from the vent at 240 DEG C and the polymer after devolatilization was extruded in a molten state. After water cooling, To obtain a pellet-shaped methacrylic resin (i).

The obtained pellet-shaped methacrylic resin composition was analyzed by pyrolysis gas chromatography under the following conditions, and the respective peak areas corresponding to methyl methacrylate and acrylic ester were measured. As a result, the methacrylic resin (i) had a structural unit derived from methyl methacrylate of 97.5% by mass and a structural unit derived from methyl acrylate of 2.5% by mass.

(Pyrolysis condition)

Sample preparation: The methacrylic resin composition was precisely weighed (standard: 2 to 3 mg), placed in the central part of a metal cell having a trough shape, and the metal cell was folded and both ends were lightly pinched by pressing.

Pyrolysis apparatus: CURIE POINT PYROLYZER JHP-22 (manufactured by Nihon Bunseki Kogyo Co., Ltd.)

Metal cell: Pyrofoil F590 (manufactured by Nippon Bunseki Co., Ltd.)

Setting temperature of thermostat: 200 ℃

Setting temperature of heat pipe: 250 ℃

Pyrolysis temperature: 590 ℃

Pyrolysis time: 5 seconds

(Gas chromatographic analysis conditions)

Gas chromatographic analysis apparatus: GC-14B (manufactured by Shimadzu Corporation)

Detection method: FID

Column: 7G 3.2 m x 3.1 mm? (Manufactured by Shimadzu Corporation)

Filler: FAL-M (manufactured by Shimadzu Corporation)

Carrier gas: Air / N2 / H2 = 50/100/50 (kPa), 80 ml / min

The temperature of the column was raised to 150 캜 at a rate of 10 캜 / minute, maintained at 150 캜 for 14 minutes

INJ Temperature: 200 ° C

DET temperature: 200 DEG C

(A ₁ ) corresponding to the methyl methacrylate which is detected when the decomposition product produced is pyrolyzed under the pyrolysis conditions and the measurement is carried out under the conditions of the gas chromatography analysis, and the peak corresponding to the acrylic acid ester The area (b ₁ ) was measured. Then, the peak area ratio A (= b ₁ / a ₁ ) was obtained from these peak areas. On the other hand, methacrylic by the weight ratio of the acrylic ester units to acid methyl units pyrolysis the standard of the methacrylic resin W ₀ (base (旣知)) to the pyrolysis conditions, measuring the generated degradation product to the gas chromatographic analysis conditions (A ₀ ) corresponding to the methyl methacrylate and a peak area (b ₀ ) corresponding to the acrylic acid ester which are detected at the time when the peak area ratio A ₀ (= b ₀ / a ₀ ). Then, a factor f (= W ₀ / A ₀ ) was obtained from the peak area ratio A ₀ and the weight ratio W ₀ .

The weight ratio W of the acrylic acid ester units to the methyl methacrylate units in the copolymer contained in the methacrylic resin composition was determined by multiplying the peak area ratio A by the factor f to obtain methyl methacrylate (Mass%) of the methyl methacrylate units relative to the total of the acrylic acid ester units and the acrylic ester units and the ratio (mass%) of the acrylic acid ester units to the total.

(Production Example 2)

A methacrylic resin (ii) in the form of pellets was obtained in the same manner as in Production Example 1, except that 95.0 parts by mass of methyl methacrylate, 5.0 parts by mass of methyl acrylate, and 0.08 parts by mass of chain transfer agent were changed, . The methacrylic resin (ii) had a structural unit derived from methyl methacrylate of 94.7% by mass and a structural unit derived from methyl acrylate of 5.3% by mass.

(Production Example 3)

A methacrylic resin (iii) in the form of pellets was obtained in the same manner as in Production Example 1 except that 97.7 parts by mass of methyl methacrylate, 2.3 parts by mass of methyl acrylate and 0.05 part by mass of chain transfer agent were changed, . The methacrylic resin (iii) had a structural unit derived from methyl methacrylate of 97.0% by mass and a structural unit derived from methyl acrylate of 3.0% by mass.

Table 1 shows the (meth) acrylic resin used in Examples and their physical properties. The methacrylic resins (i) to (iii) are the methacrylic resins obtained in the above-mentioned production examples, and the AlTiGlas (registered trademark) HT121 is an acrylic resin used for the thermoplastic resin layer. In the table, &quot; MA &quot; represents the content ratio of the structural units derived from methyl acrylate in the methacrylic resin.

The weight average molecular weight (Mw) of the (meth) acrylic resin was measured by gel permeation chromatography (GPC). For preparing the calibration curve of GPC, a calibration curve was prepared from the elution time and the molecular weight using a methacrylic resin made by Showa Denko Co., Ltd. having a narrow molecular weight distribution and a known molecular weight as a standard reagent. The weight average molecular weight . Specifically, 40 mg of the resin was dissolved in 20 ml of a tetrahydrofuran (THF) solvent to prepare a measurement sample. Two TSKgel SuperHM-H columns and one SuperH2500 column, which were columns made by Tosoh Corporation, were arranged in series and a detector employing an RI detector was used as the measuring apparatus. The measured molecular weight distribution curve was fitted using the normal distribution function of the following equation by taking fitting of the normal distribution function by taking the logarithm of the molecular weight of the horizontal axis.

In the examples, "Regispie (registered trademark) R-200" manufactured by Denka Co., Ltd. was used as the thermoplastic resin other than the (meth) acrylic resin used for forming the thermoplastic resin layer. This resin had a Vicat softening temperature of 132 캜 and an MFR of 1.8 g / 10 min.

Table 2 shows the vinylidene fluoride resin used in Examples and their physical properties.

The weight average molecular weight (Mw) of vinylidene fluoride was measured by GPC. To prepare a calibration curve of GPC, polystyrene was used as a standard reagent, and a calibration curve was prepared from the elution time and the molecular weight, and the weight average molecular weight of each resin was measured. Specifically, 40 mg of the resin was dissolved in 20 ml of N-methylpyrrolidone (NMP) solvent to prepare a measurement sample. Two TSKgel SuperHM-H columns and one SuperH2500 column, which were columns made by Tosoh Corporation, were arranged in series and a detector employing an RI detector was used as the measuring apparatus.

In the examples, the following polycarbonate resins were used for the thermoplastic resin layer. All are products of Sumikastaron Polycarbonate Co., Ltd.

Caliber 301-15: MVR 10cm ^3/10 minutes, and the resin of Mw 38,500.

Resins MVR 22cm ^3/10 min, and Mw 35,000: Caliber 301-22.

Caliber 301-30: MVR 30cm ^3/10 minutes, and the resin of Mw 32,200.

Caliber SD2201W: MVR 118cm ^3/10 min, and the resin of Mw 13,600.

The weight average molecular weight of the polycarbonate resin was measured by gel permeation chromatography (GPC). For preparing the calibration curve of GPC, a calibration curve was prepared from the elution time and the molecular weight using a methacrylic resin made by Showa Denko Co., Ltd. having a narrow molecular weight distribution and a known molecular weight as a standard reagent. The weight average molecular weight . Specifically, 40 mg of the resin was dissolved in 20 ml of a tetrahydrofuran (THF) solvent to prepare a measurement sample. Two TSKgel SuperHM-H columns and one SuperH2500 column, which were columns made by Tosoh Corporation, were arranged in series and a detector employing an RI detector was used as the measuring apparatus.

(Production Example 4)

The (meth) acrylic resin and the colorant were dry-blended at a ratio shown in Table 3 in order to make the bluing agent masterbatch (MB), and the resulting mixture was melt-kneaded in a 40 mmφ single screw extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.) And melted and mixed at ~ 260 ° C to obtain a colored master batch pellet. As a colorant, a bluing agent ("Sumiplast (registered trademark) Violet B" manufactured by Sumika Chemtex Co., Ltd.) was used.

(Examples 1 to 5 and Comparative Examples 1 to 6)

When the layer formed of the resin composition of the present invention is referred to as A layer and the thermoplastic resin layer is referred to as B layer, a film having the constitution represented by B layer / A layer / B layer is manufactured as follows.

First, the (meth) acrylic resin, the vinylidene fluoride resin and the master batch pellets prepared in Production Example 1 were mixed in the combination and the ratio shown in Table 4 as a material for forming the A layer to obtain the resin composition of the present invention. Subsequently, 100 parts by mass of the methacrylic resin (i) as a material for forming the B layer was extruded through a 45 mmφ single screw extruder (2) with 65 mmφ single screw extruders 1 and 3 (manufactured by Toshiba Machine Co., Ltd.) ) (Manufactured by Hitachi, Ltd.). Subsequently, they were laminated so as to have a structure represented by the above-described B layer / A layer / B layer through a feed block 4 (manufactured by Hitachi, Ltd.) having a set temperature of 250 to 270 DEG C, (Distributed by Hitachi Shipyard Co., Ltd .; two-kind three-layer distribution) to obtain a film-like molten resin (6). The molten resin 6 thus obtained is sandwiched between the first cooling roll 7 and the second cooling roll 8 opposed to each other and then wound on the second roll 8, (10) having a three-layer structure in which the thicknesses of the respective layers are as shown in Table 4, and the rolls were wound around a third cooling roll (9) after being sandwiched between the first roll (8) and the third roll (9) &Lt; / RTI &gt; The total film thickness of the obtained film 10 was 800 占 퐉, and it was colorless transparent when observed with naked eyes.

The calculated values of the amounts of alkali metals (Na + K) contained in the A layer are shown in Tables 1 to 4.

The dielectric constant of each film was measured with a precision LCR meter HP4284A (manufactured by Agilent Technologies, Inc.) according to JIS K 6911: 1995. The permittivity is a value at 3 V to 100 kHz measured by an automatic equilibrium bridge method under the same environment in which the test sample (film) is allowed to stand under an environment of 23 캜 and a relative humidity of 50% for 24 hours.

The durability test was carried out by allowing the obtained film to stand in a constant temperature and humidity oven at 60 캜 and an absolute humidity of 90% for 120 hours. Table 5 shows the haze values measured according to JIS K7136: 2000 and the total light transmittance (Tt) measured according to JIS K7361-: 19971 for the films before and after the endurance test.

(Examples 6 to 8)

A film was obtained in the same manner as in Example 4 except that the composition of the layer B was changed to the resin composition shown in Table 6 in Example 4. Table 7 shows the results of the dielectric constant and endurance test, which were measured in the same manner as in Example 4, with respect to the obtained film.

(Comparative Examples 7 and 8)

Pellets of the resin 4 as the vinylidene fluoride resin and pellets of the methacrylic resin (iii) as the (meth) acrylic resin were uniformly mixed at the respective ratios shown in Table 8, and then extruded into a 20 mm single screw extruder (Labo Plastomill, (Manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 250 占 폚 to obtain blend pellets. Using this pellet, a film having a thickness of 800 탆 was obtained at 220 캜 by press molding. Table 8 also shows the results of the durability test conducted in the same manner as in Example 1 with respect to the obtained film.

(Example 9 and Comparative Example 9)

The pellets of the resin 1 as the vinylidene fluoride resin and the pellets of the methacrylic resin (i) as the (meth) acrylic resin were uniformly mixed at the respective ratios shown in Table 9, and then extruded into a 20 mm single screw extruder (Labo Plastomill, (Manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 250 占 폚 to obtain blend pellets. Using this pellet, a film having a thickness of 800 탆 was obtained at 220 캜 by press molding. Table 9 also shows the results of the dielectric constant and endurance test, which were measured in the same manner as in Example 1, with respect to the obtained film.

(Example 10)

By using the films obtained in Examples 1 to 9 as a front plate (display window sheet), a display device having the structure shown in the sectional view of Fig. 2 can be produced.

(Examples 11 to 18)

When a layer formed of a resin composition is referred to as A layer and a thermoplastic resin layer is referred to as B layer, a film having a constitution represented by B layer / A layer / B layer is manufactured as follows.

First, the (meth) acrylic resin, the vinylidene fluoride resin, and the master batch pellets prepared in Production Example 1 were mixed at the ratio shown in Table 10 as a material for forming the A layer to obtain the resin composition of the present invention. Except for the difference in the resin composition, the processing method was the same as in Examples 1 to 5.

The calculated values of the amounts of alkali metals (Na + K) contained in the A layer of the resultant film obtained from Tables 1 and 3 and the dielectric constant measured by the same method as above are shown in Table 11. Table 11 shows the results of an endurance test in which the obtained film was left in a constant temperature and humidity oven at 60 DEG C and an absolute humidity of 90% for 120 hours.

(Examples 19 to 22)

A film was produced in the same manner as in Examples 1 to 5 except that a polycarbonate resin was used for the B layer. Table 12 shows the blend compositions and ratios of the resins in the A layer and the B layer.

The calculated values of the amounts of the alkali metals (Na + K) contained in the layer A obtained from the Tables 1 and 3 and the dielectric constants measured by the same method as the above method are shown in Table 13. Table 13 shows the results of the durability test in which the obtained film was left in a constant-temperature and constant-humidity oven at 60 DEG C and an absolute humidity of 90% for 120 hours.

Table 14 shows the results of measurement of the fall ball strength for the obtained film. The fall strength was measured by dropping a 25 g iron hole from a predetermined height, and tearing the film.

The layer formed from the resin composition of the present invention and the film of the present invention including the same can maintain transparency even when used for a long time under a high temperature and high humidity environment while having a high permittivity and thus can be used in smart phones, portable game machines, audio players, As the front plate in the display device of the present invention.

1 1 Axial extruder (extrudes the melt of (meth) acrylic resin)
2 Single screw extruder (extruding the melt of the resin composition of the present invention)
3 1-axis extruder (extrudes the melt of (meth) acrylic resin)
4 feed blocks
5 Multi-manifold type die
6 Film-like molten resin
7 First cooling roll
8 Second cooling roll
9 Third cooling roll
10 membrane
11 Polarizer
12 Optical adhesive layer
13 liquid crystal cell
15 liquid crystal display

Claims (20)

(Meth) acrylic resin and vinylidene fluoride resin,
(Meth) acrylic resin and 65 to 55% by mass of a vinylidene fluoride resin per 100 mass% of the total of the (meth) acrylic resin and the vinylidene fluoride resin, Has a weight average molecular weight (Mw) of 100,000 to 300,000,
Wherein at least one of the resins contained in the resin composition contains an alkali metal and the content of the alkali metal is 50 ppm or less per 100 parts by mass of the total amount of the resin and the alkali metal contained in the resin composition. The method according to claim 1,
(Meth) acrylic resin is a resin of the following (a1) or (a2).
(a1) a homopolymer of methyl methacrylate,
(a2) a structural unit derived from methyl methacrylate in an amount of 50 to 99.9 mass%

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₁ is R _2, when one hydrogen atom is represents an alkyl group having 1 to 8 carbon atoms, when the R ₁ group R ₂ represents an alkyl group having a carbon number of 2 to 8 .)
And 0.1 to 50 mass% of at least one structural unit derived from a (meth) acrylic acid ester represented by the following general formula (1). 3. The method according to claim 1 or 2,
Wherein the weight average molecular weight (Mw) of the (meth) acrylic resin is 120,000 to 250,000. 4. The method according to any one of claims 1 to 3,
Wherein the vinylidene fluoride resin is polyvinylidene fluoride. 5. The method according to any one of claims 1 to 4,
And the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 30 g / 10 minutes. 6. The method according to any one of claims 1 to 5,
And a colorant. A film comprising a layer formed from the resin composition according to any one of claims 1 to 6. 8. The method of claim 7,
A membrane having a thickness of 100 to 2000 占 퐉. 9. The method according to claim 7 or 8,
A film further comprising a thermoplastic resin layer. 10. The method according to any one of claims 7 to 9,
A film comprising a thermoplastic resin layer on both sides of a layer formed from a resin composition. 11. The method according to claim 9 or 10,
Wherein the thermoplastic resin layer is a (meth) acrylic resin layer or a polycarbonate resin layer. 12. The method according to any one of claims 9 to 11,
Wherein the thermoplastic resin layer is a layer formed from a resin containing not less than 50 parts by mass of (meth) acrylic resin per 100 parts by mass of the total resin forming the thermoplastic resin layer. 13. The method according to claim 11 or 12,
Wherein the (meth) acrylic resin contained in the thermoplastic resin layer has a weight average molecular weight of 50,000 to 300,000. 14. The method according to any one of claims 9 to 13,
Wherein the thermoplastic resin layer has a thickness of 10 to 200 占 퐉. 15. The method according to any one of claims 9 to 14,
Wherein the thermoplastic resin layer has a Vicat softening temperature of 100 to 160 캜. (Meth) acrylic resin and vinylidene fluoride resin, wherein the film has a haze of 2% or less and a dielectric constant of 4.0 or more when the film is exposed for 120 hours under an environment of 60 占 폚 and a relative humidity of 90%. 17. The method according to any one of claims 7 to 16,
A film further having a coating layer on at least one surface thereof for imparting at least one function selected from the group consisting of anti-scratch, anti-reflection, anti-glare and anti-fingerprint. A display device comprising the film according to any one of claims 7 to 17. 18. A polarizing plate with a film laminated with the film according to any one of claims 7 to 17 and a polarizing plate. A display device comprising the polarizer with a film according to claim 19.

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