TW201930086A - Laminate body for polarization plate, polarization plate, laminate body film roll for polarization plate, method for manufacturing laminate body for polarization plate, and method for manufacturing polarization plate - Google Patents

Abstract

A laminate body for a polarization plate, the laminate body having a resin film comprising a cycloolefin resin, and a polyvinyl alcohol layer laminated by coating at least one surface of the resin film, wherein the cycloolefin resin includes a cycloolefin polymer, the cycloolefin polymer being a block copolymer hydride obtained by hydrogenating a block copolymer [D] comprising: a polymer block [A] having as a main component a repeating unit [I] derived from an aromatic vinyl compound; and a polymer block [B] having as a main component the repeating unit [I] derived from an aromatic vinyl compound and a repeating unit [II] derived from a chain conjugate diene compound, or a polymer block [C] having as a main component the repeating unit [II] derived from a chain conjugate diene compound.

Description

Stacker for polarizing plate, polarizing plate, stacked film roll for polarizing plate, manufacturing method of stacked body for polarizing plate, and manufacturing method of polarizing plate

The present invention relates to a stacked body for a polarizing plate, a polarizing plate, a stacked film roll for a polarizing plate, a method for producing a stacked body for a polarizing plate, and a method for producing a polarizing plate.

Conventionally, display devices such as liquid crystal display devices and organic electroluminescence (EL) display devices have been required to have a large display area, a light weight, and a small thickness. Therefore, the panels constituting the display device have been required to be thinner in the past.

In the display device, a polarizing plate having a polarizing member and a protective film for protecting the polarizing member is generally used. In order to form a thin display device, a polarizing plate is also required to be thinner. In particular, since the polarizer sometimes shrinks in the use environment of the display device, such bending due to shrinkage may become a problem in a thin and large display device. Therefore, by using a thin polarizer having a thickness of 10 μm or less, in addition to the reduction in the thickness of the display device due to the reduction in the thickness of the polarizer itself, reduction in the occurrence of the aforementioned bending can be expected.

However, in the case where a polarizing member of such a thin polyvinyl alcohol is to be produced by a conventional manufacturing method, the melting of the polarizing member frequently occurs. As a method of manufacturing such a polarizing plate that prevents the fuse from being blown and includes a thin polarizer, several methods have been proposed.

For example, in Patent Document 1, it is proposed to apply an aqueous solution containing a polyvinyl alcohol-based resin to a resin film made of an amorphous ester-based thermoplastic resin, thereby producing a polyvinyl alcohol-based resin layer to form a stacked body. After the stack is subjected to the stretching treatment, the dichroic substance is oriented to form a colored stack, and the colored stack is further subjected to a stretching treatment to obtain an optical film.

"Patent Literature"
Patent Document 1: Japanese Patent No. 4691205 (corresponding publication: US Patent No. 8314987)

When a thin polarizing plate is produced by the method described in Patent Document 1, the stacked body is stretched at a high stretching ratio, and a phase difference occurs in the resin film after the stretching treatment. In this case, since it is difficult to directly use the resin film as a polarizing plate protective film, it is peeled off and discarded, so that a wasteful material is generated. Furthermore, it is possible to add a work for separately preparing a protective film for protecting the polarizing plate and attaching it to the polarizing plate.

Accordingly, an object of the present invention is to provide a stack for a polarizing plate which can be used even if a resin film is used as a protective film, and can be efficiently manufactured even if the thickness is thin, a method for producing the same, a polarizing plate using the same, and a polarizing plate using the same A manufacturing method, and a stacked film roll for a polarizing plate using the aforementioned stacked body.

In order to solve the above problems, the inventors have found that by using a resin film having a "cycloolefin resin containing a specified cycloolefin polymer" and "stacking on at least one side of the resin film" The present invention can be accomplished by solving the above problems by stacking a polyvinyl alcohol layer.

Therefore, according to the present invention, the following [1] to [12] can be provided.

[1] A stack for a polarizing plate, comprising: a resin film made of a cycloolefin resin; and a stack of polarizing plates stacked on the polyvinyl alcohol layer on at least one side of the resin film by coating, Wherein the cycloolefin-based resin contains a cycloolefin-based polymer,
The cycloolefin-based polymer is a block copolymer hydrogenated product obtained by hydrogenating the block copolymer [D], and the block copolymer [D] is composed of:
a polymer block [A] having a repeating unit [I] derived from an aromatic vinyl compound as a main component, and a repeating unit [I] derived from an aromatic vinyl compound and a chain conjugated diene compound The repeating unit [II] is a polymer block [B] as a main component, or a polymer block [C] having a repeating unit [II] derived from a chain conjugated diene compound as a main component.

The thickness of the polyvinyl alcohol layer is 45 μm or less, and the phase difference Re2 of the in-plane direction of the extension of the resin film is 0 nm or more, and the laminate for a polarizing plate according to the above [1]. 20 nm or less, the phase difference Re2 is such that the free end of the stack for polarizing plates is uniaxially extended to 6.0 times at a temperature of 50 ° C to 120 ° C, and when the resin film is formed as the extension, the extension is The phase difference.

[3] The stack for polarizing plates according to [1], wherein the cycloolefin-based resin contains a plasticizer, a softener, or both.

[4] The stacked body for a polarizing plate according to the above aspect, wherein the plasticizer, the softener, or both are selected from one or more of an ester plasticizer and an aliphatic hydrocarbon polymer.

[5] The stacked body for a polarizing plate according to any one of [1], wherein the resin film contains an organometallic compound.

[6] The stack for polarizing plates according to any one of [1], wherein the polyvinyl alcohol layer is directly stacked on a layer body of the resin film.

[7] A polarizing plate according to any one of [1] to [6], wherein the stack for polarizing plates is uniaxially stretched.

[8] A stacked film roll for a polarizing plate which is wound into a roll and has:
The separator for a polarizing plate according to any one of [1] to [6], and a separator which is laminated on a surface of the resin film of the polarizing plate stack opposite to the polyvinyl alcohol layer.

[9] A method for producing a stack for a polarizing plate, comprising:
a first step of forming a polyvinyl alcohol resin on at least one side of a resin film made of a cycloolefin resin to form a polyvinyl alcohol layer; and a second drying of the polyvinyl alcohol layer formed in the first step a step wherein the cycloolefin-based resin contains a cycloolefin-based polymer,
The cycloolefin-based polymer is a block copolymer hydrogenated product obtained by hydrogenating the block copolymer [D], and the block copolymer [D] is composed of:
a polymer block [A] having a repeating unit [I] derived from an aromatic vinyl compound as a main component, and a repeating unit [I] derived from an aromatic vinyl compound and a chain conjugated diene compound The repeating unit [II] is a polymer block [B] as a main component, or a polymer block [C] having a repeating unit [II] derived from a chain conjugated diene compound as a main component.

[10] The method for producing a stack for a polarizing plate according to [9], wherein the polyvinyl alcohol layer is formed by one or more methods selected from the group consisting of solution coating, emulsion coating, or melt extrusion coating. .

[11] A method of producing a polarizing plate, wherein the polarizing plate stack according to any one of [1] to [6] or the polarizing plate according to [9] or [10] is used. A method for manufacturing a polarizing plate by using a stacked body of a polarizing plate obtained by a method of manufacturing a stacked body, comprising:
The third step of dyeing the stack for polarizing plates with a dichroic dye and the fourth step of uniaxially stretching the stack for polarizing plates.

[12] The method for producing a polarizing plate according to [11], comprising: after the third step, the fourth step, or the like, the polyvinyl alcohol layer of the stack for polarizing plates; The surface on the side opposite to the resin film is bonded to the fifth step of the protective film.

According to the present invention, it is possible to provide a stack for a polarizing plate which can be used even if a resin film is used as a protective film, and which can be efficiently manufactured even if the thickness is thin, a method for producing the same, a polarizing plate using the same, and a method for producing the same And a stack of film rolls for polarizing plates.

The embodiments and examples are disclosed below to explain the present invention in detail. However, the present invention is not limited by the embodiments and the examples described below, and may be arbitrarily changed and carried out without departing from the scope of the invention and the scope of the invention.

In the present application, the term "long strip" refers to a length of 5 times or more with respect to the width of the film, and preferably has a length of 10 times or more, and specifically means that it has an acceptable length. The length to which the roll is stored or transported in a roll shape. The upper limit of the ratio with respect to the length of the film width is not particularly limited, but is, for example, 100,000 times or less.

In the present application, the phase difference Re of the in-plane direction of the film and the phase difference Rth in the thickness direction are follows: Re=(nx-ny)×d and Rth={[(nx+ny)/2]-nz}×d And calculated. And the Nz coefficient of the film is a value represented by [(nx-nz)/(nx-ny)], and is also expressed as [(Rth/Re)+0.5]. Here, the refractive index in the slow axis direction of the nx-based film (the maximum refractive index in the plane), the refractive index of the ny-line in the in-plane direction perpendicular to the slow axis in the plane of the film, and the thickness direction of the nz-based film. The refractive index, the thickness (nm) of the d-type film. The measurement wavelength, unless otherwise noted, is set to a representative wavelength of 550 nm in the visible region.

[Embodiment 1: Stack for polarizing plate, manufacturing method thereof, stacked film roll for polarizing plate, polarizing plate, and manufacturing method thereof]

Hereinafter, a stack for a polarizing plate (hereinafter simply referred to as a "stack") according to a first embodiment of the present invention, a method of manufacturing the same, and a method of manufacturing the same, and a method of using the same, will be described with reference to FIG. 1 to FIG. A stack film roll for a polarizing plate, a polarizing plate using the same, and a method of manufacturing the same.

[1. Stack for polarizing plate]

The stack for a polarizing plate of the present invention comprises a resin film made of a cycloolefin resin and a polyvinyl alcohol layer stacked on at least one side of the resin film. The polyvinyl alcohol layer is a layer (coating layer) which is stacked by coating.

Fig. 1 is a cross-sectional view showing an example of a stack 10 of an embodiment 1 of the present invention. As shown in Fig. 1, the stacked body 10 of the present embodiment has a resin film 12 and a polyvinyl alcohol layer 11 provided on one surface (the upper side in the figure) of the resin film. The stacked body 10 of the present invention is used to manufacture a material of a polarizing member (polarizing plate).

[Polyvinyl alcohol layer]

In the present invention, the polyvinyl alcohol layer is a layer body of a polyvinyl alcohol resin. Hereinafter, "polyvinyl alcohol" is sometimes referred to as "PVA".

In the present invention, the PVA resin (polyvinyl alcohol resin) which forms the PVA layer is not limited, but in terms of availability, it is produced by using saponification of polyvinyl acetate obtained by polymerizing vinyl acetate. good. The PVA contained in the PVA resin is preferably in the range of 500 to 8,000, and the degree of saponification is preferably 90 mol% or more from the viewpoint of excellent extensibility or polarizing performance of the polarizer which can be obtained. Here, the degree of polymerization is an average degree of polymerization measured in accordance with the description of JIS K6726-1994, and the degree of saponification is a value measured in accordance with the description of JIS K6726-1994. The polymerization degree is preferably in the range of 1,000 to 6,000, more preferably 1,500 to 4,000. The preferred range of saponification degree is 95 mol% or more, and more preferably 99 mol% or more. PVA can also be a copolymer or graft polymer of vinyl acetate with other monomers copolymerizable.

In the present invention, the PVA resin is preferably contained in an amount of 0.01 to 30% by weight based on the PVA, such as a polyhydric alcohol such as glycerin, in order to improve the mechanical properties and work fluency in secondary processing, and to improve the workability. The film appearance or the like is preferably 0.01 to 1% by weight based on the surfactant containing an anionic surfactant or a nonionic surfactant with respect to PVA.

The PVA resin may further contain an optional component such as an antioxidant, a UV absorber, a slip agent, a pH adjuster, an inorganic fine particle, a colorant, a preservative, a fungicide, a polymer compound other than the above components, and moisture. The PVA resin may contain one or more of these other components.

The thickness T of the PVA layer is preferably 45 μm or less, preferably 35 μm or less, more preferably 25 μm or less, more preferably 5 μm or more, more preferably 10 μm or more, and 15 μm or more. good. When the thickness of the PVA layer is less than or equal to the upper limit of the above range, the contraction force of the polarizing plate can be effectively reduced, and a polarizing plate having sufficiently high polarizing performance can be obtained by being equal to or higher than the lower limit of the above range.

The phase difference Re1 in the in-plane direction of the PVA layer is preferably 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less, more preferably 0 nm or more, and preferably 3 nm or more. When the phase difference Re1 in the in-plane direction of the PVA layer is equal to or less than the upper limit of the above range, the stacked body can be sufficiently stretched to obtain a polarizing plate having high polarization performance.

[Resin film]

The resin film is made of a cycloolefin resin. The cycloolefin resin is a resin containing a cycloolefin polymer. In the present invention, as the cycloolefin resin, a resin having flexibility which can be extended at a high stretching ratio (for example, 6.0 times) at a low temperature (for example, 50 to 120 ° C) is preferred.

[cycloolefin resin]

The cycloolefin polymer contained in the cycloolefin resin is a block copolymer hydrogenated product obtained by hydrogenating the block copolymer [D], and the block copolymer [D] is derived from an aromatic vinyl group. The polymer block [A] as a main component of the repeating unit [I] of the compound is the same as the repeating unit [I] derived from the aromatic vinyl compound and the repeating unit [II] derived from the chain conjugated diene compound The polymer block [B] of the main component or the polymer block [C] having the repeating unit [II] derived from the chain conjugated diene compound as a main component. Examples of such a block copolymer hydride include WO2000/32646, WO2001/081957, Japanese Patent Publication No. 2002-105151, Japanese Patent Publication No. 2006-195242, and Japanese Patent Publication No. 2011- A polymer described in, for example, No. 13378 and WO2015/002020.

[plasticizers and softeners]

In the present invention, the cycloolefin resin forming the resin film preferably contains a plasticizer and/or a softener (either or both of a plasticizer and a softener). By containing a plasticizer and/or a softening agent, the phase difference generated in the resin film when the polarizing plate is obtained by extending the stacked body can be reduced.

As the plasticizer and the softener, those which can be uniformly dissolved or dispersed to form a cycloolefin-based resin which forms a resin film are used. Specific examples of the plasticizer and the softening agent include an ester-based plasticizer composed of a polyhydric alcohol and a monocarboxylic acid (hereinafter referred to as "polyol ester-based plasticizer") and a polycarboxylic acid and An ester-based plasticizer such as an ester-based plasticizer (hereinafter referred to as "polycarboxylic acid ester-based plasticizer"), a phosphate-based plasticizer, a sugar ester-based plasticizer, and other polymerizations. Softener.

The polyol which is a raw material of the ester-based plasticizer which is preferably used in the present invention is not particularly limited, but ethylene glycol, glycerin or trimethylolpropane is preferred.

Examples of the polyol ester-based plasticizer include a glycol ester-based plasticizer, a glyceride-based plasticizer, and other polyol ester-based plasticizers.

Examples of the polycarboxylic acid ester-based plasticizer include a dicarboxylic acid ester plasticizer and other polycarboxylic acid ester plasticizers.

Specific examples of the phosphate ester plasticizer include alkyl phosphates such as triethyl decyl phosphate and tributyl phosphate; cycloalkyl phosphates such as tricyclopentyl phosphate and cyclohexyl phosphate; and triphenyl phosphate. An aryl phosphate such as an ester or a tricresyl phosphate.

Specific examples of the sugar ester plasticizer include glucose pentaacetate, glucose pentapropionate, glucose pentabutyrate, sucrose octaacetate, sucrose octacarboxylate, and the like. Sucrose octaacetate is preferred.

Specific examples of the polymer softener include an aliphatic hydrocarbon polymer, an alicyclic hydrocarbon polymer, polyethyl acrylate, polymethyl methacrylate, methyl methacrylate and -2-hydroxy methacrylate. Acrylic polymer such as copolymer of ethyl ester, methyl methacrylate and copolymer of methyl acrylate and 2-hydroxyethyl methacrylate; polyvinyl isobutyl ether, poly-N-ethylene hydropyrrolidone Ethylene polymer; styrene polymer such as polystyrene or poly-4-hydroxystyrene; polyester such as polybutylene succinate, polyethylene terephthalate or polyethylene naphthalate Polyethers such as polyethylene oxide and polypropylene oxide; polyamines, polyurethanes, polyureas, and the like.

Specific examples of the aliphatic hydrocarbons include low molecular weight substances such as polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, and ethylene-α-olefin copolymer, and hydrogenation thereof. a low molecular weight substance such as a polyisoprene, a polyisoprene-butadiene copolymer, a hydride thereof, or the like. The aliphatic hydrocarbon-based polymer preferably has a number average molecular weight of from 300 to 5,000 from the viewpoint of being easily dissolved uniformly or even dispersed to a cycloolefin resin.

These polymer softeners may be homopolymers composed of one repeating unit or copolymers having a plurality of repeating structures. Further, the above polymers may be used in combination of two or more kinds.

In the present invention, as the plasticizer and/or the softening agent, it is preferable that the compatibility with the resin forming the resin film is particularly excellent, and one or more selected from the group consisting of an ester plasticizer and an aliphatic hydrocarbon polymer is preferred. .

The ratio of the plasticizer and/or softener (hereinafter also referred to as "plasticizer") in the resin film is preferably 0.2 parts by weight or more based on 100 parts by weight of the cycloolefin resin forming the resin film. It is preferably 0.5 parts by weight or more, more preferably 1.0 part by weight or more, more preferably 50 parts by weight or less, and still more preferably 40 parts by weight or less. By setting the ratio of the plasticizer or the like within the above range, even if the manufacturing process of the polarizing plate including the stretching treatment is carried out, the resin film can be made sufficiently low in phase difference.

[organometallic compound]

In the present invention, the resin film preferably contains an organometallic compound. By including the organometallic compound, the occurrence of peeling of the resin film in the case where the stacked body is stretched at a high stretching ratio (for example, wet stretching at a stretching ratio of 6.0) can be more effectively suppressed.

The organometallic compound is a compound containing at least one of a chemical bond between a metal and carbon and a chemical bond between a metal and oxygen, and is a metal compound having an organic group. Examples of the organometallic compound include an organic ruthenium compound, an organic titanium compound, an organoaluminum compound, and an organic zirconium compound. Among these, an organic ruthenium compound, an organic titanium compound, and an organic zirconium compound are preferred, and an organic ruthenium compound is preferred because it is excellent in reactivity with polyvinyl alcohol. The organometallic compound may be used alone or in combination of two or more.

The organometallic compound is, for example, an organic ruthenium compound represented by the following formula (1), but is not limited thereto.
R ¹ _a Si(OR ² ) _{3 − a} (1)
(In the formula (1), R ¹ and R ² are each independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an epoxy group, an amine group, a decyl group, an isocyanate group, and a carbon atom. A group of groups of 1 to 10 organic groups, and a represents an integer of 0 to 3.)

In the formula (1), a preferred example is as R ¹ , and examples thereof include an epoxy group, an amine group, a decyl group, an isocyanate group, a vinyl group, an aryl group, an acryl group, and a carbon number of 1 to 8. The alkyl group, -CH ₂ OC _n H _{2n + 1} (n represents an integer of 1-4), and the like.

Further, in the formula (1), a preferable example is as R ² , and examples thereof include a hydrogen atom, a vinyl group, an aryl group, an acryl fluorenyl group, an alkyl group having 1 to 8 carbon atoms, and -CH ₂ OC _{n .} H _{2n + 1} (n represents an integer of 1 to 4).

Examples of the organic ruthenium compound include epoxy-based organic ruthenium compounds such as 3-glycidoxypropyltrimethoxydecane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. An amine-based organic ruthenium compound such as 3-aminopropyltrimethoxydecane or N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, or isocyanuric acid (trimethoxydecyl) An isocyanate-based organic ruthenium compound such as an isocyanate-based organic ruthenium compound such as a propyl) ester or an oxime-based organic ruthenium compound such as 3-mercaptopropyltrimethoxydecane or 3-isocyanatopropyltriethoxydecane.

Examples of the organic titanium compound include titanium alkoxide such as tetraisopropyl titanate, titanium chelate compound such as titanium acetylacetonate, and titanium oxytitanate such as titanium isostearate.

Examples of the organic zirconium compound include zirconium alkoxide such as n-propyl zirconate, zirconium chelate such as zirconium tetraacetate acetone, and zirconium zirconium oxide such as zirconium stearate.

Examples of the organoaluminum compound include aluminum alkoxides such as alkane alumina such as secondary butoxide aluminum and aluminum triacetate.

The proportion of the organometallic compound in the resin film is preferably 0.05 parts by weight or more, more preferably 0.01 parts by weight or more, and more preferably 0.03 parts by weight or more, based on 100 parts by weight of the cycloolefin resin forming the resin film. Preferably, it is preferably 1.0 part by weight or less, more preferably 0.5 part by weight or less. By setting the ratio of the organometallic compound within the above range, the occurrence of peeling of the resin film in the case of wet-extending the stacked body at a high rate (for example, elongation ratio of 6.0) can be more effectively suppressed.

[arbitrary component]

The resin film contains an optional component in addition to a resin, a plasticizer, an organometallic compound, or the like. Examples of the optional component include stabilizers such as antioxidants, ultraviolet absorbers, and light stabilizers; resin modifiers such as slip agents; colorants such as dyes and pigments; and antistatic agents. These admixtures may be used singly or in combination of two or more kinds, and the blending amount thereof may be appropriately selected.

[Method for Producing Resin Film]

The resin film is formed into a film shape by an arbitrary molding method by a composition (hereinafter also referred to as "resin composition") containing a component (a cycloolefin resin and a component added as required) for forming a resin film. Manufacturing.

Examples of the method of forming the resin composition into a film shape include a casting method, a extrusion molding method, and an inflation molding method.

The thickness of the resin film is preferably 1 μm or more, more preferably 3 μm or more, and most preferably 50 μm or less, and preferably 20 μm or less. When the thickness of the resin film is equal to or greater than the lower limit of the above range, a stacked body having a good bonding surface state can be obtained, and when the thickness is less than or equal to the upper limit of the above range, the polarizing plate can be reduced when the stacked body is extended. The phase difference produced in the resin film.

The shape and size of the resin film are appropriately adjusted to correspond to the intended use. In terms of manufacturing efficiency, the resin film is preferably a long film.

[Re2 of resin film]

The phase difference Re2 in the in-plane direction of the extension of the resin film is preferably 0 nm or more and 20 nm or less. Re2 is preferably 0 nm or more, and preferably 10 nm or less, and more preferably 5 nm or less. When Re2 is equal to or less than the upper limit, the phase difference which appears in the resin film when the stacked body 10 is stretched to form a polarizing plate can be reduced.

Re2, the free end of the stack 10 is uniaxially stretched to 6.0 times at a temperature of 50 ° C to 120 ° C, and when the resin film in the stack is made into an extension, the extension of the resin film has an in-plane The phase difference of the direction. That is, Re2 is not the phase difference of the resin film itself in the stack, but the phase difference generated in the extension of the resin film after a specific stretching treatment is applied to the stacked body.

The extension temperature for obtaining such an extension may be any temperature in the range of 50 °C to 120 °C. Thus, a number of operating conditions for obtaining an extension of the extension are contemplated. In the case where the extension exhibits a phase difference of 0 nm or more and 20 nm or less in any of a plurality of operating conditions, the stack satisfies the aforementioned requirements.

However, it is preferable that the extension exhibits a phase difference of 0 nm or more and 20 nm or less due to all of the plurality of operating conditions obtained. In this case, in the manufacture of the polarizing plate that has passed through the stacked body for a polarizing plate of the present invention, a high degree of "degree of freedom in setting extension conditions" can be obtained.

In general, in this temperature range, when the extension temperature is low, a large phase difference appears. Therefore, as long as the "phase difference between the extensions formed by the extension of 50 ° C" and the "phase difference of the extensions formed by the extension of 120 ° C" are in the range of 0 nm or more and 20 nm or less, It is judged that the extension exhibits a phase difference of 0 nm or more and 20 nm or less due to all of the aforementioned plurality of operating conditions.

[2. Method of manufacturing stacked body]

The method for producing a stacked body according to this embodiment includes, in order, a first step of forming a PVA resin on at least one side of a resin film made of a cycloolefin-based resin to form a PVA layer, and in the first step A second step of drying the formed PVA layer. The cycloolefin-based polymer contained in the resin film used in the production of the stacked body is a block copolymer hydrogenated product obtained by hydrogenating the block copolymer [D], and the block copolymer [D] is composed of: a polymer block [A] having a repeating unit [I] derived from the above aromatic vinyl compound as a main component, and a repeating unit [I] derived from an aromatic vinyl compound and a chain conjugated diene compound The repeating unit [II] is a polymer block [B] as a main component, or a polymer block [C] having a repeating unit [II] derived from a chain conjugated diene compound as a main component.

[Manufacturing device of stack]

Fig. 2 is a schematic view showing an example of a manufacturing apparatus 200 used in the method of manufacturing a stacked body according to the present embodiment. The manufacturing apparatus 200 includes a winding device 201, a coating device 202, a winding device 203, and a drying device 205.

[Manufacturing method of stack]

As shown in FIG. 2, in the coating device 202, a PVA resin is coated on the surface of the resin film 12 taken up from the unwinding device 201 to form a PVA layer 11 (first process), and then subjected to drying in the drying device 205. The drying process (second process), thereby obtaining the stacked body 10. The stacked body 10 produced can be wound into a roll shape by the winding device 203 for further processing. Each step will be described below.

[First Process]

The first step is a step of forming a PVA layer 11 by coating a PVA resin on at least one surface of a resin film 12 made of a cycloolefin resin. The method of coating the PVA resin on the resin film 12 (method of coating) is not particularly limited, but it is preferably one or more methods selected from, for example, solution coating, emulsion coating or melt extrusion coating. A PVA layer which can be coated at a high speed and which can obtain a uniform film thickness is preferably coated with a solution.

In the case of solution coating, PVA (PVA or PVA film) used for formation of the PVA layer 11 and components added as needed are dissolved in a solvent to form a PVA composition, and the PVA composition is coated. Covered with the resin film 11. That is, the term "coating resin" includes both "in the case of coating only a resin" and "in the case of coating a resin composition containing a resin and components other than the resin".

[Second process]

The second step is a step of drying the PVA layer formed in the first step.

In the second step, it is preferred to dry the PVA layer in a dryer at a temperature of from 50 ° C to 120 ° C for from 0.5 minutes to 10 minutes. The drying temperature of the PVA layer is preferably 60 ° C or higher, and preferably 100 ° C or lower. By setting the drying temperature to the lower limit or lower, the drying time can be shortened, and the occurrence of cracking of the PVA layer can be prevented, and by setting the drying temperature to the upper limit or lower, crystallization of the PVA layer can be suppressed.

[any process]

The method for producing a stacked body of the present invention may further include a step of performing an easy-bonding treatment on a surface of the resin film on which the PVA layer is to be formed, before the first step. Examples of the method of the easy-bonding treatment in this step include corona treatment, saponification treatment, primer treatment, anchor coating treatment, and the like. In this step, by performing the easy-bonding treatment on the surface of the resin film, the adhesion between the resin film and the PVA layer can be improved, and the PVA layer can be prevented from being peeled off when the PVA layer is formed.

[Use of stack]

The stacked body 10 of the present invention is a material for manufacturing a polarizing plate. The stacked body is subjected to a predetermined process such as elongation processing and dyeing treatment, and is then formed into a polarizing plate. In the case where the stacked body 10 is used as the material of the polarizing plate, the stacked body wound up by the winding device 203 shown in Fig. 2 can be directly used, or the resin film of the stacked body 10 wound by the winding device 203 can be used. 12 stacked on the separator, wound into a roll, and then made into a stack of film rolls for reuse. The stacked film roll and the polarizing plate of this embodiment using the stacked body 10 of the present embodiment will be described in order below.

[3. Stack film roll for polarizing plate]

Fig. 3 is a schematic cross-sectional view showing a stacked film roll for a polarizing plate using the stacked body according to the embodiment.

As shown in FIG. 3, the stacked film roll 15 for a polarizing plate of the present embodiment has a stacked body 10, and a side of the resin film 12 stacked on the opposite side of the PVA layer 11 of the stacked body 10 (the lower side of the figure is shown) The separator 13 is a film roll wound into a roll. The stacked film roll 15 of the present embodiment has a stack 10 of "having a resin film 12 and a PVA layer 11 stacked on one side of the resin film 12", and is opposite to the PVA layer 11 of the resin film 12 stacked on the stacked body 10. The separator 13 on the side of the side.

The separator 13 is not particularly limited as long as it is a material that can be peeled off from the resin film 12, and may be selected from, for example, a cycloolefin resin, an acrylic resin, a polyethylene terephthalate resin, or a polyethylene. A film of one or more resins of a resin, a polypropylene resin, and a triacetyl cellulose resin.

[4. Method of manufacturing polarizing plate]

The polarizing plate 100 of the present invention can be obtained by uniaxially stretching the stacked body 10 of the present embodiment. FIG. 4 is a schematic view showing an example of a manufacturing apparatus for manufacturing a polarizing plate using the stacked body for a polarizing plate according to the present embodiment.

The method for producing a polarizing plate of the present invention comprises a third step of dyeing the stacked body with a dichroic dye and a fourth step of uniaxially stretching the stacked body.

Further, the method for producing a polarizing plate of the present invention may include, after the third step and/or the fourth step, bonding the fifth surface of the protective film to the surface of the PVA layer of the stacked body opposite to the resin film. Process. In the present embodiment, the polarizing plate is manufactured by a manufacturing method that does not include the fifth step.

[Device for manufacturing polarizing plate]

As shown in FIG. 4, the manufacturing apparatus 300 for manufacturing a polarizing plate is provided with the winding-out apparatus 301 & 307, the processing apparatus 302-305, the drying apparatus 306 & 309, the bonding apparatus 308, and the winding-up apparatus 310.

[Method of Manufacturing Polarizing Plate]

In the present embodiment, the stacked body 10 taken out from the unwinding device 301 is transported to the processing apparatuses 302 to 305, and the dyeing process (the third process) of dyeing the PVA layer 11 of the stacked body 10 is performed, and the stack is stacked. The extension process of the shaft extension (fourth process), and the specified process. The polarizing plate 100 can be obtained by performing a process of "drying the stacked body in the drying device 306 after the treatment has been performed" (drying step). Each step will be described in detail below.

[third process]

The third step is a step of dyeing the PVA layer 11 of the stacked body 10.

Examples of the dyeing of the PVA layer in the third step include dichroic materials, and examples of the dichroic material include iodine and an organic dye. The dyeing method using these dichroic substances is arbitrary. For example, the PVA layer may also be dyed by immersing it in a dye solution containing a dichroic substance. Further, when iodine is used as the dichroic substance, the dyeing solution may contain an iodide such as potassium iodide from the viewpoint of improving the dyeing efficiency. The dichroic substance is not particularly limited. However, when a polarizing plate is used for a display device for a vehicle, an organic dye is preferable as the dichroic substance.

[Fourth process]

The fourth step is a step of uniaxially stretching the stack. The method of extending the stacked body is not particularly limited, but it is preferably wet-extended. The fourth step may be performed before the third step, after the third step, or at the same time as the third step. Further, the fourth step may be performed once or multiple times (two or more times). When the fourth step is performed a plurality of times, it may be carried out separately at two or more of the above times, or may be performed a plurality of times in a single time.

The stretching ratio of the stacked body is preferably 5.0 or more, more preferably 5.5 or more, and most preferably 7.0 or less, and more preferably 6.5 or less. When the stretching ratio of the stacked body is equal to or less than the upper limit of the above range, even if the manufacturing process of the polarizing plate including the stretching treatment is performed, the phase difference of the resin film can be reduced, and the occurrence of breakage of the polarizing plate can be prevented. When the stretching ratio is set to be equal to or higher than the lower limit of the above range, a polarizing plate having sufficient polarizing performance can be obtained. When the stacking of the stack is performed twice or more, it is preferable that the total stretch ratio expressed by the product of the respective stretch ratios is within the above range.

The stretching temperature of the stacked body is not particularly limited, but is preferably 30 ° C or higher, preferably 40 ° C or higher, more preferably 50 ° C or higher, and preferably 140 ° C or lower, and preferably 90 ° C or lower. It is especially preferable to be below 70 °C. The elongation can be smoothly performed by extending the temperature to be equal to or higher than the lower limit of the above range, and effective stretching can be performed by extending the extension below the upper limit of the above range. The range of the extension temperature is preferably either dry extension or wet extension, but it is particularly preferable in the case of wet stretching.

The stacking process may be performed by any one of the following: a longitudinal stretching process extending along the longitudinal direction of the film, a lateral stretching process extending along the width direction of the film, and a slanting direction that is neither parallel nor perpendicular to the width direction of the film. The oblique extension process is performed to extend. The extension of the stack is preferably uniaxially extended at the free end, preferably uniaxially extending at the free end of the longitudinal direction.

[Drying process]

The drying step is a step of drying the stacked body through the treatment steps such as the third step and the fourth step. In the drying step, it is preferred to dry the stack after the treatment step in a dryer at a temperature of 50 ° C to 100 ° C for 0.5 minutes to 10 minutes. The drying temperature of the above-mentioned stacked body is preferably 60 ° C or higher, and preferably 90 ° C or lower. By setting the drying temperature to the lower limit or lower, the drying time can be shortened, and the occurrence of cracking of the PVA layer can be prevented, and by setting the drying temperature to the upper limit or lower, the cracking of the PVA layer can be prevented. The drying time of the above-mentioned stacked body is preferably 1 minute or more, and preferably 5 minutes or less. The above-mentioned stacked body can be sufficiently dried by setting the drying time to the lower limit or more, and by setting it to the upper limit or less, the crack of the PVA layer in the stacked body can be prevented.

In the polarizing material of the film formed of the conventional PVA resin, cracking may occur after the drying step. However, in the polarizing plate of the present embodiment, a resin containing a PVA layer and a cycloolefin resin is used. Since the film is produced in a stacked body, the occurrence of cracking of the polarizer can be suppressed even after the drying process.

[5. Polarizer]

According to the method for producing a polarizing plate of the present embodiment described above, a polarizing plate can be obtained. The polarizing plate of this embodiment is a polarizing plate in which the stacked body of the present embodiment is uniaxially extended. Fig. 5 is a schematic cross-sectional view showing a polarizing plate manufactured by using the stacked body according to the embodiment.

As shown in FIG. 5, in the polarizing plate 100, a resin film 112 is stacked on one surface (the side surface below the drawing) of the PVA layer 111.

[Characteristics of layers in a polarizing plate]

The thickness of the PVA layer 111 in the polarizing plate 100 is preferably 20 μm or less, more preferably 10 μm or less, more preferably 3 μm or more, and most preferably 5 μm or more. When the thickness is equal to or less than the upper limit, the thickness of the polarizing plate can be reduced, and if the thickness is equal to or greater than the lower limit, a polarizing plate having sufficiently high polarizing performance can be obtained.

The phase difference in the in-plane direction of the resin film in the polarizing plate is preferably 20 nm or less, preferably 15 nm or less, more preferably 10 nm or less, and more preferably 0 nm or more. When the phase difference in the in-plane direction of the resin film in the polarizing plate is within the above range, the black shift when the polarizing plate is mounted on the liquid crystal display device can be suppressed.

[Use of polarizing plate]

The polarizing plate produced by using the stacked body for a polarizing plate of the present invention can be used as a material of a liquid crystal display device.

In general, the liquid crystal display device includes a light source, a light source side polarizing plate, a liquid crystal cell, and a viewing side polarizing plate in this order. However, the polarizing plate obtained by the present invention can be used for any of the light source side polarizing plate and the viewing side polarizing plate. . The liquid crystal display device can be manufactured by stacking the polarizing plate of the present invention as a light source side polarizing plate and a viewing side polarizing plate, or stacking them on a liquid crystal panel.

Further, the polarizing plate produced by using the stacked body for a polarizing plate of the present invention is used as a material such as an organic EL display device or an inorganic EL display device.

In general, the organic EL display device includes a substrate, a transparent electrode, a light-emitting layer, and a metal electrode layer in this order from the light-emitting side. However, the polarizing plate obtained by the manufacturing method of the present invention can be disposed on the light-emitting side of the substrate.

The EL display device has two substrates, a light-emitting layer interposed therebetween, and a polarizing plate disposed on the outer side of one of the two substrates. The display device can be manufactured by stacking the polarizing plate of the present invention to an organic EL panel or an inorganic EL panel.

[6. Action and effect of this embodiment]

In the present embodiment, since the polarizing plate is manufactured by extending the stacked body having the resin film and the PVA layer stacked on the resin film, the PVA can be suppressed even in the case where the stacked body is stretched at a high magnification at a low temperature. The occurrence of the melting of the layer can suppress the appearance of the phase difference in the resin film after the stretching. As a result, according to the present embodiment, the resin film can be directly used as a protective film on one side of the PVA layer, and the wasted material can be reduced, so that "the resin film can be used as a protective film," Moreover, the method of manufacturing a polarizing plate can be efficiently manufactured even if the thickness is thin.

Further, according to the present embodiment, since the PVA layer 11 is directly stacked on the stack of the resin film 12, there is no other material between the resin film 12 and the PVA layer 11, so that the fracture suppressing effect is excellent and the production environment can be prevented. Environmental pollution caused by other substances in the medium, or prevention of defects in the product (mixing foreign matter).

[Embodiment 2: Polarizing plate and manufacturing method thereof]

Hereinafter, a polarizing plate 120 according to Embodiment 2 and a method of manufacturing the same will be described with reference to FIGS. 4 and 6. The polarizing plate 120 according to this embodiment is manufactured using the polarizing plate 100 according to the first embodiment. The same structures and aspects as those of the embodiment 1 are denoted by the same reference numerals, and the description thereof will be omitted.

[Polarizer]

Fig. 6 is a cross-sectional view showing a polarizing plate 120 according to Embodiment 2 of the present invention. In this polarizing plate 120, as shown in FIG. 6, a resin film 112 is stacked on one surface (the lower side in the drawing) of the PVA layer 111, and the other side of the PVA layer 111 (the upper side in the figure) is stacked and protected. Film 115. In Fig. 6, 114 is a bonding agent.

The method for producing the polarizing plate 120 of the present embodiment includes a fifth step of bonding the protective film to the surface of the PVA layer of the stacked body opposite to the resin film after the third step and the fourth step. The details are described below.

The polarizing plate 120 of this embodiment is manufactured using the apparatus shown in FIG. In the method of manufacturing the polarizing plate 120 of the present embodiment, after the dyeing treatment (the third step) of dyeing the PVA layer of the stacked body 10 and the stretching treatment (fourth step) of uniaxially stretching the stacked body, The polarizing plate 100 obtained by drying in the drying device 306.

The polarizing plate 120 can transport the polarizing plate 100 obtained by the dyeing process (third process) and the elongation process (fourth process) to the bonding device 308 on the opposite side of the PVA layer of the stack from the resin film. The surface (the side on the side where the resin film is not stacked: the upper side surface of the drawing) is coated with the bonding agent 114 and bonded to the protective film 115 (the fifth step) which is wound up from the winding device 307. The obtained polarizing plate 120 can be wound into a roll shape by the winding device 310 for further processing.

The bonding agent 114 used for bonding the protective film 115 to the PVA layer 111 used in the fifth step is not particularly limited, and examples thereof include an acrylic adhesive, an epoxy adhesive, and an amine ester. A bonding agent, a polyester-based bonding agent, a polyvinyl alcohol-based bonding agent, a polyolefin-based bonding agent, a modified polyolefin-based bonding agent, a polyvinyl alkyl ether-based bonding agent, a rubber-based bonding agent, vinyl chloride-vinyl acetate Ester-based bonding agent, SEBS (styrene-ethylene-butylene-styrene copolymer) bonding agent, ethylene-based bonding agent such as ethylene-styrene copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene - An acrylate-based bonding agent such as an ethyl (meth)acrylate copolymer.

The protective film 115 used in the fifth step is exemplified by one or more resins selected from the group consisting of a cycloolefin resin, an acrylic resin, a polyethylene terephthalate resin, and a triacetyl cellulose resin. film.

The polarizing plate of this embodiment is also the same as the polarizing plate of the first embodiment. The polarizing plate is manufactured by extending a stack of a resin film and a PVA layer directly stacked on the resin film, so that it has an embodiment 1 The same effect.

Further, according to the present embodiment, since the protective film 115 is provided on the surface of the PVA layer 111 on the side where the resin film 112 is not stacked, the surface of the PVA layer 111 is prevented from being scratched.

[Other implementations]

(1) In the first embodiment, a stack for a polarizing plate in which a PVA layer is stacked on one surface of a resin film is disclosed. In Embodiments 1 and 2, a polarizing plate manufactured by using the above stacked body is disclosed, but The invention is not limited thereto. The stack for polarizing plates may be a stacked body in which PVA layers are stacked on both sides of the resin film, and the polarizing plate may be a polarizing plate manufactured using the above stacked body.

(2) In the embodiment 1, a stack for a polarizing plate having a resin film and a PVA layer directly stacked on the resin film is disclosed, but it may be "between the resin film and the PVA layer, the resin is further improved. A stack of layers of bonding force between the film and the PVA layer.

『Example』

The invention will be further described in detail below with reference to the examples and comparative examples, but the invention is not limited by the following examples. The "parts" and "%" of the ratios of the ingredients below indicate the parts by weight unless otherwise noted.

[Evaluation method]

[Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)]

The molecular weight of the block copolymer and the block copolymer hydride was measured at 38 ° C as a standard polystyrene equivalent value of GPC which is a lysate of THF. A HLC8020GPC manufactured by TOSOH Corporation was used as a measuring device.

[hydrogenation rate]

The hydrogenation rate of the block copolymer hydride was calculated by ¹ H-NMR spectroscopy or GPC analysis. The region where the hydrogenation rate is 99% or less is calculated by measuring the ¹ H-NMR spectrum, and the region exceeding 99% is calculated from the ratio of the peak areas of the UV detector and the RI detector by GPC analysis.

[Measurement method of phase difference]

The phase difference Re1 in the in-plane direction of the polyvinyl alcohol layer, the phase difference Re2 in the in-plane direction of the extension of the resin film, and the phase difference in the in-plane direction of the resin film in the polarizing plate are phase difference meters (OPTO) Manufactured by SCIENCE, INC., trade name "Mueller matrix polarimeter (AxoScan)". When measuring, the measurement wavelength was set at 550 nm.

The measurement of the phase difference Re2 measures the phase difference in the in-plane direction of the resin film produced when the free end of the stack is uniaxially stretched to 6.0 times at a specified temperature (50 ° C and 120 ° C). In the present application, as long as "the phase difference in the in-plane direction of the resin film produced when the free end of the stack is uniaxially extended to 6.0 times at a temperature of 50 ° C" and "the temperature will be stacked at a temperature of 120 ° C" When the phase difference of the in-plane direction of the resin film generated when the free end of the body is uniaxially extended to 6.0 times is in the range of 0 nm or more and 20 nm or less, it is judged that "at a temperature of 50 ° C to 120 ° C The phase difference Re2" in the in-plane direction of the resin film produced when the free end of the stacked body is uniaxially extended to 6.0 times is 0 nm or more and 20 nm or less.

[Measurement method of thickness]

The thickness of each layer (polyvinyl alcohol layer and resin film) included in the stack and the thickness of each layer body included in the polarizing plate are thickness gauges (manufactured by Mitutoyo Corporation, trade name "ABS Digital Thickness Gauge" (547- 401)") The measurement was performed 5 times, and the average value was defined as the thickness of each layer.

[Evaluation of adhesion]

In the process from the manufacture of the polarizing plate of each of the examples to the second stretching treatment, the peeling between the polyvinyl alcohol layer and the resin film is defined as A, and the portion where the peeling is found is defined as B, which is completely The stripper is set to C.

[Evaluation of drying processability]

In the drying process at 70 ° C for 5 minutes in the production of the polarizing plate of each example, the crack was not determined to be A in the case where the polarizer was not cracked, and the crack was determined as C.

[black offset]

The liquid crystal display panel is removed from the liquid crystal display device (trade name "IPS panel display (23MP47), manufactured by LG Electronics Japan, Inc.), and the polarizing plate disposed on the viewing side is peeled off, and the resin film is attached to the panel side. The polarizing plates produced in the examples and comparative examples were combined. Further, a single unprotected film polarizer was attached to the polarizing plate produced in the examples and the comparative examples to recombine the liquid crystal display device. The absorption axes of the polarizing plates produced in the examples and the comparative examples and the polarizers of the single unprotected film were bonded in the same direction as the absorption axis of the polarizing plate before peeling.

When the direction of the absorption axis of the polarizing plate disposed on the viewing side is set to an azimuth angle of 0°, and the vertical direction of the panel is set to a polar angle of 0°, the panel is set to a black display state (ie, the entire display screen of the panel) The black state is displayed, and the azimuth angle is 45° and the polar angle is 45°. The same color change as in the case of the non-protective film polarizer is judged as A, and some color changers are judged as B, which will change. The big one is judged as C.

[Example 1]

(1-1) Production of Polymer X

According to the production example described in Japanese Laid-Open Patent Publication No. 2002-105151, after 25 parts of the styrene monomer is polymerized in the first stage, 30 parts of the styrene monomer and 25 parts of the isoprene monomer are obtained in the second stage. After polymerization, 20 parts of the styrene monomer was polymerized in the third stage to obtain a block copolymer [D1], and then the block copolymer was hydrogenated to synthesize a block copolymer hydride [E1]. The block copolymer hydride [E1] had a Mw of 84,500, a Mw/Mn of 1.20, and a hydrogenation ratio of the main chain and the aromatic ring of almost 100%.

In the 100 parts of the block copolymer hydride [E1], melt-kneaded 肆{3-[3,5-di(tributyl)-4-hydroxyphenyl]propanoic acid} pentaerythritol ester (Songyuan) 0.1 part of the product name "Songnox 1010" manufactured by Industrial Co., Ltd. was blended as an antioxidant, and then pelletized to obtain a polymer X for molding.

(1-2) Manufacture of resin film

After dissolving the polymer X produced in (1-1) in cyclohexane, 40 parts by weight of polyisobutylene (JX Nippon Mining & Energy Co., Ltd. "Nissan Polybutene" was added to 100 parts by weight of the polymer X. HV-300", a number average molecular weight of 1,400), and 0.1 part by weight of an organic ruthenium compound (3-aminopropyltriethoxydecane, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a coating liquid for casting film formation.

The obtained coating liquid for film formation was applied to a separator ("MRV38" manufactured by Mitsubishi Chemical Corporation) using a die coater and dried. Thereby, a resin film made of a polymer X having a width of 650 mm, a length of 500 m, and a thickness of 10 μm was obtained.

(1-3) Fabrication of the stack

An unstretched polyvinyl alcohol resin film (having an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol%, and a thickness of 20 μm, hereinafter also referred to as "PVA20") was dissolved in hot water at 95 ° C to prepare a polycondensate having a concentration of 10% by weight. Aqueous vinyl alcohol solution. The resin film produced in (1-2) was coated with the above aqueous polyvinyl alcohol solution, and then dried at 100 ° C for 10 minutes to obtain a long stack of polyvinyl alcohol layers having a width of 600 mm and a thickness of 5 μm. .

The thickness of the resin film in the obtained stacked body, the thickness of the polyvinyl alcohol layer and the phase difference Re1 in the in-plane direction, and the phase difference Re2 (temperature conditions of 50 ° C, 120 ° C) were measured. The results are disclosed in Table 1.

(1-4) Manufacture of polarizing plates

The stacked intermediate guide rolls manufactured in (1-3) were continuously conveyed in the longitudinal direction while performing the following operations.

The above-mentioned stacked body is subjected to a swell treatment of immersion in water, a dyeing treatment immersed in a dyeing solution containing iodine and potassium iodide, and a first stretching treatment of extending the dyed processed stack. Subsequently, the second extension treatment in which the stack after the first extension treatment is extended in a bath containing boric acid and potassium iodide is performed. The total stretch ratio indicated by the product of the stretch ratio at the time of the first stretching process and the stretch ratio at the time of the second stretching process is set to 6.0. The extension temperature was set at 57 °C. The second stretched laminate was dried in a dryer at 70 ° C for 5 minutes (drying step) to obtain a polarizing plate.

The adhesion was evaluated in the process up to the second extension process, and the drying processability was evaluated in the drying process, and the obtained polarizing plate was evaluated for black shift. The evaluation results are disclosed in Table 1.

Further, the thickness and phase difference of the resin film in the obtained polarizing plate and the thickness of the polyvinyl alcohol layer were measured. The measurement results are disclosed in Table 1.

[Example 2]

In addition to the addition of 0.1 part by weight of an organotitanium compound (tetraisopropyl titanate, ORGATIX TA-8, manufactured by Matsumoto Fine Chemical Co., Ltd.) in an amount of 0.1 part by weight, in addition to (1-2) of Example 1, A stack and a polarizing plate were produced in the same manner as in Example 1 except that a resin film was formed by using a coating liquid for film formation of an organic cerium compound, and the evaluation was carried out in accordance with Example 1. The results are disclosed in Table 1.

[Example 3]

In addition to the addition of 0.1 part by weight of an organic zirconium compound (n-propyl zirconate, ORGATIX ZA-45, manufactured by Matsumoto Fine Chemical Co., Ltd.) in an amount of 0.1 part by weight, in addition to the organic compound (1-2) of Example 1, A stack and a polarizing plate were prepared in the same manner as in Example 1 except that the resin film was formed by the coating liquid for film formation of the cerium compound, and evaluated in the same manner as in Example 1. The results are disclosed in Table 1.

[Example 4]

In the case of performing the operation of applying the coating liquid for film formation to the separator and drying it by using a die coater, the coating amount and the like are adjusted to produce a resin having a thickness of 5 μm. A laminate and a polarizing plate were produced in the same manner as in Example 1 except that the film (the width and the length were the same as in Example 1), and evaluated in the same manner as in Example 1. The results are disclosed in Table 1.

[Example 5]

A stack and a polarizing plate were produced in the same manner as in Example 1 except that polyisobutylene was not used in Example (1-2), and evaluation was carried out in accordance with Example 1. The results are disclosed in Table 2.

[Example 6]

In the operation of (1-2) of the first embodiment, the organic ruthenium compound is not used, and when the coating liquid for coating film is applied to the separator and dried using a die coater, the coating amount or the like is adjusted to produce a thickness of A stack and a polarizing plate were prepared in the same manner as in Example 1 except that a 5 μm long resin film (having the same width and length as in Example 1) was used and evaluated in the same manner as in Example 1. The results are disclosed in Table 2.

[Comparative Example 1]

In (1-3) of Example 1, only the unstretched polyvinyl alcohol resin film (PVA20) was used instead of the stack produced in (1-2), and the same operation as (1-3) was carried out. As a result, the first stretching treatment and the second stretching treatment were performed many times in the first stretching treatment and the second stretching treatment, and the fracture occurred many times in the drying step, and the adhesion and the black offset could not be evaluated.

[Comparative Example 2]

In addition to the (1-3) of the first embodiment, a cycloolefin resin film (Zeonor Film, a ring-opening polymer hydride of an alicyclic hydrocarbon, manufactured by Nippon Zeon Co., Ltd., thickness: 13 μm) was used instead of (1-2). The stack was produced in the same manner as in Example 1 except for the resin film produced in . As a result of performing the same operation as (1-4) of Example 1 using this stacked body, breakage occurred in the first stretching treatment, and a polarizing plate could not be produced.

The evaluation results of the examples and comparative examples are shown in Tables 1 and 2.

In the table, "COP" means a cycloolefin resin.

In the table, "Re2 (50 ° C)" means a phase difference in the in-plane direction of the resin film which is produced when the free end of the stack is uniaxially stretched to 6.0 times at a temperature of 50 ° C. (120 ° C)" means a phase difference in the in-plane direction of the resin film which is produced when the free end of the stack is uniaxially stretched to 6.0 times at a temperature of 120 °C.

In the table, "Re1" means a phase difference in the in-plane direction of the polyvinyl alcohol layer in the stack.

In the table, "coating" means that a PVA layer is formed by applying a polyvinyl alcohol aqueous solution to a resin film.

"Table 1"

"Table 2"

As is apparent from the results of Tables 1 and 2, according to the present invention, it is possible to reduce the phase difference exhibited by the resin film after the step of extending the stacked body, and to obtain a polarizing plate excellent in adhesion, drying processability, and optical physical properties. . According to the above, it is possible to provide a stack for a polarizing plate which can be used even if the resin film is used as a protective film, and which can be efficiently produced even if the thickness is thin, a method for producing the same, a polarizing plate using the same, and a method for producing the same And a stack of film rolls for polarizing plates.

10‧‧‧Stacks (stacks for polarizers)

11‧‧‧ Polyvinyl alcohol layer (PVA layer)

12‧‧‧Resin film

13‧‧‧Separator

15‧‧‧Stack film roll

100, 120‧‧‧ polarizing plate

111‧‧‧ Polyvinyl alcohol layer (PVA layer)

112‧‧‧Resin film

114‧‧‧Adhesive layer

115‧‧‧Protective film

200‧‧‧ manufacturing equipment

201, 202‧‧‧ rolled out device

203‧‧‧ Winding device

205‧‧‧Drying device

300‧‧‧ manufacturing equipment

301, 307‧‧‧ rolled out device

302～305‧‧‧Processing device

306, 309‧‧‧Drying device

308‧‧‧Fitting device

310‧‧‧Winding device

Fig. 1 is a schematic cross-sectional view showing a stack for a polarizing plate according to Embodiment 1 of the present invention.

Fig. 2 is a schematic view showing an example of a manufacturing apparatus of a stack for a polarizing plate according to Embodiment 1.

Fig. 3 is a schematic cross-sectional view showing a stacked film roll for a polarizing plate manufactured by using the stacked body for a polarizing plate according to Embodiment 1 of the present invention.

FIG. 4 is a schematic view showing an example of a manufacturing apparatus for manufacturing a polarizing plate using the stacked body for a polarizing plate according to the first embodiment.

Fig. 5 is a schematic cross-sectional view showing a polarizing plate manufactured by using the stacked body for a polarizing plate according to Embodiment 1 of the present invention.

Fig. 6 is a cross-sectional view showing a polarizing plate according to an embodiment 2 of the present invention.

Claims (12)

A stack for a polarizing plate, comprising: a resin film made of a cycloolefin resin; and a stack of polarizing plates stacked on the polyvinyl alcohol layer on at least one side of the resin film by coating, wherein the ring The olefin-based resin contains a cycloolefin-based polymer which is a block copolymer hydrogenated product obtained by hydrogenating the block copolymer [D], and the block copolymer [D] is derived from: The repeating unit of the aromatic vinyl compound [I] as the main component of the polymer block [A], and the repeating unit derived from the aromatic vinyl compound [I] and the repeating unit derived from the chain conjugated diene compound [ II] A polymer block [B] as a main component or a polymer block [C] having a repeating unit [II] derived from a chain conjugated diene compound as a main component. The stack for polarizing plates according to claim 1, wherein the polyvinyl alcohol layer has a thickness T of 45 μm or less, and a phase difference Re2 of the in-plane direction of the extension of the resin film is 0 nm or more and 20 nm or less. The phase difference Re2 is uniaxially extended to 6.0 times the free end of the stack for a polarizing plate at a temperature of 50 ° C to 120 ° C, and when the resin film is formed into the extension, the extension has Phase difference. The stack for a polarizing plate according to claim 1 or 2, wherein the cycloolefin resin contains a plasticizer, a softener or both. The stack for polarizing plates according to claim 3, wherein the plasticizer, the softener or both are selected from one or more of an ester plasticizer and an aliphatic hydrocarbon polymer. The stack for a polarizing plate according to claim 1 or 2, wherein the resin film contains an organometallic compound. The stack for a polarizing plate according to claim 1 or 2, wherein the polyvinyl alcohol layer is directly stacked on the layer of the resin film. A polarizing plate which is a uniaxially stretched body of the polarizing plate stack according to any one of claims 1 to 6. A stacked film roll for a polarizing plate, which is wound into a roll, and has a stack for a polarizing plate according to any one of claims 1 to 6, and a resin film stacked on the stack for the polarizing plate A separator on the side opposite to the side of the polyvinyl alcohol layer. A method for producing a stack for a polarizing plate, comprising: a first step of coating a polyvinyl alcohol resin to form a polyvinyl alcohol layer on at least one side of a resin film made of a cycloolefin resin; a second step of drying the polyvinyl alcohol layer formed in the first step; wherein the cycloolefin resin comprises a cycloolefin polymer, and the cycloolefin polymer is a block obtained by hydrogenating the block copolymer [D] a copolymer hydride [D] consisting of a polymer block [A] having a repeating unit [I] derived from an aromatic vinyl compound as a main component, and a compound derived from an aromatic vinyl compound a repeating unit [I] and a polymer block [B] derived from a repeating unit [II] of a chain conjugated diene compound as a main component, or a repeating unit derived from a chain conjugated diene compound [II] A polymer block [C] as a main component. The method for producing a stack for a polarizing plate according to claim 9, which is formed by one or more methods selected from the group consisting of solution coating, emulsion coating or melt extrusion coating. A method of producing a polarizing plate, which is obtained by using the stack for a polarizing plate according to any one of claims 1 to 6 or the method for producing a stack for a polarizing plate according to claim 9 or 10. A method for producing a polarizing plate by using a stacked body of a polarizing plate, comprising: a third step of dyeing the polarizing plate stack with a dichroic dye; and a fourth step of extending the stack for the polarizing plate uniaxially. The method for producing a polarizing plate according to claim 11, comprising: after the third step, the fourth step, or the like, the polyvinyl alcohol layer and the resin film in the stack for the polarizing plate The opposite side of the surface is attached to the fifth step of the protective film.