KR20210118823A - A laminate, a polarizing plate, a manufacturing method of a laminate, a manufacturing method of a polarizing plate, and a manufacturing method of a display device - Google Patents

Abstract

A laminate having a polarizer material film and a resin layer formed directly on the polarizer material film, wherein the retardation Re1 in the in-plane direction of the polarizer material film is greater than 50 nm, and the thickness T1 of the polarizer material film is 45 μm or less. The polarizer material film is preferably a polarizer material film obtained by stretching at a specific stretching ratio X times. The polarizing plate obtained using the said laminated body, the manufacturing method of a laminated body, the manufacturing method of a polarizing plate, and the manufacturing method of a display device are also provided.

Description

A laminate, a polarizing plate, a manufacturing method of a laminate, a manufacturing method of a polarizing plate, and a manufacturing method of a display device

The present invention relates to a laminate, a polarizing plate, a manufacturing method of a laminate, a manufacturing method of a polarizing plate, and a manufacturing method of a display device.

DESCRIPTION OF RELATED ART Conventionally, as a display apparatus, such as a liquid crystal display device and an organic electroluminescent (EL) display device, a large display area, light weight, and thin thickness are calculated|required. Therefore, a thin panel is also conventionally calculated|required for the panel which comprises a display apparatus.

A polarizing plate provided with a polarizer and the protective film which protects a polarizer is generally used for a display apparatus. In order to configure a thin display device, a thinner polarizing plate is also required. In particular, since a polarizer may shrink in the use environment of a display device, in a display device with a thin and large area, the curvature by such shrinkage|contraction may become a problem. Therefore, by employing 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 warpage as described above can be expected.

By the way, when it is going to manufacture the light polarizer of polyvinyl alcohol with such a thin thickness by the conventional manufacturing method, melting and cutting of a light polarizer is frequent. Several methods have been proposed as a method for preventing the melting of such a polarizer and manufacturing a polarizing plate including a thin polarizer.

For example, in Patent Document 1, an unstretched polyvinyl alcohol-based film is affixed to a base film made of unstretched high-density polyethylene to obtain a laminate, and after stretching the laminate, the base film is peeled and polyvinyl alcohol A method for obtaining a system film has been proposed.

Japanese Unexamined Patent Publication No. 2016-505404 (corresponding publication: Specification of U.S. Patent Application Laid-Open No. 2016/084990)

When manufacturing a thin polarizing plate by the method of patent document 1, it originates in extending|stretching a laminated body at a high draw ratio, and retardation may generate|occur|produce in the base film after an extending|stretching process. In such a case, it is difficult to use a base film as a polarizing plate protective film as it is, and since it peels and discards, useless material arises.

Therefore, it was examined manufacturing a polarizing plate using the laminated body which bonded together the stretched polyvinyl alcohol resin film and the unstretched base film through the polyvinyl alcohol-type adhesive agent. However, by this method, when a polyvinyl alcohol-type adhesive agent permeates into the polyvinyl alcohol resin film after extending|stretching, in a laminated body and a polarizing plate, wrinkles and a void may generate|occur|produce.

Therefore, according to the present invention, the resin layer can also be used as a protective film, can be efficiently manufactured even if the thickness is thin, and the laminate and its manufacturing method that prevent the occurrence of wrinkles and voids, and a polarizing plate using the laminate And it aims at providing the manufacturing method, and the manufacturing method of the display device using the said polarizing plate.

As a result of studying in order to solve the said subject, this inventor solves the said subject by using the laminated body which has a polarizer material film which has a predetermined retardation and predetermined thickness, and the resin layer formed directly on the polarizer material film. Finding out what could be done, the present invention was completed.

Accordingly, according to the present invention, the following [1] to [21] are provided.

[1] A laminate having a polarizer material film and a resin layer directly formed on the polarizer material film, comprising:

The retardation Re1 in the in-plane direction of the polarizer material film is greater than 50 nm,

The laminated body whose thickness T1 of the said polarizer material film is 45 micrometers or less.

[2] The laminate according to [1], wherein the polarizer material film is a film obtained by stretching at a draw ratio X times.

[3] The laminate according to [2], wherein X satisfies 1.5 ≤ X ≤ 5.5.

[4] the retardation Re2 in the in-plane direction of the stretched resin layer is 0 nm or more and 20 nm or less,

The stretched resin layer is a stretched product of the resin layer in a stretched laminate, and the stretched laminate is a stretched product obtained by uniaxially stretching the laminate at a free end by 4.0 times under a temperature condition of 50°C to 120°C. , The laminate according to any one of [1] to [3].

[5] The laminate according to any one of [1] to [4], wherein the polarizer material film is a polyvinyl alcohol resin film.

[6] The laminate according to [5], wherein the polyvinyl alcohol resin film has a transmittance of light having a wavelength of 550 nm of 50% or more.

[7] The laminate according to any one of [1] to [6], wherein the resin layer is made of a cycloolefin-based resin.

[8] The cycloolefin-based resin includes a cycloolefin-based polymer,

The cycloolefin-based polymer comprises a polymer block [A] mainly comprising a repeating unit [I] derived from an aromatic vinyl compound;

A polymer block [B] mainly comprising a repeating unit [I] derived from an aromatic vinyl compound and a repeating unit [II] derived from a chain conjugated diene compound, or a repeating unit [II] derived from a chain conjugated diene compound as a main component The laminate according to [7], which is a block copolymer hydride obtained by hydrogenating a block copolymer [D] comprising a polymer block [C].

[9] The resin layer is a layer made of a resin,

The resin has a melt flow rate of 1 g/10 min or more, and a tensile modulus E of 50 MPa or more and 1200 MPa or less,

The laminate according to any one of [1] to [8], wherein the melt flow rate is a value measured at 190°C and a load of 2.16 kg.

[10] The laminate according to any one of [1] to [9], wherein the resin layer contains a plasticizer, a softener, or both.

[11] The laminate according to [10], wherein the plasticizer, the softener, or both of them are at least one selected from the group consisting of an ester plasticizer and an aliphatic hydrocarbon polymer.

[12] The laminate according to any one of [1] to [11], wherein the resin layer contains an organometallic compound.

[13] A polarizing plate, which is a uniaxially stretched product of the laminate according to any one of [1] to [12].

[14] A first step of stretching a raw film containing a material for a polarizer to obtain a film of a polarizer material;

a second step of applying a resin to one surface of the polarizer material film to form an application layer;

The manufacturing method of the laminated body including the 3rd process of drying the said application layer in this order.

[15] The method for producing a laminate according to [14], wherein in the first step, the draw ratio of the drawing is X times, and X satisfies 1.5 ≤ X ≤ 5.5.

[16] The method for producing a laminate according to [14] or [15], including a fourth step of activating the surface of the polarizer material film before the second step.

[17] A method for manufacturing a polarizing plate, comprising:

A step of preparing the laminate according to any one of [1] to [12] or manufacturing the laminate by the method for producing the laminate according to any one of [14] to [16];

a fifth step of dyeing the laminate with a dichroic dye;

The manufacturing method of the polarizing plate including the 6th process of uniaxially stretching the said laminated body.

[18] The method for producing a polarizing plate according to [17], wherein in the sixth step, the stretching ratio is Z times, and Z satisfies 1.2 ≤ Z ≤ 5.0.

[19] The method for producing a polarizing plate according to [17] or [18], wherein X and Z satisfy 5.1 ≤ X * Z ≤ 9.0.

[20] After passing through said 5th process, said 6th process, or both of these, among the surface on the side of the said polarizer material film of the said laminated body, and the surface on the side of the said resin layer, on one or both surfaces, a protective film The manufacturing method of the polarizing plate in any one of [17]-[19] including the 7th process of bonding together.

[21] A method of manufacturing a display device, comprising:

A step of manufacturing a polarizing plate by the method for manufacturing a polarizing plate according to any one of [17] to [20], and

an eighth step of laminating the polarizing plate to the panel;

The method for manufacturing a display device, wherein the panel is a panel selected from a liquid crystal panel, an organic electroluminescent panel, and a micro LED panel.

According to the present invention, the resin layer can also be used as a protective film, can be efficiently manufactured even if the thickness is thin, and further, a laminate and a method for manufacturing the same, which prevents the generation of wrinkles and voids, a polarizing plate using the laminate, and The manufacturing method and the manufacturing method of the display device using the said polarizing plate can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed typically the laminated body which concerns on Embodiment 1. FIG.
It is the schematic which showed typically an example of the manufacturing apparatus used for the manufacturing method of the laminated body which concerns on Embodiment 1. FIG.
It is the schematic which showed typically an example of the manufacturing apparatus used for the manufacturing method of the polarizing plate which concerns on Embodiment 1. FIG.
4 is a cross-sectional view schematically showing a polarizing plate manufactured using the laminate according to the first embodiment.
5 is a cross-sectional view schematically showing a polarizing plate manufactured by the method for manufacturing a polarizing plate according to the second embodiment.
6 is a cross-sectional view schematically showing a display device manufactured by the method for manufacturing a display device according to the third embodiment.
7 is a cross-sectional view schematically showing a display device manufactured by the method for manufacturing a display device according to the fourth embodiment.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be implemented by changing arbitrarily within a range not departing from the scope of the claims of the present invention and its equivalents.

In the present application, the "long" film refers to a film having a length of 5 times or more with respect to the width of the film, preferably having a length of 10 times or more, and specifically, it is wound in a roll shape and stored or transported. means having a length. Although the upper limit of the ratio of the length with respect to the width|variety of a film is not specifically limited, For example, it can be 100,000 times or less.

In the present application, the retardation Re in the in-plane direction and the retardation Rth in the thickness direction of the film are, according to the formula Re = (nx - ny) × d, and Rth = [{(nx + ny)/2} - nz] × d Calculate. In addition, the Nz coefficient of a film is a value represented by [(nx - nz)/(nx - ny)], and can also be represented by [(Rth/Re) + 0.5]. where nx is the refractive index in the in-plane slow axis direction of the film (in-plane maximum refractive index), ny is the refractive index in the in-plane direction perpendicular to the in-plane slow axis of the film, nz is the refractive index in the thickness direction of the film, , d is the thickness (nm) of the film. The measurement wavelength is 550 nm, which is a typical wavelength in the visible region, unless otherwise specified.

[Embodiment 1: Laminate product and its manufacturing method, polarizing plate and its manufacturing method]

EMBODIMENT OF THE INVENTION Hereinafter, the laminated body of Embodiment 1 which is one Embodiment of this invention, its manufacturing method, and the polarizing plate using the said laminated body, and its manufacturing method are demonstrated, referring FIGS.

[One. laminate]

The laminate of the present invention has a polarizer material film and a resin layer directly formed on the polarizer material film. The laminate of this invention WHEREIN: The retardation Re1 of the in-plane direction of a polarizer material film is larger than 50 nm, and thickness T1 of a polarizer material film is 45 micrometers or less.

As is clear from context, in this invention, a "resin layer" is a layer different from a polarizer material film.

In the present invention, the "resin layer formed directly on the polarizer material film" is formed on the surface of the layer of the material constituting the polarizer material film, and as a result, it is a resin layer in a state in direct contact with the surface of the polarizer material film. .

1 : is an example of sectional drawing which showed typically the laminated body 10 of Embodiment 1 which concerns on this invention. As shown in FIG. 1, the laminated body 10 of this embodiment contains the polarizer material film 11 and the resin layer 12 formed in one surface (illustration upper side surface) of the polarizer material film 11. do. The laminate 10 of this invention is a material for manufacturing a polarizer and a polarizing plate provided with a polarizer.

[Polarizer material film]

A polarizer material film is a film (film for polarizers) for manufacturing a polarizer. In this invention, retardation Re1 of the in-plane direction of a polarizer material film is larger than 50 nm, and thickness T1 is a film whose thickness T1 is 45 micrometers or less. A polarizer material film can be obtained by extending|stretching an unstretched film containing the material of a polarizer so that retardation Re1 in in-plane direction may be larger than 50 nm, and thickness T1 may become 45 micrometers or less. A polarizer material film is a (stretched) film containing the material of a polarizer. In the present invention, a film for obtaining a polarizer material film that is not subjected to stretching treatment to obtain a predetermined retardation and thickness (unstretched film containing a polarizer material) is called a “raw film”. The raw film contains the material of the polarizer.

In this invention, although it will not necessarily limit if the objective of this invention can be achieved as a raw film, From the height of cost performance, a polyvinyl alcohol resin film is preferable.

In the present invention, the polyvinyl alcohol resin film that can be used as a raw film (hereinafter, may be referred to as "PVA resin film") is not necessarily limited, but from the viewpoint of availability, vinyl acetate is polymerized and It is preferable to use what was manufactured by saponifying the polyvinyl acetate obtained. Polyvinyl alcohol (hereinafter, may be referred to as "PVA") contained in the PVA resin film is excellent in stretchability and polarization performance of the obtained polarizer, and the polymerization degree is preferably in the range of 500 to 8000. and the degree of saponification is preferably 90 mol% or more. Here, the degree of polymerization is an average degree of polymerization measured according to the description of JIS K6726-1994, and the degree of saponification is a value measured according to the description of JIS K6726-1994. The more preferable range of polymerization degree is 1000-6000, More preferably, it is 1500-4000. A more preferable range of the degree of saponification is 95 mol% or more, and still more preferably 99 mol% or more. PVA may be a copolymer of vinyl acetate and another monomer copolymerizable with, or a graft polymer.

In this invention, the manufacturing method of the PVA resin film which can be used as a raw film is not specifically limited, It can manufacture by arbitrary methods, such as a well-known method. Examples of the manufacturing method include a film forming method using a PVA solution in which PVA is dissolved in a solvent as a film forming undiluted solution, a wet film forming method (discharging into a poor solvent), a dry and wet film forming method, a gel film forming method (a PVA aqueous solution is once cooled and gelled) Then, the method by extracting and removing a solvent to obtain a PVA resin film), and the method by these combinations are mentioned. As a further example of a manufacturing method, the melt-extrusion film forming method which melt|melted PVA containing a solvent as a film forming undiluted|stock solution is mentioned. Among these, the film-casting method and the melt-extrusion film forming method are preferable at the point which transparency is high and the PVA resin film with little coloring is obtained, and the melt-extrusion film forming method is more preferable at the point which can obtain a high film forming rate.

In the present invention, the PVA resin film that can be used as a raw film contains a plasticizer such as polyhydric alcohol such as glycerin, 0.01 to 30 weight per PVA, in order to improve mechanical properties and process passability during secondary processing. %, and, in order to improve handleability and film appearance, it is preferable to contain 0.01 to 1% by weight of surfactants such as anionic surfactants and nonionic surfactants with respect to PVA.

The PVA resin film that can be used as a raw film is, if necessary, an antioxidant, a UV absorber, a lubricant, a pH adjuster, inorganic fine particles, a colorant, a preservative, an anti-mold agent, other high molecular compounds other than the above components, moisture, and other optional components may contain more. The PVA resin film may contain 1 type, or 2 or more types of the said arbitrary components.

The thickness of the raw film is preferably 60 µm or less, more preferably 45 µm or less, still more preferably 30 µm or less, preferably 10 µm or more, more preferably 15 µm or more, still more preferably 20 µm or more. When the thickness of the raw film is more than the lower limit of the range, a polarizing plate having a sufficiently high degree of polarization can be obtained, and by being less than or equal to the upper limit of the range, the resistance to bending of the polarizing plate can be effectively increased.

A polarizer material film can be made into the film obtained by extending|stretching. A polarizer material film can be obtained by extending|stretching a raw film. As a method of an extending|stretching process, dry extending|stretching, wet extending|stretching, etc. are mentioned. Since dry-type extending|stretching has a simple installation and process compared with wet extending|stretching, as a polarizer material film, what is obtained by dry extending|stretching is preferable. As dry stretching, stretching methods, such as tenter stretching, float stretching, and hot roll stretching, can be used. Dry stretching means the method of the extending|stretching process extending|stretching in the gas atmosphere of high temperature (for example, 100 degreeC or more). The gas used in dry stretching is air.

The conditions for extending|stretching at the time of extending|stretching a raw film and setting it as a polarizer material film can be suitably selected so that a desired polarizer material film may be obtained. For example, the aspect of extending|stretching at the time of extending|stretching a raw film and setting it as a polarizer material film can be made into arbitrary aspects, such as uniaxial stretching and biaxial stretching. In addition, when the raw film is a long film, the stretching direction is longitudinal (direction parallel to the longitudinal direction of the long film), transverse direction (direction parallel to the width direction of the long film), and oblique direction ( direction which is neither a vertical direction nor a horizontal direction) may be sufficient.

A polarizer material film can be made into the film stretched|stretched by the draw ratio X times. X preferably satisfies 1.5 ≤ X ≤ 5.5. Such a polarizer material film can be obtained by extending|stretching a raw film by the draw ratio X times. In this invention, X becomes like this. Preferably it is 1.5 or more, More preferably, it is 2.0 or more, More preferably, it is 2.5 or more, Preferably it is 5.5 or less, More preferably, it is 4.5 or less, More preferably, it is 3.5 or less. That is, the polarizer material film is preferably a film stretched at a draw ratio of 1.5 times or more and 5.5 times or less, more preferably a film stretched at a draw ratio of 2.0 times or more and 4.5 times or less, and 2.5 times or more and 3.5 times or less. It is more preferable that it is a film stretched by a draw ratio. When X is below the upper limit of the said range, when extending|stretching a raw film and setting it as a polarizer material film, generation|occurrence|production of a fracture|rupture can be prevented. Moreover, when X shall be more than the lower limit of the said range, the draw ratio at the time of extending|stretching a laminated body and obtaining a polarizing plate can be made low. When extending|stretching of a raw film by extending|stretching to two or more directions, such as biaxial stretching, draw ratio X is the product of the magnification|multiplying_factor of each extending|stretching.

The stretching temperature at the time of dry stretching the raw film to obtain a polarizer material film is preferably 100°C or higher, more preferably 110°C or higher, and preferably 150°C or lower, more preferably 140°C or lower. When the temperature of dry extending|stretching is the said range, the polarizer material film of a uniform film thickness is obtained.

It is preferable that a polarizer material film is a PVA resin film. As the PVA resin film usable as the polarizer material film, a film having a transmittance of light having a wavelength of 550 nm (hereinafter referred to as “transmittance of light at a wavelength of 550 nm” is also referred to as “light transmittance”) is preferably 50% or more. As the PVA resin film, an uncolored film can be used. The light transmittance of such a PVA resin film becomes like this. Preferably it is 55 % or more, More preferably, it is 60 % or more, Preferably it is 99 % or less, More preferably, it is 97 % or less.

The thickness T1 of the polarizer material film is preferably 45 µm or less, more preferably 35 µm or less, still more preferably 25 µm or less, preferably 5 µm or more, more preferably 7 µm or more, still more preferably 10 µm or more. . When the thickness of a polarizer material film is below the upper limit of the said range, the contractile force of a polarizing plate can be lowered effectively, and when it is more than the lower limit of the said range, the polarizing plate which has a sufficiently high polarization degree can be obtained.

The retardation Re1 in the in-plane direction of the polarizer material film is preferably 50 nm or more, more preferably more than 50 nm, still more preferably 100 nm or more, particularly preferably 150 nm or more, preferably 1500 nm or less, more preferably less than 1000 nm. When the retardation Re1 in the in-plane direction of the polarizer material film is equal to or greater than the lower limit of the above range, the draw ratio when the laminate is stretched to obtain a polarizing plate can be suppressed low, and the retardation of the resin layer after the stretching process can be kept low.

The shape and dimension of a polarizer material film can be suitably adjusted to the thing according to a desired use. From the viewpoint of production efficiency, the polarizer material film is preferably a long film.

[resin layer]

The resin layer is a layer made of resin. The resin layer may be a resin layer formed by applying a resin to the polarizer material film. Alternatively, the resin layer can be formed by directly thermocompression bonding the film-like resin onto the polarizer material film. "Direct thermocompression bonding" on the polarizer material film means that the polarizer material film and the film-like resin serving as the resin layer are pressed between the polarizer material film and the resin layer without intervening an adhesive or an adhesive.

In the present invention, the resin constituting the resin layer is preferably a resin having flexibility that can be stretched at a high draw ratio (for example, 6.0 times) at a low temperature (for example, 50 to 120° C.). Examples of such a resin include a cycloolefin-based resin containing a cycloolefin-based polymer, and a resin having a melt flow rate of 1 g/10 min or more and a tensile modulus E of 50 MPa or more and 1200 MPa or less. can The melt flow rate here is a value measured at 190°C and a load of 2.16 kg. Hereinafter, "the melt flow rate measured at 190 degreeC and a load of 2.16 kg" is also simply called "MFR".

[profit]

The cycloolefin-based resin is a resin containing a cycloolefin-based polymer. Examples of the cycloolefin-based polymer contained in the cycloolefin-based resin include a polymer block [A] mainly comprising a repeating unit [I] derived from an aromatic vinyl compound, a repeating unit [I] derived from an aromatic vinyl compound, and a chain conjugated diene Hydrogenation of a block copolymer [D] comprising a polymer block [B] mainly composed of a compound-derived repeating unit [II] or a polymer block [C] containing a chain-type conjugated diene compound-derived repeating unit [II] as a main component One block copolymer hydride is preferred. Examples of such block copolymer hydrides include WO2000/32646, WO2001/081957, Japanese Patent Application Laid-Open No. 2002-105151, Japanese Patent Application Laid-Open No. 2006-195242, Japanese Patent Application Laid-Open No. 2011-13378, WO2015/002020 Polymers as described in etc. are mentioned. The cycloolefin resin preferably has an MFR of 1 g/10 min or more and a tensile modulus E of 50 MPa or more and 1200 MPa or less, but MFR, the tensile modulus E, or both may be outside the above range.

Further, in the present invention, the "polymer block [A] mainly comprising the repeating unit [I] derived from an aromatic vinyl compound" is "a polymer block [A] containing more than 60 mass % of the repeating unit derived from an aromatic vinyl compound" ' can be done. "Polymer block [B] mainly comprising a repeating unit [I] derived from an aromatic vinyl compound and a repeating unit [II] derived from a chain conjugated diene compound" is "a repeating unit derived from an aromatic vinyl compound [I] and a chain conjugated It can be set as the polymer block [B]" which the sum total of the repeating unit [II] derived from a diene compound contains more than 60 mass %. "Polymer block [C] mainly composed of repeating units [II] derived from a chain conjugated diene compound" is defined as "Polymer block [C] containing more than 60 mass % of repeating units derived from a chain conjugated diene compound" can

In the present invention, the resin constituting the resin layer is preferably a resin having a melt flow rate of 1 g/10 min or more and a tensile modulus E of 50 MPa or more and 1200 MPa or less. The resin having an MFR of 1 g/10 min or more and a tensile modulus E of 50 MPa or more and 1200 MPa or less is preferably a cycloolefin-based resin, but may be a resin other than the cycloolefin-based resin.

The resin has an MFR of preferably 1 g/10 min or more, more preferably 3 g/10 min or more, still more preferably 5 g/10 min or more, preferably 300 g/10 min or less, and more preferably preferably less than 100 g/10 min. By making MFR of resin more than a lower limit, when it is set as a polarizing plate, retardation can be suppressed small, and heat resistance can be improved by making MFR or less into an upper limit.

MFR of resin can be measured on condition of a temperature of 190 degreeC and a load of 2.16 kg using a melt indexer based on JIS-K-7210.

In the present invention, the tensile modulus E of the resin constituting the resin layer is preferably 50 MPa or more, more preferably 100 MPa or more, still more preferably 200 MPa or more, preferably 1200 MPa or less, more preferably preferably 1000 MPa or less, more preferably 800 MPa or less. By making the tensile modulus E of the resin equal to or greater than the lower limit, the retardation of the resin layer is reduced when the laminate is stretched to obtain a polarizing plate, and by the upper limit or less, the occurrence of breakage of the resin layer when stretching the laminate can be prevented. have.

The tensile modulus of elasticity can be measured using a tensile tester (manufactured by Instron Japan Co., Ltd., trade name "electromechanical universal material tester 5564") based on JIS K7127.

[Plasticizer and Softener]

In this invention, it is preferable that resin which comprises a resin layer contains a plasticizer, a softener, or these both. By containing a plasticizer, a softener, or these both, when a laminated body is extended|stretched and a polarizing plate is obtained, the retardation which generate|occur|produces in a resin layer can be made small.

As the plasticizer and the softener, those that can be uniformly dissolved or dispersed in the resin constituting the resin layer can be used. Specific examples of the plasticizer and softener include an ester plasticizer composed of a polyhydric alcohol and a monohydric carboxylic acid (hereinafter referred to as a "polyhydric alcohol ester plasticizer"), and an ester system composed of a polyhydric carboxylic acid and a monohydric alcohol. ester plasticizers such as plasticizers (hereinafter, referred to as "polycarboxylic acid ester plasticizers"); and phosphate ester plasticizers; carbohydrate ester plasticizers; and other polymer softeners.

Although it does not specifically limit as an example of the polyhydric alcohol which is a raw material of the ester plasticizer used preferably in this invention, Ethylene glycol, glycerol, and trimethylol propane are preferable.

Examples of the polyhydric alcohol ester plasticizer include ethylene glycol ester plasticizers, glycerin ester plasticizers, and other polyhydric alcohol ester plasticizers.

As an example of polyhydric carboxylate type plasticizer, a dicarboxylic acid ester type plasticizer and another polyhydric carboxylic acid ester type plasticizer are mentioned.

Specific examples of the phosphate ester plasticizer include: phosphate alkyl esters such as triacetyl phosphate and tributyl phosphate; phosphoric acid cycloalkyl esters such as tricyclopentyl phosphate and cyclohexyl phosphate; and phosphoric acid aryl esters such as triphenyl phosphate and tricresyl phosphate.

Specific examples of the carbohydrate ester plasticizer include glucose pentaacetate, glucose pentapropionate, glucose pentabutyrate, saccharose octaacetate, and saccharose octabenzoate, and among these, saccharose octaacetate is more preferable. .

Specific examples of the polymer softener include an aliphatic hydrocarbon polymer, an alicyclic hydrocarbon polymer, ethyl polyacrylate, polymethyl methacrylate, a copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate, and methacrylic acid. acrylic polymers such as a copolymer of methyl, methyl acrylate, and 2-hydroxyethyl methacrylate; vinyl polymers such as polyvinyl isobutyl ether and poly N-vinyl pyrrolidone; styrenic polymers such as polystyrene and poly4-hydroxystyrene; polyesters such as polybutylene succinate, polyethylene terephthalate, and polyethylene naphthalate; polyethers such as polyethylene oxide and polypropylene oxide; Polyamide, polyurethane, polyurea, etc. are mentioned.

Specific examples of the aliphatic hydrocarbon polymer include low molecular weight substances such as polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, and ethylene/α-olefin copolymer, and hydrides thereof; Low molecular weight substances, such as polyisoprene and a polyisoprene-butadiene copolymer, and its hydride, etc. are mentioned. It is preferable that the aliphatic hydrocarbon-type polymer has a number average molecular weight of 300-5,000 from a viewpoint of being easy to melt|dissolve or disperse|distribute uniformly in a cycloolefin resin.

These polymer softeners may be a homopolymer composed of one type of repeating unit, or may be a copolymer having a plurality of repeating structures. Moreover, you may use the said polymer in combination of 2 or more types.

In the present invention, the plasticizer, the softener, or both (hereinafter also referred to as "plasticizer, etc.") is selected from ester plasticizers and aliphatic hydrocarbon polymers from the viewpoint of particularly excellent compatibility with the resin constituting the resin layer. More than one species is preferred.

The proportion of the plasticizer in the resin layer, with respect to 100 parts by weight of the resin constituting the resin layer, is preferably 0.2 parts by weight or more, more preferably 0.5 parts by weight or more, still more preferably 1.0 parts by weight or more. , On the other hand, preferably 50 parts by weight or less, more preferably 40 parts by weight or less. By making the ratio of a plasticizer etc. into the said range, even if it goes through the manufacturing process of a polarizing plate including an extending|stretching process for a resin layer, expression of retardation can be made low enough.

[Organic metal compound]

In the present invention, the resin layer preferably contains an organometallic compound. By including an organometallic compound, generation|occurrence|production of peeling of a resin layer in the case where a laminated body is extended|stretched by a high draw ratio (for example, wet-stretched at a draw ratio 6.0) can be suppressed more effectively.

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. As an organometallic compound, an organosilicon compound, an organotitanium compound, an organoaluminum compound, an organozirconium compound, etc. are mentioned. Among these, since it is excellent in reactivity with polyvinyl alcohol, an organosilicon compound, an organotitanium compound, and an organozirconium compound are preferable, and an organosilicon compound is more preferable. You may use an organometallic compound 1 type or in combination of 2 or more type.

Examples of the organometallic compound include, but are not limited to, an organosilicon compound represented by the following formula (1).

R ¹ _a Si(OR ² ) _4-a (1)

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an epoxy group, an amino group, a thiol group, an isocyanate group, and 1 carbon atom. to 10 represents a group selected from the group consisting of organic groups, and a represents an integer from 0 to 4.)

In Formula (1), ^{for example, preferable as R 1} , an epoxy group, an amino group, a thiol group, an isocyanate group, a vinyl group, an acryl group, an aryl group, —CH ₂ OC _n H _2n+1 (n is 1-4 An integer is shown.) A C1-C8 alkyl group etc. are mentioned.

Further, formula (1), as R ^2, for preferred examples, hydrogen atom, vinyl group, aryl group, acrylic group, the carbon atom number of 1 to 8 alkyl group, -CH ₂ OC _n H _{2n + 1} (n is the An integer of 1-4 is shown.) etc. are mentioned.

Examples of the organosilicon compound include epoxy-based organosilicon compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. , amino-based organosilicon compounds such as N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, isocyanurate-based organosilicon compounds such as tris-(trimethoxysilylpropyl)isocyanurate; Isocyanate-type organosilicon compounds, such as mercapto type organosilicon compounds, such as 3-mercaptopropyl trimethoxysilane, and 3-isocyanate propyl triethoxysilane, are mentioned.

Examples of the organic titanium compound include titanium alkoxides such as tetraisopropyl titanate, titanium chelates such as titanium acetylacetonate, and titanium acylates such as titanium isostearate.

Examples of the organic zirconium compound include zirconium alkoxides such as normal propyl zirconate, zirconium chelates such as zirconium tetraacetylacetonate, and zirconium acylates such as zirconium stearate.

Examples of the organoaluminum compound include aluminum alkoxides such as aluminum secondary butoxide and aluminum chelates such as aluminum trisacetylacetonate.

The ratio of the organometallic compound in the resin layer is preferably 0.005 parts by weight or more, more preferably 0.01 parts by weight or more, still more preferably 0.03 parts by weight or more, with respect to 100 parts by weight of the resin constituting the resin layer. and, on the other hand, preferably 1.0 part by weight or less, more preferably 0.5 part by weight or less. By making the ratio of an organometallic compound into the said range, generation|occurrence|production of peeling of a resin layer in the case of wet-stretching a laminated body at high magnification (for example, draw ratio 6.0) can be suppressed more effectively.

[Optional Ingredients]

The resin layer may contain an optional component in addition to a resin, a plasticizer, an organometallic compound, and the like. Examples of the optional component include stabilizers such as antioxidants, ultraviolet absorbers, and light stabilizers; resin modifiers such as lubricants; colorants such as dyes and pigments; and antistatic agents. These compounding agents can be used individually by 1 type or in combination of 2 or more type, The compounding quantity is selected suitably.

[Thickness of resin layer]

3 micrometers or more are preferable, as for the thickness of the resin layer in a laminated body, 5 micrometers or more are more preferable, 60 micrometers or less are preferable, and 20 micrometers or less are more preferable. When the thickness of the resin layer is equal to or more than the lower limit of the above range, melting of the polarizer in the polarizing plate forming step can be effectively prevented, and by being below the upper limit of the above range, the resin layer is generated by stretching the laminate to obtain a polarizing plate The phase difference can be made small.

[Re2 of the resin layer]

It is preferable that Re2 of a resin layer is 0 nm or more and 20 nm or less. Re2 is more preferably 0 nm or more, more preferably 10 nm or less, and particularly preferably 5 nm or less. When Re2 is below an upper limit, when the laminated body 10 is extended|stretched and it is set as a polarizing plate, the retardation expressed in a resin layer can be made small.

Re2 is a free-end uniaxial stretching of the laminate 10 by 6.0 times under a temperature condition of 50°C to 120°C to make a stretched laminate, whereby the resin layer in the laminate is stretched to the resin layer, that is, the resin layer. When it is set as a stretched object, it is the retardation of such a stretched resin layer in an in-plane direction. That is, Re2 is not the phase difference of the resin layer itself in a laminated body, but a phase difference which arises in the stretched material of a resin layer after giving a specific extending|stretching process to a laminated body.

Any temperature within the range of 50 degreeC - 120 degreeC may be sufficient as the extending|stretching temperature for obtaining such a stretched material. Accordingly, a plurality of operating conditions for stretching to obtain a stretched product are conceivable. When the stretched product exhibits a phase difference of 0 nm or more and 20 nm or less under any one of these plural operating conditions, the laminate satisfies the above requirements.

However, it is preferable that a stretched material expresses the phase difference of 0 nm or more and 20 nm or less by all the said some operation conditions which can be taken. In that case, manufacture of the polarizing plate by the laminated body for polarizing plates of this invention WHEREIN: The freedom degree of high extending|stretching condition setting can be acquired.

Generally, in the said temperature range, when extending|stretching temperature is lower, a larger phase difference expresses. Therefore, if both the phase difference of the stretched product by stretching at 50°C and the phase difference of the stretched product by stretching at 120°C are within the range of 0 nm or more and 20 nm or less, the stretched product is 0 nm or more and 20 nm or less by all of the above-described operating conditions. It can be determined that the phase difference is expressed.

[2. Manufacturing method of laminate]

The manufacturing method of the laminated body which concerns on this embodiment extends|stretches the raw film containing the material of a polarizer, The 1st process of obtaining a polarizer material film, Applying resin to one surface of a polarizer material film, and forming an application layer The 2nd process of doing this, and the 3rd process of drying the application layer formed in the 2nd process are included in this order.

In addition, the manufacturing method of a laminated body may include the 4th process of activating the surface of a polarizer material film before a 2nd process.

[Apparatus for manufacturing a laminate]

2 : is the schematic which showed typically an example of the manufacturing apparatus 200 used in the manufacturing method of the laminated body which concerns on this embodiment. The manufacturing apparatus 200 is equipped with the unwinding apparatus 201, the coating apparatus 202, the winding apparatus 203, the extending|stretching apparatus 204, the processing apparatus 205 which performs an activation process, and the drying apparatus 206. . A1 is the conveyance direction.

[Method for producing a laminate]

As shown in FIG. 2, the polarizer material film 11 is obtained by conveying the raw film 1 unwound from the unwinding apparatus 201 to the extending|stretching apparatus 204, and performing an extending|stretching process with the extending|stretching apparatus 204. (Step 1). After conveying the polarizer material film 11 to the processing apparatus 205 and performing an activation process (4th process) in the processing apparatus 205, an application layer is formed in the coating apparatus 202 (2nd process) , the laminate 10 is obtained through a step (third step) of drying in the drying device 206 . The manufactured laminated body 10 is wound up by the winding-up apparatus 203, it can be made into the shape of a roll, and can be used for an additional process. Hereinafter, each process is demonstrated.

[Step 1]

A 1st process is a process of extending|stretching the raw film containing the material of a polarizer, and obtaining a polarizer material film.

The stretching treatment of the raw film in the first step is [1. It is preferable to carry out under the conditions and method (stretching process method, extending|stretching aspect, a draw ratio, extending|stretching temperature) demonstrated in the section of [Polarizer material film] of [Laminate body]. It is specifically, preferable that the draw ratio of the extending|stretching of the raw film in a 1st process is X times, and X satisfy|fills 1.5<=X<=5.5. A more preferable range of X is [1. It is as described in the section of [Polarizer material film] of [Laminate body].

[Second process]

A 2nd process is a process of apply|coating resin to one surface of the polarizer material film 11, and forming an application layer. Although the method (application method) of applying the resin to the polarizer material film 11 is not particularly limited, for example, it is preferable that it is one or more methods selected from solution coating, emulsion coating, or melt extrusion coating, and high-speed application Solution coating is more preferable in that a resin layer having a uniform film thickness is obtained.

When forming an application layer by solution coating, resin used for formation of an application layer, and the component added as needed are melt|dissolved in a solvent, it is set as a resin composition, and the said resin composition is apply|coated to the polarizer material film 11. That is, the phrase "applying a resin" includes both the case of apply|coating only resin, and the case of apply|coating the resin composition containing resin and other components.

[3rd process]

A 3rd process is a process of drying the application layer formed in the 2nd process. The resin layer 12 is formed in one surface of the polarizer material film 11 by performing a 3rd process.

In a 3rd process, it is preferable to dry an application layer for 0.5 minute - 10 minutes in the dryer of the temperature of 50 degreeC - 120 degreeC. The drying temperature of the said coating layer becomes like this. More preferably, it is 60 degreeC or more, More preferably, it is 70 degreeC or more, More preferably, it is 100 degrees C or less, More preferably, it is 90 degreeC or less. By making drying temperature more than a lower limit, drying time can be shortened, and crystallization of a polarizer material film can be suppressed by making drying temperature below an upper limit.

[4th process]

A 4th process is a process of activating the surface of a polarizer material film before a 2nd process. In this invention, the said 4th process is an arbitrary process, The manufacturing method of this invention may or may not include the 4th process. In the fourth step, by activating the surface of the polarizer material film, the plasticizer or the like that bleed on the surface of the polarizer material film is removed, and the adhesiveness of the resin layer is improved by oxidizing the surface of the polarizer material film, and the resin layer is formed. It can suppress that a stratum peels off.

As the method of activation treatment, corona treatment, plasma treatment, saponification treatment, primer treatment, anchor coating treatment, etc. are mentioned, for example.

The timing for performing the fourth step is not limited as long as it is before the second step, and in the case of performing the heat treatment step described later, it may be performed before the heat treatment step, after the heat treatment step, and simultaneously with the heat treatment step. Since a plasticizer etc. contained in a polarizer material film may bleed to the surface of a polarizer material film by a heat treatment process, it is especially preferable to perform a 4th process after a heat treatment process.

[Heat treatment process]

A heat treatment process is a process of heat-processing a polarizer material film before a 2nd process. In the present invention, the heat treatment step is an arbitrary step, and the manufacturing method of the present invention may or may not include the heat treatment step. By heat-processing a polarizer material film in a heat processing process, the wrinkle which exists in a polarizer material film can be removed, and planarity can be improved. By smoothing a polarizer material film, the film thickness precision of the resin layer formed at a 2nd process can be improved. The heating temperature of the polarizer material film is preferably 50°C or higher, more preferably 60°C or higher, preferably 100°C or lower, and more preferably 90°C or lower.

[Use of laminate]

The laminate 10 of the present invention is a material for manufacturing a polarizing plate. The laminate can become a polarizing plate after processing such as stretching treatment and dyeing treatment. When the laminated body 10 is used as the material of the polarizing plate, the laminated body wound up by the winding device 203 shown in FIG. 2 may be used as it is, and the resin layer 12 of the laminated body wound up by the winding device 203. You may use, after laminating|stacking a separator film, winding up in roll shape, and setting it as a laminated body film roll. Hereinafter, the polarizing plate of this embodiment using the laminated body 10 of this embodiment is demonstrated.

[3. Polarizer]

[summary]

The polarizing plate of this invention is obtained by uniaxial stretching of the laminated body of this invention. It is the schematic which showed typically an example of the manufacturing apparatus which manufactures a polarizing plate using the laminated body which concerns on this embodiment. 4 is a cross-sectional view schematically showing a polarizing plate manufactured using the laminate according to the present embodiment.

[Polarizer]

The polarizing plate 100 of this embodiment is a polarizing plate obtained by uniaxially stretching the laminated body of this embodiment. As shown in FIG. 4 , in the polarizing plate 100 , the resin layer 112 is laminated on one surface (upper side surface in the illustration) of the polarizer material film 111 .

[Characteristics of each layer in a polarizing plate]

30 micrometers or less are preferable, and, as for the thickness of the polarizer material film 111 in the polarizing plate 100, 20 micrometers or less are more preferable, 3 micrometers or more are preferable, and 5 micrometers or more are more preferable. When thickness is below an upper limit, the thickness of a polarizing plate can be made small, and when thickness is more than a lower limit, the polarizing plate which has a sufficiently high polarization degree can be obtained.

It is preferable that the retardation of the in-plane direction of the resin layer in a polarizing plate is 20 nm or less, 15 nm or less is more preferable, 10 nm or less is still more preferable, 0 nm or more is preferable. When the phase difference of the in-plane direction of the resin layer in a polarizing plate is in the said range, the black color shift at the time of mounting a polarizing plate in a liquid crystal display device can be suppressed.

[4. Manufacturing method of polarizing plate]

[summary]

The manufacturing method of the polarizing plate of this invention is a method of manufacturing a polarizing plate using the laminated body of this invention or the laminated body obtained by the manufacturing method of the laminated body of this invention. The manufacturing method of the polarizing plate of this invention contains the 5th process of dyeing a laminated body with a dichroic dye, and the 6th process of uniaxially stretching a laminated body. That is, the manufacturing method of the polarizing plate of this invention is the process of manufacturing the laminated body of the said this invention by arbitrary methods, or the process of manufacturing a laminated body by the manufacturing method of the said laminated body of this invention, The laminated body The 5th process of dyeing|staining with a dichroic dye, and the 6th process of uniaxially stretching a laminated body are included.

Moreover, after the manufacturing method of the polarizing plate of this invention passes through a 5th process, a 6th process, or these both, one or both surfaces of the surface on the side of the polarizer material film of a laminated body, and the surface on the side of a resin layer are protected The 7th process of bonding a film together may be included. A 7th process is an arbitrary process, and in this embodiment, the example which manufactures a polarizing plate with the manufacturing method which does not include a 7th process is demonstrated.

[Device for manufacturing polarizer]

As shown in FIG. 3, manufacturing apparatus 300 which manufactures a polarizing plate is unwinding apparatus 301, 307, processing apparatus 302-305, drying apparatus 306, bonding apparatus 308, and winding apparatus ( 310) is provided.

[Manufacturing method of polarizing plate]

In this embodiment, the dyeing process (5th process) which conveys the laminated body 10 unwound from the unwinding apparatus 301 to the processing apparatuses 302-305, and dyes the laminated body 10 with a dichroic dye. And the extending|stretching process (6th process) of uniaxially stretching a laminated body is performed. When the process (drying process) which dries the laminated body after performing these processes with the drying apparatus 306 is performed, the polarizing plate 100 will be obtained. Hereinafter, each process is demonstrated in detail.

[Step 5]

A 5th process is a process of dyeing|staining the laminated body 10 with a dichroic dye. In this embodiment, in a 5th process, the polarizer material film of a laminated body is dye|stained. In this invention, it is preferable that the polarizer material film contained in the laminated body which performs a 5th process is undyed, but dyeing of a polarizer material film may be performed with respect to the polarizer material film before forming a laminated body.

As a dichroic dye (dichroic substance) which dye|stains the laminated body in a 5th process, an iodine, an organic dye, etc. are mentioned. The dyeing method using these dichroic dyes is arbitrary. For example, you may dye|stain by immersing the layer of a polarizer material film in the dyeing solution containing a dichroic dye. Moreover, when using an iodine as a dichroic dye, from a viewpoint of improving dyeing efficiency, the dyeing solution may contain iodide, such as potassium iodide. Although there is no restriction|limiting in particular in a dichroic dye, When using a polarizing plate in the display apparatus for vehicle mounting, as a dichroic dye, an organic dye is preferable.

[Step 6]

A 6th process is a process of uniaxially stretching a laminated body. Although it does not specifically limit as a method of extending|stretching a laminated body, Wet extending|stretching is preferable. You may perform a 6th process at any time of before a 5th process, after a 5th process, and simultaneous with a 5th process. In addition, the 6th process may be divided|segmented and performed multiple times before the 5th process, after a 5th process, at any one time simultaneously with the 5th process. An extending process may be performed once and may be performed twice or more.

The draw ratio of the laminated body in a 6th process is Z times, and Z can be made into 1.2<=Z<=5.0. Z is preferably 1.2 or more, more preferably 1.5 or more, preferably 5.0 or less, and more preferably 4.0 or less. When the draw ratio of the laminate is below the upper limit of the above range, the expression of the retardation of the resin layer is still low even after the manufacturing process of the polarizing plate including the stretching treatment, and the occurrence of breakage of the polarizing plate can be prevented, and stretching When magnification is more than the lower limit of the said range, the polarizing plate which has sufficient polarization performance can be obtained. When extending|stretching of a laminated body is performed twice or more, it is preferable to make it become the said range for the total draw ratio represented by the product of the draw ratio of each time.

It is preferable that the draw ratio X of the raw film in a 1st process, and the draw ratio Z of the laminated body in a 6th process satisfy|fill 5.1<=X*Z<=9.0. X*Z is the product of X and Z (product of draw ratio). X*Z is preferably 5.1 or more, more preferably 5.5 or more, preferably 9.0 or less, and more preferably 7.0 or less. When X * Z is less than or equal to the upper limit of the above range, even if it goes through the manufacturing process of a polarizing plate including an extending|stretching process, expression of the retardation of a resin layer can still be made low, and generation|occurrence|production of the fracture|rupture of a polarizing plate can be prevented. When X*Z is more than the lower limit of the said range, the polarizing plate which has sufficient polarization performance can be obtained.

The stretching temperature of the laminate is not particularly limited, but is preferably 30°C or higher, more preferably 40°C or higher, particularly preferably 50°C or higher, preferably 140°C or lower, more preferably 90°C or lower. , particularly preferably 70°C or less. When extending|stretching temperature is more than the lower limit of the said range, extending|stretching can be performed smoothly, and effective orientation can be performed by extending|stretching because it is below the upper limit of the said range. The range of the stretching temperature is preferably any of dry stretching and wet stretching, but is particularly preferable in the case of wet stretching.

The stretching treatment of the laminate is a longitudinal stretching treatment in which stretching is performed in the longitudinal direction of the film, a transverse stretching treatment in which stretching is performed in the film width direction, and an oblique stretching treatment in which stretching is performed in an oblique direction that is neither parallel nor perpendicular to the film width direction. may be done. Free-end uniaxial stretching is preferable and, as for the extending|stretching process of a laminated body, free-end uniaxial stretching of the longitudinal direction is more preferable.

[Drying process]

A drying process is a process of drying the laminated body which passed through the 5th process and the 6th process. In this invention, a drying process is an arbitrary process. In a drying process, it is preferable to dry a laminated body for 0.5 minute - 10 minutes in the dryer of the temperature of 50 degreeC - 100 degreeC. The drying temperature of the said laminated body becomes like this. More preferably, it is 60 degreeC or more, More preferably, it is 90 degrees C or less. Drying time can be shortened by making drying temperature more than a lower limit, and the crack of a polarizer material film can be prevented by making drying temperature below an upper limit. The drying time of the said laminated body becomes like this. More preferably, it is 1 minute or more, More preferably, it is 5 minutes or less. The crack of the polarizer material film in a laminated body can be prevented by making drying of the said laminated body sufficient by making drying time more than a lower limit, and using below an upper limit.

In the conventional thin film polarizer made of only PVA resin, cracks may occur after the drying process, but the polarizing plate of this embodiment uses a laminate having a polarizer material film and a resin layer directly laminated on the polarizer material film. Since it manufactures by doing this, generation|occurrence|production of the crack of a polarizer can be suppressed even after going through a drying process.

[5. [Operation and effect of this embodiment]

In this embodiment, since a polarizing plate is manufactured by extending|stretching a laminated body which has a polarizer material film which has a predetermined retardation Re1 and has a small thickness T1, and the resin layer formed directly on the polarizer material film, the laminated body is extended|stretched and a polarizing plate The draw ratio at the time of manufacturing can be made low. Thereby, expression of the phase difference in the resin layer after extending|stretching a laminated body can be suppressed. As a result, according to this embodiment, it can be used as a protective film on one side of the polarizer material film as it is without peeling the resin layer, and since waste materials can be reduced, the resin layer can also be used as a protective film, It is possible to provide a laminate for a polarizing plate and a method for manufacturing the same, which can be efficiently manufactured even if the thickness is thin, a polarizing plate and a manufacturing method using the laminate, and a manufacturing method for a display device using the polarizing plate.

In addition, in the laminated body 10 of this embodiment, since the resin layer 12 is formed directly on the polarizer material film 11 without interposing an adhesive agent etc., wrinkles and voids by penetration of an adhesive agent etc. occurrence can be prevented. As a result, according to this embodiment, the laminated body which prevented generation|occurrence|production of wrinkles and a void, its manufacturing method, a polarizing plate, its manufacturing method, and the manufacturing method of a display device can be provided.

Moreover, according to this embodiment, since another material does not interpose between the resin layer 12 and the polarizer material film 11, it is excellent in a fracture|rupture suppression effect, and prevention of environmental pollution by other substances in a production environment. However, it is possible to prevent contamination (incorporation of foreign substances) into the product.

[Embodiment 2: Polarizing plate and manufacturing method thereof]

Hereinafter, the polarizing plate 120 and its manufacturing method according to Embodiment 2 will be described with reference to FIGS. 3 and 5 . The polarizing plate 120 according to the present embodiment is manufactured using the polarizing plate 100 according to the first embodiment. About the same structure and aspect as Embodiment 1, the same code|symbol is attached|subjected, and the overlapping description is abbreviate|omitted.

[Polarizer]

5 is a cross-sectional view schematically showing the polarizing plate 120 according to the second embodiment of the present invention. In this polarizing plate 120, as shown in FIG. 5, the resin layer 112 is laminated|stacked on one surface (illustration upper side surface) of the polarizer material film 111, and the other side of the polarizer material film 111 is The protective film 115 is laminated|stacked on the surface side (lower surface in figure).

[Manufacturing method of polarizing plate]

The manufacturing method of the polarizing plate 120 of this embodiment includes the 7th process of bonding a protective film together on the surface by the side of the polarizer material film of a laminated body, after passing a 5th process and a 6th process. It will be described in detail below.

In the manufacturing method of the polarizing plate 120 of this embodiment, the dyeing process (5th process) which dye|stains the polarizer material film 11 of the laminated body 10, and the extending|stretching process (6th process) which uniaxially stretches a laminated body. ), the polarizing plate 100 obtained by drying in the drying apparatus 306 is used.

As shown in FIG. 3, the polarizing plate 120 conveys the polarizing plate 100 obtained through a dyeing process (5th process) and an extending|stretching process (6th process) to the pasting apparatus 308, The polarizer of a laminated body It is obtained by bonding the protective film 115 unwound from the unwinding apparatus 307 to the surface by the side of a material film (7th process). The obtained polarizing plate 120 can be wound up by the winding-up device 310, it can be set as the shape of a roll, and can be used for an additional process.

As the protective film 115 used in the 7th process, the film which consists of 1 or more types of resin chosen from a cycloolefin resin, an acrylic resin, a polyethylene terephthalate resin, and a triacetyl cellulose resin is mentioned.

The bonding of the protective film 115 to the polarizing plate 100 is not particularly limited and may be performed by a method such as thermocompression bonding (refer to FIG. 5 ). You may perform bonding to the polarizing plate 100 of the protective film 115 through an adhesive agent, an adhesive, etc. The polarizing plate after passing through the 5th and 6th processes WHEREIN: Since the polarizer material film is hardened|cured, the problem of generation|occurrence|production of the wrinkles resulting from permeation of an adhesive agent etc. is hard to generate|occur|produce.

As the adhesive and pressure-sensitive adhesive used for bonding the protective film and the polarizing plate, for example, acrylic adhesive, epoxy adhesive, urethane adhesive, polyester adhesive, polyvinyl alcohol adhesive, polyolefin adhesive, modified polyolefin adhesive, poly Ethylene-based adhesives such as vinyl alkyl ether-based adhesives, rubber-based adhesives, vinyl chloride-vinyl acetate-based adhesives, SEBS (styrene-ethylene-butylene-styrene copolymer) adhesives, ethylene-styrene copolymers, ethylene-(meth)acrylic acid Acrylic acid ester adhesives, such as a methyl copolymer and an ethylene- (meth)acrylic-acid ethyl copolymer, etc. are mentioned.

The polarizing plate 120 of this embodiment also manufactures a polarizing plate by extending|stretching the laminated body which has a polarizer material film and the resin layer laminated|stacked directly on the surface of a polarizer material film similarly to the polarizing plate of Embodiment 1. It has the same action and effect.

Moreover, according to this embodiment, since the protective film 115 is provided in the surface on the side where the resin layer 112 of the polarizer material film 111 is not laminated|stacked, scratches etc. on the surface of the polarizer material film 111 It also has the effect of preventing it from happening.

[Outline of the manufacturing method of the display device of the present invention]

The polarizing plate manufactured using the laminated body of this invention can become a material of display apparatuses, such as a liquid crystal display device, an organic electroluminescent display, and an inorganic electroluminescent display device, and a micro LED display device.

The manufacturing method of the display device of this invention is a method of manufacturing a display device using the polarizing plate obtained by the manufacturing method of the polarizing plate of this invention, Comprising: The 8th process of laminating|stacking a polarizing plate on a panel is included. In the manufacturing method of the polarizing plate of this invention, a panel is a panel chosen from a liquid crystal panel, an organic electroluminescent panel, and a micro LED panel.

[Embodiment 3: Manufacturing method of display device]

Hereinafter, a display device 400 according to a third embodiment including the polarizing plate 100 manufactured using the laminate 10 of the first embodiment will be described with reference to FIGS. 4 and 6 .

The manufacturing method of the display device of this embodiment includes the process (8th process) of laminating|stacking the polarizing plate 100 shown in FIG. 4 on a panel. In this embodiment, the example of manufacturing a liquid crystal display device using a liquid crystal panel as a panel is demonstrated.

Usually, a liquid crystal display device is equipped with a light source, a light source side polarizing plate, a liquid crystal cell, and a visual recognition side polarizing plate in this order. The polarizing plate obtained by this invention can be used for a light source side polarizing plate, a visual recognition side polarizing plate, or both.

In this embodiment, a liquid crystal display device is manufactured by laminating|stacking the polarizing plate 100 on a liquid crystal panel as a light source side polarizing plate and a viewing side polarizing plate, respectively, in an 8th process.

6 is a cross-sectional view schematically showing a display device manufactured by the method for manufacturing a display device according to Embodiment 3 of the present invention. As shown in FIG. 6 , the display device 400 is disposed on the outside of two substrates 410 and 420 , a liquid crystal layer 430 positioned therebetween, and the two substrates 410 and 420 , respectively. It has the polarizing plates 100 and 100 which become The two polarizing plates 100 are the polarizing plates 100 manufactured using the laminated body 10 of Embodiment 1. FIG. As shown in FIG. 6, the two polarizing plates 100 are laminated|stacked so that the resin layer 112 of a polarizing plate may be arrange|positioned between the polarizer material film 111 of a polarizing plate, and the liquid crystal layer 430, respectively.

According to this embodiment, a resin layer can be used also as a protective film, can manufacture efficiently even if thickness is thin, and the display apparatus provided with the polarizing plate which prevented generation|occurrence|production of wrinkles and a void can be provided.

[Embodiment 4: Manufacturing method of display device]

Hereinafter, a display device 500 according to a fourth embodiment including the polarizing plate 120 manufactured in the second embodiment will be described with reference to FIGS. 5 and 7 .

The manufacturing method of the display device of this embodiment includes the process (8th process) of laminating|stacking the polarizing plate 120 shown in FIG. 5 on a panel. In this embodiment, the example of manufacturing an organic electroluminescent display using an organic electroluminescent panel as a panel is demonstrated.

Usually, although an organic electroluminescent display is provided with a board|substrate, a transparent electrode, a light emitting layer, and a metal electrode layer in order from the light output side, the polarizing plate obtained by the manufacturing method of this invention is arrange|positioned on the light output side of a board|substrate.

Usually, an organic electroluminescent display has two board|substrates, the light emitting layer located between them, and the polarizing plate arrange|positioned on the outer side of one board|substrate among two board|substrates. The said organic electroluminescence display can be manufactured by providing the polarizing plate of this invention to an organic electroluminescent panel.

In this embodiment, an organic electroluminescence display is manufactured by laminating|stacking the polarizing plate 120 on an organic electroluminescent panel in an 8th process.

7 is a cross-sectional view schematically showing a display device manufactured by the method for manufacturing a display device according to Embodiment 4 of the present invention. As shown in FIG. 7 , the display device 500 includes two substrates 510 and 520 , a light emitting layer 530 positioned therebetween, and an outer side (lower side of the drawing) of the lower substrate 510 . It has a polarizing plate 120 . The polarizing plate 120 is the polarizing plate 120 of Embodiment 2 manufactured using the laminated body 10 . 7, the polarizing plate 120 is laminated|stacked so that the resin layer 112 of a polarizing plate may be arrange|positioned between the polarizer material film 111 of a polarizing plate, and the light emitting layer 530. As shown in FIG.

According to this embodiment, a resin layer can be used also as a protective film, can manufacture efficiently even if thickness is thin, and the display apparatus provided with the polarizing plate which prevented generation|occurrence|production of wrinkles and a void can be provided.

[Other embodiment]

(1) In Embodiment 2, although the example which pasted the protective film only on the surface by the side of the polarizer material film of a laminated body was shown, a protective film may be pasted only on the surface by the side of the resin layer of a laminated body, and the polarizer material film of a laminated body You may bond a protective film together on both the surface by the side and the surface by the side of a resin layer.

(2) In Embodiment 3 and 4, although the example was shown in which a panel is a liquid crystal panel and an organic electroluminescent panel, the panel which laminates|stacks a polarizing plate may be a micro LED panel.

(3) In Embodiment 3, although the manufacturing method of the liquid crystal display device which laminated|stacked the two polarizing plates 100 demonstrated in Embodiment 1 was shown, it is not limited to this. Two polarizing plates 120 demonstrated in Embodiment 2 may be laminated|stacked, two types of polarizing plates may be laminated|stacked, and one polarizing plate may be laminated|stacked.

(4) In Embodiment 4, although the manufacturing method of the organic electroluminescent display which laminates|stacks the polarizing plate 120 of Embodiment 2 was shown, instead of the polarizing plate 120, you may use the polarizing plate 100.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, "parts" and "%" regarding the ratio of components represent parts by weight unless otherwise specified.

[Assessment Methods]

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

The molecular weight of the block copolymer and the hydrogenated block copolymer was measured at 38°C as a standard polystyrene conversion value by GPC using THF as the eluent. As a measuring apparatus, the Tosoh Corporation make, HLC8020GPC was used.

[Hydrogenation rate]

The hydrogenation rate of the block copolymer hydride ^{was computed by <1>} H-NMR spectrum or GPC analysis. The region with a hydrogenation rate of 99% or less was ^{calculated by measuring 1} H-NMR spectrum, and the region exceeding 99% was calculated from the ratio of the peak areas by the UV detector and the RI detector by GPC analysis.

[Measurement of MFR (melt flow rate measured at 190°C and load of 2.16 kg)]

The coating liquid for film forming used in each example was apply|coated to the separator film (made by Mitsubishi Chemical Corporation, "MRV38") using a die coater, and it dried, and formed the film containing the polymer X with a thickness of 10 micrometers. The film containing the said polymer X was peeled from the separator film, and it was set as the sample film. MFR was measured by the following method using this sample film.

MFR was measured under the conditions of a temperature of 190°C and a load of 2.16 kg using an extrusion-type plastometer (manufactured by Tateyama Scientific Industries, Ltd., trade name “melt indexer (L240)”) as a measuring device based on JIS K7210. .

[Measurement of tensile modulus]

The tensile modulus of elasticity was measured using the sample film produced by the method similar to "the sample film" demonstrated in the term of "measurement of MFR".

The tensile modulus of elasticity was measured by the following method using a tensile tester (manufactured by Instron Japan Co., Ltd., trade name "Electromechanical Universal Material Tester 5564") based on JIS K7127.

The sample film was punched out in the shape of the test piece type 1B of JISK7127 description, and the stress at the time of pulling and deforming this test piece in the long side direction was measured. The stress measurement conditions were a temperature of 23°C, a humidity of 60±5%RH, a distance between chucks of 115 mm, and a tensile rate of 50 mm/min. The measurement of the stress was performed 5 times. From the measured stress and the measurement data of the strain corresponding to the stress, 4 points of measurement data (that is, the strain is 0.6%, 0.8%, 1.0% and Measurement data at the time of 1.2%) was selected, and the tensile modulus was computed using the least squares method from the measurement data of 4 points|pieces (total of 20 points|pieces) of 5 measurements.

[Method of measuring phase difference]

The phase difference Re1 in the in-plane direction of the polarizer material film, the phase difference Re2, and the phase difference in the in-plane direction of the resin layer in the polarizing plate are measured using a phase difference meter (manufactured by Opto Science Co., Ltd., Muller matrix polarometer, trade name "Axo Scan") measured. At the time of measurement, the measurement wavelength was set to 550 nm.

The retardation Re2 was measured by measuring the retardation in the in-plane direction generated in the stretched resin layer, ie, the resin layer obtained by uniaxially stretching the stretched resin layer at a predetermined temperature (50° C. and 120° C.) at 6.0 times at the free end. In the present application, the phase difference in the in-plane direction of the resin layer that occurs when the laminate is uniaxially stretched at the free end by 6.0 times under the temperature condition of 50° C., and when the laminate is uniaxially stretched at the free end by 6.0 times under the temperature condition of 120° C. If both of the phase differences in the in-plane direction of the generated resin layer are within the range of 0 nm or more and 20 nm or less, the in-plane of the resin layer that occurs when the laminate is uniaxially stretched at the free end at 6.0 times under the temperature condition of 50 ° C to 120 ° C. It was judged that the phase difference Re2 of a direction was 0 nm or more and 20 nm or less.

[Measuring method of thickness]

The thickness of each film (polarizer material film and resin layer) contained in the laminate and the thickness of each film contained in the polarizing plate are measured by a thickness gauge (manufactured by Mitsutoyo Co., Ltd., trade name "ABS Digimatic Thickness Gauge (547-401)" ') was measured 5 times, and the average value was made into the thickness of each film.

[Evaluation of the surface state of the polarizing plate]

The surface of the polarizing plate of each example was observed visually, and the number of wrinkles and voids per 10 cm square was measured. The measurement was performed with respect to five places of a polarizing plate, the average value was computed, and the following evaluation criteria evaluated it.

A: Wrinkles and voids are not observed.

B: The number of wrinkles is 1 or more and 3 or less, or the number of voids is 1 or more and less than 10.

C: The number of wrinkles is 4 or more, or the number of voids is 10 or more.

[Evaluation of adhesion]

In the process up to the 2nd extending|stretching process in manufacture of the polarizing plate of each case WHEREIN: The thing which peeling did not generate|occur|produce between the polarizer material film and the resin layer was made into A, what peeled in a part, B, and what peeled completely made C.

[Evaluation of drying fairness]

70 degreeC in manufacture of the polarizing plate of each example, and the drying process for 5 minutes WHEREIN: The thing which a crack did not generate|occur|produce in the polarizer was made into A, and the thing which a crack generate|occur|produced was made into C.

[Black Color Shift]

The liquid crystal display panel is removed from the liquid crystal display device (manufactured by LG Electronics Japan, trade name "IPS panel monitor (23MP47)"), the polarizing plate disposed on the viewing side is peeled off, and the polarizing plates produced in Examples and Comparative Examples , it bonded together so that a resin layer might become a panel side. Moreover, the polarizer single-piece|unit without a protective film was pasted together next to the polarizing plate produced by the Example and the comparative example, and the liquid crystal display device was reassembled. The polarizing plate created in the Example and the comparative example, and the absorption axis of the polarizer single-piece|unit without a protective film were bonded so that it might become 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 viewer side is 0° in azimuth and 0° in the vertical direction of the panel, the panel is in a black display state (that is, black is displayed on the entire display screen of the panel). Therefore, when viewed at an azimuth angle of 45° and polarization angle of 45°, it was judged that A was the same color change as in the case of a polarizer without a protective film, B was a slight color change, and C was a large change.

[Example 1]

(1-1) Preparation of polarizer material film

As the raw film, an unstretched polyvinyl alcohol film (average degree of polymerization of about 2400, degree of saponification of 99.9 mol%, thickness of 20 µm, hereinafter also referred to as "PVA20") was used.

The raw film was dry-stretched by the draw ratio 1.5 times (X=1.5) in the longitudinal direction at the extending|stretching temperature of 130 degreeC using a longitudinal uniaxial stretching machine, and the polarizer material film was obtained. The thickness T1 of the polarizer material film was 16 µm, and Re1 was 320 nm.

(1-2) Preparation of Polymer X

With reference to the production example described in Japanese Patent Application Laid-Open No. 2002-105151, after polymerizing 25 parts of a styrene monomer in a first step, 30 parts of a styrene monomer and 25 parts of an isoprene monomer are polymerized in a second step, and then in the third step After polymerizing 20 parts of a styrene monomer to obtain a block copolymer [D1], the block copolymer was hydrogenated to synthesize a hydrogenated block copolymer [E1]. Mw of the hydrogenated block copolymer [E1] was 84,500, Mw/Mn was 1.20, and the hydrogenation ratio of the main chain and the aromatic ring was approximately 100%.

To 100 parts of block copolymer hydride [E1], pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (Matsubara Industrial Co., Ltd.) as an antioxidant Manufacture, product name "Songnox1010") After melt-kneading 0.1 part and mix|blending, it was set as pellets and the polymer X for shaping|molding was obtained.

(1-3) Preparation of laminate

After dissolving the polymer X prepared in (1-2) in cyclohexane, 40 parts by weight of polyisobutene (“Niseki Polybutene HV-300” manufactured by JX Nikko Niseki Energy Co., Ltd., water based on 100 parts by weight of the polymer X), water Average molecular weight of 1,400) and 0.1 parts by weight of an organosilicon compound (3-aminopropyltriethoxysilane, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to prepare a coating liquid A for film forming (resin composition A).

The obtained coating liquid A for film forming was apply|coated to one surface of the polarizer material film manufactured by (1-1) using the die-coater, and it dried. Thereby, the elongate laminated body which consists of a polarizer material film and the resin layer (600 mm in width, 10 micrometers in thickness) containing the polymer X was obtained.

In the obtained laminate, the thickness of the resin layer, thickness T1 of the polarizer material film, retardation Re1 in the in-plane direction, and retardation Re2 (temperature conditions 50°C, 120°C) were measured. In addition, MFR and tensile modulus of resin which comprise the resin layer were measured by the method demonstrated by the evaluation method. A result is shown in Table 1.

(1-4) Preparation of polarizing plate

The following operation was performed, continuously conveying the laminated body manufactured by (1-3) in the longitudinal direction through a guide roll.

The above laminate was subjected to a swelling treatment immersed in water, a dyeing treatment immersed in a dyeing solution containing iodine and potassium iodide, and a first stretching treatment for stretching the laminate after the dyeing treatment. Next, the 2nd extending|stretching process of extending|stretching the laminated body after a 1st extending|stretching process in the bath containing boric acid and potassium iodide was performed. It was set so that the total draw ratio represented by the product of the draw ratio in 1st drawing process and the draw ratio in 2nd drawing process might become 4.0 times (Z = 4.0). The extending|stretching temperature was 57 degreeC. The laminated body after a 2nd extending|stretching process was dried in the dryer at 70 degreeC for 5 minutes (drying process), and the polarizing plate was obtained.

Adhesive evaluation was performed in the process until a 2nd extending process, and drying process property was evaluated in a drying process. About the polarizing plate obtained, evaluation of a plane state and evaluation of a black color shift were performed. An evaluation result is shown in Table 1.

Moreover, the thickness and retardation of the resin layer in the obtained polarizing plate, and the thickness of the polarizer material film were measured, and the measurement result was shown in Table 1.

[Example 2]

The same operation as in Example 1 was performed except that the draw ratio of the raw film was 5.5 times (X = 5.5), and the draw ratio of the laminate was 1.2 times (Z = 1.2), and a laminate and a polarizing plate were manufactured and evaluated in the same manner as in Example 1. A result is shown in Table 1.

[Example 3]

When the draw ratio of the raw film was 2.0 times (X = 2.0), in (1-3) of Example 1, when performing the operation of applying and drying the coating liquid A for film forming, the application amount etc. were adjusted, The same operation as in Example 1 was performed except that the resin layer was formed to have a thickness of 5 µm (the width was the same as in Example 1), and the draw ratio of the laminate was set to 3.0 times (Z = 3.0), and the laminate was formed. and a polarizing plate, and evaluated in the same manner as in Example 1. A result is shown in Table 1.

[Example 4]

The same operation as in Example 1 was performed except that the draw ratio of the raw film was 3.0 times (X = 3.0), and the draw ratio of the laminate was 2.0 times (Z = 2.0), to manufacture a laminate and a polarizing plate and evaluated in the same manner as in Example 1. A result is shown in Table 1.

[Example 5]

What made the draw ratio of the raw film 3.0 times (X = 3.0), the thing which used the coating liquid B for film forming instead of the coating liquid A for film formation, and the thing which made the draw ratio of the laminated body 2.0 times (Z = 2.0) Other than that, operation similar to Example 1 was performed, the laminated body and a polarizing plate were manufactured, and it evaluated similarly to Example 1. A result is shown in Table 1.

The coating liquid B for film forming was produced with the following method.

After dissolving the polymer X prepared in (1-2) of Example 1 in cyclohexane, 0.1 parts by weight of an organosilicon compound (3-aminopropyltriethoxysilane, KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) based on 100 parts by weight of the polymer X. ) was added to prepare a coating liquid B for film forming (resin composition B).

[Example 6]

What made the draw ratio of the raw film 3.0 times (X = 3.0), the thing which used the film forming coating liquid C instead of the film forming coating liquid A, and the thing which made the draw ratio of the laminated body 2.0 times (Z = 2.0) Other than that, operation similar to Example 1 was performed, the laminated body and a polarizing plate were manufactured, and it evaluated similarly to Example 1. A result is shown in Table 2.

The coating liquid C for film forming was produced with the following method.

After dissolving the polymer X prepared in (1-2) of Example 1 in cyclohexane, 40 parts by weight of polyisobutene (“Niseki Polybutene HV- 300", a number average molecular weight of 1,400), and 0.1 parts by weight of an organic titanium compound (tetraisopropyl titanate, Orgatyx TA-8, manufactured by Matsumoto Fine Chemicals) was added to prepare a film forming coating liquid C (resin composition C) produced.

[Example 7]

The thing which made the draw ratio of the raw film 2.0 times (X = 2.0), the thing which used the film forming coating liquid D instead of the film forming coating liquid A, and the thing which made the draw ratio of the laminated body 3.0 times (Z = 3.0) Other than that, operation similar to Example 1 was performed, the laminated body and a polarizing plate were manufactured, and it evaluated similarly to Example 1. A result is shown in Table 2.

The coating liquid D for film forming was produced with the following method.

After dissolving the polymer X prepared in (1-2) of Example 1 in cyclohexane, 40 parts by weight of polyisobutene (“Niseki Polybutene HV- 300", a number average molecular weight of 1,400), and 0.1 parts by weight of an organic zirconium compound (normal propyl zirconate, Orgatyx ZA-45, manufactured by Matsumoto Fine Chemicals) was added to prepare a film forming coating solution D (resin composition D) produced.

[Example 8]

As the raw film, instead of PVA20, an unstretched polyvinyl alcohol film having a thickness of 45 μm (average degree of polymerization of about 2400, degree of saponification of 99.9 mol%, hereinafter also referred to as “PVA45”) was used, and the draw ratio of the raw film was 2.0 The same operation as in Example 1 was performed, except that the multiplier (X = 2.0) and the draw ratio of the laminate were set to 3.0 (Z = 3.0), the laminate and the polarizing plate were manufactured, and Example 1 and Evaluation was performed similarly. A result is shown in Table 2.

[Example 9]

Examples of the raw film, except that PVA45 was used instead of PVA20, the draw ratio of the raw film was 3.0 times (X = 3.0), and the draw ratio of the laminate was 2.0 times (Z = 2.0) Operation similar to 1 was performed, the laminated body and the polarizing plate were manufactured, and it evaluated similarly to Example 1. A result is shown in Table 2.

[Example 10]

As the raw film, instead of PVA20, an unstretched polyvinyl alcohol film having a thickness of 60 μm (average degree of polymerization of about 2400, saponification degree of 99.9 mol%, hereinafter also referred to as “PVA60”) was used, and the draw ratio of the raw film was 2.0 The same operation as in Example 1 was performed, except that the multiplier (X = 2.0) and the draw ratio of the laminate were set to 3.0 (Z = 3.0), the laminate and the polarizing plate were manufactured, and Example 1 and Evaluation was performed similarly. A result is shown in Table 2.

[Example 11]

Example 1, except that the draw ratio of the raw film was 3.0 times (X = 3.0), the coating liquid E for film forming was used instead of the coating liquid A for film forming, and the draw ratio Z of the laminate was 2.0. The same operation was performed, the laminated body and the polarizing plate were manufactured, and it evaluated similarly to Example 1. A result is shown in Table 3.

The coating liquid E for film forming was produced with the following method.

After dissolving the polymer X prepared in (1-2) of Example 1 in cyclohexane, 40 parts by weight of polyisobutene (“Niseki Polybutene HV- 300", number average molecular weight 1,400) was added, and the coating liquid E (resin composition E) for film forming was produced.

[Comparative Example 1]

In (1-4) of Example 1, (1-4) of Example 1, except that PVA20 (unstretched polyvinyl alcohol resin film) was used instead of the laminate prepared in (1-3) As a result of performing the same operation, melting occurred frequently in the first stretching treatment and the second stretching treatment, and fractures occurred frequently in the drying process, and evaluation of the surface state, adhesiveness, and black color shift was not possible.

[Comparative Example 2]

(C2-1) Preparation of polarizer material film

Using PVA20 as a raw film, it dry-stretched by the draw ratio 2.0 times (X=2.0) in the longitudinal direction at the extending|stretching temperature of 130 degreeC using a longitudinal uniaxial stretching machine, and obtained the polarizer material film. The thickness T1 of the polarizer material film was 14 µm, and Re1 was 350 nm.

(C2-2) Preparation of laminate

The coating liquid A for film forming prepared in (1-3) of Example 1 was applied to a separator film (manufactured by Mitsubishi Chemical Corporation, "MRV38") using a die coater and dried to have a width of 650 mm, a length of 500 m, and a thickness of 10 µm. A long film (resin film) containing the polymer X was obtained.

100 parts by weight of water, 3 parts by weight of a polyvinyl alcohol-based adhesive ("Z-200" manufactured by Nippon Synthetic Chemicals Co., Ltd.), and 0.3 parts by weight of a crosslinking agent ("SPM-01" manufactured by Nippon Synthetic Chemicals) were mixed to obtain an adhesive. This adhesive agent was apply|coated to one surface of the said resin film, and the polarizer material film manufactured by (C2-1) was pasted together. In this state, the adhesive was dried by heating at 70°C for 5 minutes to obtain a laminate. About the obtained laminated body, operation similar to (1-4) of Example 1 was performed, and the polarizing plate was obtained. About the obtained laminated body and a polarizing plate, it evaluated similarly to Example 1. A result is shown in Table 3.

In the table, "Re2 (50°C)" means the phase difference in the in-plane direction of the resin layer that occurs when the laminate is uniaxially stretched at the free end by 6.0 times under the temperature condition of 50°C, and "Re2 (120°C)" means the phase difference in the in-plane direction of the resin layer that occurs when the laminate is uniaxially stretched at the free end by 6.0 times under the temperature condition of 120°C.

In a table|surface, "Re1" means the retardation of the in-plane direction of the polarizer material film in a laminated body.

In the table, "direct application" indicates that the resin layer was formed by directly applying the coating liquid for film forming (resin composition) to the polarizer material film, and "bonding" refers to the resin film as a polarizer material film through an adhesive. indicates that it is attached to

In a table|surface, "polarizer" shows the polarizer material film in a polarizing plate.

From the results of Tables 1 to 3, according to the present invention, the retardation expressed in the resin layer after the step of stretching the laminate can be reduced, and a polarizing plate having excellent adhesion, drying processability, and optical properties can be obtained. it can be seen that Moreover, according to this invention, it turns out that generation|occurrence|production of wrinkles and a void can be prevented. Thereby, the resin layer can be used also as a protective film, and can be efficiently manufactured even if it is thin, and the laminated body and its manufacturing method which prevented the generation|occurrence|production of wrinkles and voids, a polarizing plate using the said laminated body, and its manufacturing method, And it turns out that the manufacturing method of a display device can be provided.

One… fabric film
10… laminate
11… polarizer material film
12… resin layer
100, 120… Polarizer
111… polarizer material film
112… resin layer
115… protective film
200… manufacturing device
201… unwinding device
202… applicator
203... winding device
204… stretching device
205… activation processing unit
206... drying device
300… manufacturing device
301, 307... unwinding device
302 to 305… processing unit
306… drying device
308… bonding device
310… winding device
400… Display device (liquid crystal display device)
410, 420... Board
430… liquid crystal layer
500… Display device (organic EL display device)
510, 520... Board
530… light emitting layer

Claims (21)

A laminate having a polarizer material film and a resin layer formed directly on the polarizer material film, comprising:
The retardation Re1 in the in-plane direction of the polarizer material film is greater than 50 nm,
The laminated body whose thickness T1 of the said polarizer material film is 45 micrometers or less. The method of claim 1,
The laminated body whose said polarizer material film is a film obtained by extending|stretching X times a draw ratio. 3. The method of claim 2,
X satisfies 1.5 ≤ X ≤ 5.5. 4. The method according to any one of claims 1 to 3,
The retardation Re2 in the in-plane direction of the stretched resin layer is 0 nm or more and 20 nm or less,
The stretched resin layer is a stretched product of the resin layer in a stretched laminate, and the stretched laminate is a stretched product obtained by uniaxially stretching the laminate at a free end by 4.0 times under a temperature condition of 50°C to 120°C, laminate. 5. The method according to any one of claims 1 to 4,
The laminate in which the said polarizer material film is a polyvinyl alcohol resin film. 6. The method of claim 5,
The laminate of the said polyvinyl alcohol resin film whose transmittance|permeability of the light of wavelength 550nm is 50 % or more. 7. The method according to any one of claims 1 to 6,
The laminated body which the said resin layer consists of a cycloolefin resin. 8. The method of claim 7,
The cycloolefin-based resin includes a cycloolefin-based polymer,
The cycloolefin-based polymer comprises a polymer block [A] mainly comprising a repeating unit [I] derived from an aromatic vinyl compound;
A polymer block [B] mainly comprising a repeating unit [I] derived from an aromatic vinyl compound and a repeating unit [II] derived from a chain conjugated diene compound, or a repeating unit [II] derived from a chain conjugated diene compound as a main component A laminate which is a block copolymer hydride obtained by hydrogenating a block copolymer [D] composed of a polymer block [C]. 9. The method according to any one of claims 1 to 8,
The resin layer is a layer made of a resin,
The resin has a melt flow rate of 1 g/10 min or more, and a tensile modulus E of 50 MPa or more and 1200 MPa or less,
The melt flow rate is a value measured at 190°C and a load of 2.16 kg, the laminate. 10. The method according to any one of claims 1 to 9,
The laminate in which the said resin layer contains a plasticizer, a softener, or these both. 11. The method of claim 10,
The said plasticizer, a softener, or these both are 1 or more types chosen from an ester plasticizer and an aliphatic hydrocarbon polymer, The laminated body. 12. The method according to any one of claims 1 to 11,
The laminate in which the said resin layer contains an organometallic compound. The polarizing plate which is a uniaxial stretched product of the laminated body in any one of Claims 1-12. A first step of stretching a raw film containing a material for a polarizer to obtain a film of a polarizer material;
a second step of applying a resin to one surface of the polarizer material film to form an application layer;
The manufacturing method of the laminated body including the 3rd process of drying the said application layer in this order. 15. The method of claim 14,
In the said 1st process, the draw ratio of the said extending|stretching is X times, The manufacturing method of the laminated body with which X satisfy|fills 1.5<=X<=5.5. 16. The method of claim 14 or 15,
The manufacturing method of the laminated body including the 4th process of activating the said surface of the said polarizer material film before a said 2nd process. As a manufacturing method of a polarizing plate,
The process of preparing the laminated body in any one of Claims 1-12, or manufacturing a laminated body by the manufacturing method of the laminated body in any one of Claims 14-16;
a fifth step of dyeing the laminate with a dichroic dye;
The manufacturing method of the polarizing plate including the 6th process of uniaxially stretching the said laminated body. 18. The method of claim 17,
The magnification of the said extending|stretching in a said 6th process is Z times, and Z satisfy|fills 1.2 ≤ Z ≤ 5.0, The manufacturing method of the polarizing plate. 19. The method according to claim 17 or 18,
X and Z satisfy 5.1 ≤ X * Z ≤ 9.0, the manufacturing method of the polarizing plate. 20. The method according to any one of claims 17 to 19,
After passing through the said 5th process, the said 6th process, or these both, a protective film is pasted by one or both surfaces among the surface on the side of the said polarizer material film of the said laminated body, and the surface on the side of the said resin layer. A manufacturing method of a polarizing plate including a 7th process. A method of manufacturing a display device, comprising:
The process of manufacturing a polarizing plate by the manufacturing method of the polarizing plate in any one of Claims 17-20, and
an eighth step of laminating the polarizing plate to the panel;
The method for manufacturing a display device, wherein the panel is a panel selected from a liquid crystal panel, an organic electroluminescent panel, and a micro LED panel.

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